Next Article in Journal
A DFT Study of the Copolymerization of Methyl Vinyl Sulfone and Ethylene Catalyzed by Phosphine–Sulfonate and α-Diimine Palladium Complexes
Next Article in Special Issue
Use of Deep Eutectic Solvents in Plastic Depolymerization
Previous Article in Journal
Stable Sulfonic MCM-41 Catalyst for Furfural Production from Renewable Resources in a Biphasic System
Previous Article in Special Issue
Metal-Catalyzed Cascade Reactions between Alkynoic Acids and Dinucleophiles: A Review
 
 
Search for Articles:
Title / Keyword
Author / Affiliation / Email
Journal
Article Type
 
 
Advanced Search
 
Section
Special Issue
Volume
Issue
Number
Page
 
Journals
Catalysts
Volume 13
Issue 6
10.3390/catal13061025
catalysts-logo
Submit to this Journal Review for this Journal Propose a Special Issue
► Article Menu

Article Menu

share Share announcement Help format_quote Cite question_answer Discuss in SciProfiles thumb_up
...
Endorse textsms
...
Comment
first_page
settings
Order Article Reprints
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Review

An Overview of Catalytic Carbonylative Double Cyclization Reactions

by
Bartolo Gabriele
1,*,
Raffaella Mancuso
1,
Nicola Della Ca’
2,
Lucia Veltri
1 and
Ida Ziccarelli
1
1
Laboratory of Industrial and Synthetic Organic Chemistry (LISOC), Department of Chemistry and Chemical Technologies, University of Calabria, Via P. Bucci 12/C, Arcavacata, 87036 Rende, Italy
2
Department of Chemistry, Life Sciences and Environmental Sustainability (SCVSA) University of Parma, Parco Area delle Scienze, 17/A, 43124 Parma, Italy
*
Author to whom correspondence should be addressed.
Catalysts 2023, 13(6), 1025; https://doi.org/10.3390/catal13061025
Submission received: 29 May 2023 / Revised: 16 June 2023 / Accepted: 18 June 2023 / Published: 20 June 2023
(This article belongs to the Special Issue Exclusive Review Papers in Catalysis in Organic and Polymer Chemistry)
Browse Figures
Versions Notes

Abstract

:
This short review is aimed at giving an overview of catalytic carbonylative double cyclization reactions, which are processes in which suitable organic substrates and carbon monoxide are sequentially activated by a promoting a catalyst to form two new cycles with the concomitant incorporation of carbon monoxide as a carbonyl function in the final product. Paradigmatic examples of this powerful synthetic methodology, which allows the one-step synthesis of complex molecular architectures from simple building blocks using the simplest and readily available C-1 unit (CO), are illustrated and discussed. The review is divided into five sections: (1) Introduction, (2) Functionalized Olefinic Substrates, (3) Functionalized Acetylenic Substrates, (4) Functionalized Halides, (5) Conclusions and Future Perspectives.

Graphical Abstract

1. Introduction

The importance of carbon monoxide as a C-1 unit in organic synthesis can hardly be overemphasized [1]. It is a readily available feedstock that can be easily obtained by steam reforming of light hydrocarbons (including natural gas), partial oxidation of petroleum hydrocarbons, or gasification of coal to give syngas (CO and H2) [2]. It can be installed into an organic substrate, usually under catalytic conditions, leading to the direct formation of high value-added carbonylated compounds with 100% atom economy (carbonylation reactions) [1]. It should also be noted that recent progress in the chemical utilization of carbon dioxide has led to the implementation of efficient methods for reducing CO2 to CO [3]. Therefore, carbonylation reactions may also represent a very important indirect method for the conversion of carbon dioxide (the main waste currently produced by human activities, and principal responsible for the greenhouse effect [4]) into useful chemicals and materials.
Since their discovery at the beginning of the 19th century, carbonylation reactions have acquired steadily increasing importance both at the industrial and academic level. A huge number of examples of these important processes have been reported in the scientific as well as the patent literature [1]. In particular, the development of more efficient and selective catalytic systems associated with the use of suitably functionalized starting materials has opened the way to achieving sophisticated synthetic processes, with the formation of complex carbonylated molecular architectures that have potential applications in many fields of science (including drug discovery and material science) in one step. Among these processes, carbonylative double cyclization represents a particularly important methodology as it makes possible the construction of two new cycles in one synthetic procedure with formation of carbonylated polycyclic structures starting from readily available and suitably functionalized substrates.
The present short review is aimed at offering a description of paradigmatic synthetic methodologies based on catalytic carbonylative double cyclization reactions.

2. Functionalized Olefinic Substrates

It is well-know that palladium(II)-based catalysts activate unsaturated carbon–carbon bonds towards the attack of a variety of nucleophilic groups (mainly oxygen- or nitrogen-based). The intramolecular version of this reactivity is of particular importance as it allows the construction of heterocyclic derivatives in a straightforward manner and under mild reaction conditions (Pd(II)-catalyzed heterocyclization reactions) [5]. On the other hand, it is also very well known that Pd(II) catalysts promote many important kinds of carbonylation processes, particularly under oxidative conditions, including cyclization processes in which carbon monoxide is inserted as a carbonyl function inside the newly formed ring (cyclocarbonylation reactions) [6]. It is therefore not surprising that several important methods have been developed in which a single Pd(II)-based catalytic system promotes, in one synthetic step, the sequential heterocyclization−cyclocarbonylation of suitably functionalized olefinic substrates that carry two nucleophilic moieties placed in appropriate positions to undergo double cyclization.
Pioneering studies on this kind of reactivity were conducted by the Semmelhack and Yoshida research groups during the 1980s. In 1984, Semmelhack et al. reported the Pd(II)-promoted stereoselective carbonylative double cyclization of 1-(2-(hydroxymethyl)phenyl)prop-2-en-1-ols to give 3,3a,5,9b-tetrahydro-2H-furo[3,2-c]isochromen-2-ones with a cis junction between the newly formed rings using a stoichiometric amount of Pd(OAc)2 [7]. The process started with the intramolecular 6-exo-trig nucleophilic attack of the benzylic hydroxyl group to the double bond, activated by coordination to the Pd(II) center. This led to the formation of a cis-type alkylpalladium intermediate stabilized by chelation of the second hydroxyl group. The final bicyclic product was then formed through CO migratory insertion followed by intramolecular nucleophilic displacement by the hydroxyl, possibly via the formation of a palladacycle followed by reductive elimination (Scheme 1).
Interestingly, when an oxidant for Pd(0) such as CuCl2 was employed to make the process catalytic, the reaction led to the formation of (E)-(2-(3-chloroprop-1-en-1-yl)phenyl)methanol from allylic chlorination (74% yield) [7]. Later on, however, suitable conditions were elaborated by the Yoshida group for performing the carbonylative double cyclization of 3-hydroxy-4-pentenoic acids to stereoselectively give tetrahydrofuro[3,2-b]furan-2,5-diones with a cis junction between the rings under Pd(II) catalysis (10 mol% PdCl2 in the presence of 3 equiv of CuCl2 and 3 equiv of AcONa, in glacial acetic acid as the solvent, at room temperature and under 1 atm of CO) (Scheme 2) [8]. The process took place through 5-exo-trig cyclization by the intramolecular nucleophilic attack of the carboxylic group to the double bond coordinated to the metal center, stabilized by hydroxyl chelation, to give a cis-type alkylpalladium complex followed by CO insertion and intramolecular nucleophilic displacement, possibly via the formation of a palladacycle followed by reductive elimination (Scheme 2) [8].
The same research group then published the carbonylative double cyclization of 4-ene-1,3-diols under similar reaction conditions to obtain tetrahydrofuro[3,2-b]furan-2(3H)-ones (Scheme 3) [9].
Considering that the bicyclic tetrahydrofuro[3,2-b]furan-2(3H)-one substructure is largely found in natural and biologically active molecules, the methods disclosed by Semmelhack and Yoshida for constructing this important core by the carbonylative double cyclization of enediol derivatives have been largely employed as the key step in the semi- or total synthesis of natural products and bioactive compounds. Representative examples are shown in Table 1.
Interestingly, using the appropriate enantiopure ligand, a kinetic resolution of (±)-pent-4-ene-1,3-diols was possible with the formation of the corresponding bicyclic lactone in noracemic form. This was exemplified by the Pd(OAc)2-catalyzed carbonylation of (±)-pent-4-ene-1,3-diol performed in the presence of an enantiopure bis(oxazoline) ligand and p-benzoquinone as an external oxidant to give (3aR,6aR)-tetrahydrofuro[3,2-b]furan-2(3H)-one in 29% yield and 62% ee (Scheme 4) [32].
More recently, the kinetic resolution of (±)-pent-4-ene-1,3-diols to give nonracemic tetrahydrofuro[3,2-b]furan-2(3H)-ones [2-(S,S) up to 80% ee, 2-(R,R) up to 57% ee] has been realized under similar conditions [4 mol% of Pd(OAc)2, 12 mol% of 2,6-bis[(4R)-4-phenyl-2-oxazolinyl]pyridine as enantiopure ligand, 0.5 equiv of p-benzoquinone, and 10 equiv AcOH] using an ionic liquid as the solvent (such as 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [Bmim][NTf2], 10 equiv), as shown in Scheme 5 [33].
Interestingly, the Gracza group reported that the use of iron pentacarbonyl as an in situ liquid CO source may lead to improved results (significantly shorter reaction times, in particular) in the Pd(II)-catalyzed carbonylative double cyclization of enediols with a terminal double bond, as shown in Scheme 6 [29,34,35].
The same research group recently reported their reaction under flow conditions using a continuous microflow system, as shown in Scheme 7 [31,36].
The carbonylative double cyclization process of enediols has also been reported to occur with 4-ene-1,2-diol derivatives. In this case, after the initial 5-exo-trig O-cyclization, in the cyclocarbonylation it is the free hydroxyl at C-2 that acts as internal nucleophile, with the formation of a 6-membered ring. This is illustrated by the formation of 8-((tert-butyldimethylsilyl)oxy)-2,6-dioxabicyclo[3.2.1]octan-3-one from 3-((tert-butyldimethylsilyl)oxy)pent-4-ene-1,2-diol, as shown in Scheme 8 [37].
The nucleophilic group undergoing initial heterocyclization can also be nitrogen-based. Thus, as early as 1985 the Tamaru and Yoshida group found that the Pd(II)-catalyzed carbonylative double cyclization of the N-protected 5-aminopent-1-en-3-ols yielded N-protected 6-hydroxyhexahydro-2H-furo[3,2-b]pyrrol-2-ones, using the same conditions employed for 4-penten-1,3-diols [38]. Among the protective groups tested, the –CO2Me group turned out as the most suitable, as exemplified in Scheme 9 [39].
As predicted, owing to the higher degrees of freedom of the alkyl chain, N-protected 6-aminohex-1-en-3-ols were significantly less reactive, and relatively good results were usually observed with P = CONHPh, as shown in Scheme 10 [39].
Later on, Jäger et al. reported the carbonylation of benzyl ((2R,3S)-2,3-dihydroxypent-4-en-1-yl)carbamate (Scheme 11a) as a key step in the synthesis of novel 1,4-iminoglycitol derivatives as potential glycosidase inhibitors [40]. On the other hand, the PdCl2-catalyzed carbonylation of benzyl ((2S,3S)-2,3-dihydroxypent-4-en-1-yl)carbamate gave benzyl (3aR,6S,6aS)-6-hydroxy-2-oxohexahydro-4H-furo[3,2-b]pyrrole-4-carboxylate in a 14% yield (Scheme 11b) [41].
Kinetic resolution of N-protected 5-aminopent-1-en-3-ols in the Pd(II)-catalyzed carbonylative double cyclization has been reported by Gracza et al. Thus, using enantiopure bisoxazoline ligands, nonracemic hexahydro-2H-furo[3,2-b]pyrrol-2-ones could be obtained as in Scheme 12 [42].
The gaseous CO-free conditions elaborated by the Gracza group for the carbonylation of 4-ene-1,3-diols, involving the use of liquid [Fe(CO)5] as an in situ CO source (Scheme 6), have also been successfully employed by the same research team in the Pd(II)-catalyzed carboylative double cyclization of N-protected 5-aminopent-1-en-3-ols, as in Scheme 13 [34].
An interesting carbonylative double cyclization process has recently been developed by the Li group [43]. It involved the reaction of N-(2-aminoethyl)pent-4-enamide or N-(2-hydroxyethyl)pent-4-enamide derivatives with CO (1 atm) in the presence of PdCl2 as a catalyst (1 mol%) and p-benzoquinone as an oxidant (1.2 equiv) (Scheme 14). As shown in Scheme 14, the initial 5-exo-trig N-cyclization was followed by CO insertion and intramolecular nucleophilic displacement via the formation of an 8-membered ring palladacycle followed by reduction elimination [43].
A general approach leading to carbonylative double cyclization is the intramolecular Pauson–Khand reaction starting from suitable diene or enyne substrates. Since several excellent reviews have been published on this reaction [44,45,46], even in the most recent literature [47,48,49], this process will not be treated here; however, a particularly striking example in Scheme 15 gives the reader an idea of the powerfulness of this synthetic method for constructing complex carbonylated polycyclic compounds [50].

3. Functionalized Acetylenic Substrates

Starting from suitably functionalized acetylenic substrates bearing a nucleophilic group in the appropriate position, Kato et al. reported an interesting Pd(II)-catalyzed carbonylative double cyclization process without incorporating CO into the rings, which leads to di(hetero)cyclic ketones [51]. According to Scheme 16, the process, which the authors call the “cyclization–carbonylation–cyclization coupling reaction” or ”CCC reaction”, starts with the electrophilic activation of the triple bond by a Pd(II) species followed by an intramolecular nucleophilic attack on the activated triple bond with the formation of the first ring. (Only the endo cyclization mode is shown in Scheme 16 for simplicity.) The ensuing cyclic vinylpalladium intermediate then undergoes carbon monoxide insertion followed by the coordination of another molecule of the acetylenic substrate. This opens the way to a second cyclization, which is followed by reductive elimination to give the final product and Pd(0). The latter is reoxidized to give catalytically active Pd(II) by the use of an external oxidant, usually p-benzoquinone. The system CuCl2/O2 has also been used occasionally [52] although it should be noted that in this case the CO–O2 mixture fell within the explosion limits. In fact, these mixtures are potentially explosive over a large range of composition: the flammability range for CO in O2 is 16.7–93.5% at room temperature and becomes even larger at higher temperatures [53].
This method has been successfully employed by the Kato group to synthesize a variety of di(heterocyclic)ketones; representative examples are shown in Table 2, entries 1–8. Entry 9 shows a recent extension of the concept to allenic substrates (2-methyl-1-phenyl-2,3-dien-1-ones, in particular) for the synthesis of bis(3-furanyl)methanones.
The Pd(II)-catalyzed carbonylative cyclization of functionalized acetylenic derivatives with CO incorporation into the cycle was disclosed by our research group a few years ago [62,63,64,65] using the PdI2/KI catalytic system, which we had already successfully used to promote a plethora of carbonylation reactions [66,67,68,69,70]. Thus, starting from readily available 4-yne-1,3-diols under oxidative conditions (using oxygen from the air as a benign oxidative agent), novel dihydrofurofuranone derivatives with antitumor activity were synthesized (Scheme 17). In particular, 5,5-dimethyl-6a-phenyl-3-(trimethylsilyl)-6,6a-dihydrofuro[3,2-b]furan-2(5H)-one showed a significant antiproliferative activity in vitro on human breast cancer cell lines, including the most aggressive triple-negative breast cancer cells (MDA-MB-231 and MDAMB-468) while being practically non-toxic to normal cells (human mammary epithelia cells, MCF-10A, as well as murine fibroblasts 3T3-L1) [62,63,64].
Mechanistically, the process involved an initial 5-exo-dig heterocyclization by an intramolecular nucleophilic attack of the terminal hydroxyl group to the triple bond coordinated to Pd(II) followed by carbon monoxide insertion. Intramolecular nucleophilic displacement then took place, probably by forming a palladacycle followed by a reductive elimination, to give the product and Pd(0). The latter was then reoxidized to PdI2 according to the mechanism we demonstrated several years ago in the PdI2/KI-catalyzed oxidative dialkoxycarbonylation of alkynes [71], which involves oxidation of 2 mol of HI (formed during the process) to give I2 followed by the oxidative addition of I2 to Pd(0) (Scheme 18; anionic iodide ligands are omitted for clarity) [64].
The method was then extended to using 2-(3-hydroxy-1-yn-1-yl)phenols as substrates to give furo[3,4-b]benzofuran-1(3H)ones in the ionic liquid BmimBF4 (1-butyl-3-methylimidazolium tetrafluoroborate) as an unconventional solvent (Scheme 19) [72]. The catalyst–solvent system could be conveniently recycled several times without appreciable loss of activity. Interestingly, this process turned out to be unselective when carried out in a classical solvent (such as DME or MeCN), in forming mixtures of the desired furobenzofuranone derivative and the simple benzofuran product from non-carbonylative heterocyclization.
In a similar way, starting from 2-(hydroxyprop-1-ynyl)anilines as the substrates, 3,4-dihydrofuro[3,4-b]indol-1-ones were synthesized in one step with yields up to 98% from an initial 5-endo-dig N-heterocyclization followed by cyclocarbonylation (Scheme 20) [65].
Interestingly, the use of the analogue substrates having a secondary propargylaminic moiety rather than the propargylacoholic group [2-(3-(alkylamino)prop-1-yn-1-yl)anilines] led to a complex reaction mixture when allowed to react under conditions similar to those shown in Scheme 20. However, a selective and novel double cyclization process was observed with the N-acyl derivatives, i.e., in the case of N-(3-(2-aminophenyl)prop-2-yn-1-yl)acetamides, with formation of 4,6-dihydro-5H-[1,3]oxazino[5,6-c]quinolin-5-ones. (Scheme 21) [73]. In this case, the reaction began with an intramolecular nucleophilic attack by the amide carbonyl oxygen on the coordinated triple bond leading to 6-endo-dig ring closure and the formation of a vinylpalladium intermediate stabilized by coordination of the aniline amino group. Carbon monoxide insertion followed by intramolecular nucleophilic displacement, possibly through the formation of a palladacycle, then delivers the product (Scheme 21) [73].
A striking carbonylative tetracyclization process was observed in the case of 2-(3-amino-3-methylbut-1-yn-1-yl)anilines having a primary propargylaminic moiety, which led to 7,7,16,16-tetramethyl-5H,14H-benzopyrido[3’’,4’’:5’,6’]pyrimido[2’,1’:2,3][1,3]oxazino[5,6-c]quinoline-6,15-diones in one step (Scheme 22) [73].
In fact, these substrates first underwent PdI2-catalyzed oxidative carbonylation of the primary amino group to give the corresponding urea [74,75], which then reacted through O-6-endo-dig cyclization from the ureidic carbonyl group followed by two successive cyclocarbonylations to yield the final product (Scheme 23) [73].
More recently, we studied the reactivity of thiophenecarboxylic acids having an ω-hydroxyalkynyl substituent in vicinal position under PdI2/KI-catalyzed oxidative carbonylation conditions and found that also these substrates underwent carbonylative double cyclization to give previously unknown 1H-furo[3,4-b]thieno[3,2-d]pyran-1,5(3H)-dione (Scheme 24a), 4H-furo[3,4-b]thieno[2,3-d]pyran-4,8(6H)-dione (Scheme 24b), 3,4-dihydro-1H,6H-pyrano[4,3-b]thieno[3,2-d]pyran-1,6-dione (Scheme 24c), and 6,7-dihydro-4H,9H-pyrano[4,3-b]thieno[2,3-d]pyran-4,9-dione (Scheme 24d) derivatives [76]. The process begins with 6-endo-dig cyclization from the carboxylic group followed by cyclocarbonylation, as exemplified in Scheme 24a to synthesize 1H-furo[3,4-b]thieno[3,2-d]pyran-1,5(3H)-diones from 3-(3-hydroxyprop-1-yn-1-yl)thiophene-2-carboxylic acids [76].
We also found that even sulfurated acetylenic substrates, under the right oxidative conditions, can undergo PdI2/KI-catalyzed carbonylative double cyclization. However, considering the instability of the free thiol group to oxygen [77,78], it was necessary to protect the sulfur atom with an easily removable methyl group. This group, in fact, could be removed after cyclization because of the presence of excess iodide anions. Accordingly, starting from 5-(methylthio)-1-yn-3-ols, we were able to synthesize 6,6a-dihydrothieno[3,2-b]furan-2(5H)-ones as a new class of S,O-bicyclic heterocycles as shown in Scheme 25 [79].
Mechanistically, the process began with 5-exo-dig S-cyclization by the intramolecular nucleophilic attack by the sulfur in the thiomethyl group on the triple bond coordinated to PdI2. This was followed by demethylation of the ensuing sulfonium cation by the iodide anion, with the formation of the corresponding vinylpalladium intermediate and methyl iodide. The latter readily reacted with water that was initially present as an impurity and then also formed in the final Pd(0) reoxidation step to give MeOH and one mol of HI. On the other hand, the vinylpalladium intermediate underwent carbon monoxide insertion followed by nucleophilic displacement to give the final product together with Pd(0) and a second mol of HI. Lastly, Pd(0) was, as usual, oxidized back to PdI2 by reacting with 2 mol of HI and 0.5 mol of O2 (Scheme 26) [79].

4. Functionalized Halides

Under non-oxidative conditions, suitably functionalized halides may undergo Pd(0)-catalyzed double cyclization leading to high value-added polycyclic heterocyclic compounds. Thus, 1,2-dibromoarenes have been reported by Beller and Wu to undergo carbonylative double cyclization when allowed to react with 2-aminobenzyl amine using Pd(OAc)2 in the presence of the catalyst precursor BuPAd2 (Ad = 1-adamantyl) in the solvent N,N-dimethylacetamide (DMA) with Et3N as the base and under 10 atm of CO. In this manner, several isoindolo[1,2-b]quinazolin-12(10H)-one derivatives (analogues of the anticancer agent batracylin) were prepared in a 36–84% yield (Scheme 27) [80].
The process started with the oxidative addition of a C–Br bond to Pd(0) followed by CO insertion. Then the more nucleophilic benzylic amino group of the diamine caused nucleophilic displacement, which was followed by a further oxidative addition and CO insertion from the second C–Br bond, intramolecular nucleophilic displacement by the second amino group, and intramolecular condensation (Scheme 28) [80].
In a similar way, and under similar conditions, isoindolo[1,2-b]quinazolin-10(12H)-ones were synthesized by the Wu group starting from 2-bromoanilines and 2-bromobenzyl amines, as shown in Scheme 29 [81].
In this case, it was the 2-bromoaniline derivative that underwent initial oxidative addition to Pd(0), followed by CO insertion (Scheme 30). This was followed by nucleophilic displacement by the 2-bromobenzyl amine, the oxidative addition to Pd(0) of the second C–Br bond, CO insertion, intramolecular nucleophilic displacement, and intramolecular condensation (Scheme 30) [81].
The Beller and Wu group also reported the Pd(0)-catalyzed reaction of 2-bromoanilines with 2-bromobenzaldehyde and CO, which resulted in a carbonylative double cyclization leading to 5H-benzo[4,5][1,3]oxazino[2,3-a]isoindole-5,11(6aH)-diones (Scheme 31a) [82]. 2-Bromobenzonitriles also underwent carbonylative double cyclization when allowed to react with 2-bromoanilines to give isoindolo[1,2-b]quinazoline-10,12-diones (Scheme 31b) [83].
As shown in Scheme 32, the process leading to 5H-benzo[4,5][1,3]oxazino[2,3-a]isoindole-5,11(6aH)-diones began with the oxidative addition of 2-bromobenzaldehyde to Pd(0), followed by CO insertion and nucleophilic displacement by the amino group of the 2-bromoaniline derivative. Then, there was an intramolecular nucleophilic attack of the nitrogen of the newly formed amido group on the formyl group, followed by the oxidative addition of the second C–Br group to Pd(0), CO insertion, and intramolecular nucleophilic displacement by the hydroxyl group. 2-Bromobenzoic acid could also be employed as a substrate in this reaction in place of 2-bromobenzaldehyde [82].
The first steps of the mechanistic pathway leading to isoindolo[1,2-b]quinazoline-10,12-diones are similar to those seen above for the reaction of 2-bromoanilines with 2-bromobenzaldehyde. Thus, the oxidative addition of the 2-bromobenzonitrile derivative was followed by CO insertion, nucleophilic displacement by the 2-bromoaniline, and an intramolecular nucleophilic attack by the nitrogen of the newly formed amide group on the cyano group, which formed the corresponding 2-(2-bromophenyl)-3-iminoisoindolin-1-one derivative (Scheme 33). Then, an unexpected isomerization of this intermediate took place, probably due to steric effects, to give a (Z)-3-((2-bromophenyl)imino)isoindolin-1-one intermediate. The oxidative addition of the C–Br bond of the latter to Pd(0) followed by CO insertion and intramolecular nucleophilic displacement delivered the final product (Scheme 33) [83].
The carbonylative double cyclization of substrates having two aryl halide bonds and a suitable nucleophile, such as an enolate formed in situ under basic conditions, in an appropriate position was also reported, as shown by the synthesis of 5H-isochromeno[3,4-b]quinoline-5,12(7H)-diones starting from N-(2-bromophenyl)-2-(2-iodophenyl)acetamides (Scheme 34) [84].
In this case, the more reactive C–I bond gave the initial oxidative addition to Pd(0), followed by CO insertion (Scheme 35). Then, intramolecular nucleophilic displacement by the enolate oxygen occurred, which led to the first cyclization. The oxidative addition of the C–Br bond to Pd(0), followed by Csp2–H activation, CO insertion, and reductive elimination, eventually gave the final product [84].

5. Conclusions and Future Perspectives

Catalytic carbonylative double cyclization is a powerful technique for constructing two novel rings in sequential order with the simultaneous incorporation of carbon monoxide in the final product. Starting from simple building blocks, it allows the direct synthesis of high value-added, complex molecular architectures.
So far, several important examples have been reported in the literature, in particular starting from suitably functionalized olefinic, acetylenic, or halide substrates and under the catalysis of either Pd(II) or Pd(0) species. These reactions led to the formation of important polycyclic heterocyclic derivatives, which have shown important biological activity (including anticancer activity) or have been used as precursors to the synthesis of bioactive natural products.
Progress in catalysis is expected to give further impetus to this very attractive field of synthetic chemistry through the discovery of novel and more efficient one-step catalytic processes that produce polycyclic heterocycles with potential applications in fields such as material science and pharmaceutical chemistry.

Author Contributions

Conceptualization, B.G.; Validation, B.G., R.M., N.D.C., L.V. and I.Z.; Investigation, all authors; writing—original draft preparation, B.G.; writing—review and editing, all authors; supervision, B.G. All authors have read and agreed to the published version of the manuscript.

Funding

This research received no external funding.

Data Availability Statement

No new data are reported with respect to those published in the original manuscripts cited in this review paper.

Conflicts of Interest

The authors declare no conflict of interest.

References

  1. Gabriele, B. (Ed.) Carbon Monoxide in Organic Synthesis—Carbonylation Chemistry; Wiley-VCH: Weinheim, Germany, 2022. [Google Scholar]
  2. Reimert, R.; Marschner, F.; Renner, H.-J.; Boll, W.; Supp, E.; Brejc, M.; Liebner, W.; Schaub, G. Gas production, 2. In Ullmann’s Encyclopedia of Industrial Chemistry; Baltes, H., Göpel, W., Hesse, J., Eds.; Wiley-VCH: Weinheim, Germany, 2011; pp. 423–479. [Google Scholar]
  3. Karl, J.; Pröll, T. Steam Gasification of Biomass in Dual Fluidized Bed Gasifiers: A Review. Renew. Sustain. Energy Rev. 2018, 98, 64–78. [Google Scholar] [CrossRef]
  4. Figueres, C.; Le Quéré, C.; Mahindra, A.; Bäte, O.; Whiteman, G.; Peters, G.; Guan, D. Emissions Are Still Rising: Ramp up the Cuts. Nature 2018, 564, 27–30. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  5. Li, J.J.; Gribble, G. (Eds.) Palladium in Heterocyclic Chemistry—A Guide for the Synthetic Chemist, 2nd ed.; Elsevier: Amsterdam, The Netherlands, 2006. [Google Scholar]
  6. Gabriele, B.; Della Ca’, N.; Mancuso, R.; Veltri, L.; Ziccarelli, I. Palladium(II)-Catalyzed Carbonylations. In Carbon Monoxide in Organic Synthesis—Carbonylation Chemistry; Gabriele, B., Ed.; Wiley-VCH: Weinheim, Germany, 2022; Chapter 7. [Google Scholar]
  7. Semmelhack, M.F.; Bodurow, C.; Baum, M. Direct Synthesis of Pyran-Lactones Related to Nafhthoquinone Antibiotics. Tetrahadron Lett. 1984, 25, 3171–3174. [Google Scholar] [CrossRef]
  8. Tamaru, H.; Higashimura, K.; Hojo, M.; Yoshida, Z. PdII-Catalyzed Stereoselective Bis-Lactonization. Angew. Chem. Int. Ed. 1985, 24, 1045–1046. [Google Scholar] [CrossRef]
  9. Tamaru, H.; Kobayashi, T.; Kawamura, S.; Hojo, M.; Yoshida, Z. Palladium Catalyzed Oxycarbonylation of 4-Penten-1,3-diols: Efficient Stereoselective Synthesis of cis 3-Hydroxytetrahydrofuran 2-Acetic Acid Lactones. Tetrahedron Lett. 1985, 26, 3207–3210. [Google Scholar] [CrossRef]
  10. Gracza, T.; Hasenöhrl, T.; Stahl, T.; Jäger, V. Synthesis of 3,5-Anhydro-2-deoxy-1,4-glyconolactones by Palladium(II)-Catalyzed, Regioselective Oxycarbonylation of C5- and C6-enitols. ω-Homologation of Aldoses to Produce Intermediates for C-Glycoside/C-Nucleoside Synthesis. Synthesis 1991, 1991, 1108–1118. [Google Scholar] [CrossRef]
  11. Kraus, G.A.; Li, J. Regiocontrol by Remote Substituents. An Enantioselective Total Synthesis of Frenolicin B via a Highly Regioselective Diels-Alder Reaction. J. Am. Chem. Soc. 1993, 115, 5859–5860. [Google Scholar] [CrossRef] [Green Version]
  12. Gracza, T.; Jäger, V. Synthesis of Natural and Unnatural Enantiomers of Goniofufurone and Its 7-Epimers from D-Glucose. Application of Palladium(II)—Catalyzed Oxycarbonylation of Unsaturated Polyols. Synthesis 1994, 1994, 1359–1368. [Google Scholar] [CrossRef]
  13. Boukouvalas, J.; Fortier, G.; Radu, I.-I. Efficient Synthesis of (−)-trans-Kumausyne via Tandem Intramolecular Alkoxycarbonylation-Lactonization. J. Org. Chem. 1998, 63, 916–917. [Google Scholar] [CrossRef]
  14. Dixon, D.J.; Ley, S.V.; Gracza, T.; Szolcsanyi, P. Total Synthesis of the Polyenoyltetramic acid Mycotoxin Erythroskyrine. J. Chem. Soc. Perkin Trans. 1 1999, 1999, 831–841. [Google Scholar] [CrossRef]
  15. Paddon-Jones, G.C.; Hungerford, N.L.; Haynes, P.; Kitching, W. Efficient Palladium(II)-Mediated Construction of Functionalized Plakortone Cores. Org. Lett. 1999, 1, 1905–1908. [Google Scholar] [CrossRef]
  16. Semmelhack, M.F.; Shanmugam, P. Development of an Approach to the Synthesis of the Plakortones. Tetrahedron Lett. 2000, 41, 3567–3571. [Google Scholar] [CrossRef]
  17. Paddon-Jones, G.C.; McErlean, C.S.P.; Haynes, P.; Moore, C.J.; Konig, W.A.; Kitching, W. Synthesis and Stereochemistry of Some Bicyclic γ-Lactones from Parasitic Wasps (Hymenoptera: Braconidae). Utility of Hydrolytic Kinetic Resolution of Epoxides and Palladium(II)-Catalyzed Hydroxycyclization-Carbonylation-Lactonization of Ene-diols. J. Org. Chem. 2001, 66, 7487–7495. [Google Scholar] [CrossRef] [PubMed]
  18. Haynes, P.Y.; Kitching, W. Total Synthesis and Absolute Stereochemistry of Plakortone D. J. Am. Chem. Soc. 2002, 124, 9718–9719. [Google Scholar]
  19. Haynes, P.Y.; Kitching, W. Synthesis of the Plakortone Series: Plakortone E. Heterocycles 2004, 62, 173–177. [Google Scholar]
  20. Babjak, M.; Kapitán, P.; Gracza, T. Synthesis of (+)-Goniothalesdiol and (+)-7-epi-Goniothalesdiol. Tetrahedron 2005, 61, 2471–2479. [Google Scholar] [CrossRef]
  21. Semmelhack, M.F.; Hooley, R.J.; Kraml, C.M. Synthesis of Plakortone B and Analogs. Org. Lett. 2006, 8, 5203–5206. [Google Scholar] [CrossRef]
  22. Boukouvalas, J.; Pouliot, M.; Robichaud, J.; MacNeil, S.; Snieckus, V. Asymmetric Total Synthesis of (−)-Panacene and Correction of Its Relative Configuration. Org. Lett. 2006, 8, 3597–3599. [Google Scholar] [CrossRef]
  23. Kapitán, P.; Gracza, T. Stereocontrolled Oxycarbonylation of 4-Benzyloxyhepta-1,6-diene-3,5-diols Promoted by Chiral Palladium(II) Complexes. Tetrahedron Asymm. 2008, 19, 38–44. [Google Scholar] [CrossRef]
  24. Nesbitt, C.L.; McErlean, C.S.P. An Expedient Synthesis of 2,5-Disubstituted-3-oxygenated Tetrahydrofurans. Tetrahedron Lett. 2009, 50, 6318–6320. [Google Scholar] [CrossRef]
  25. Nesbitt, C.L.; McErlean, C.S.P. Total Synthesis of C19 Lipid Diols Containing a 2,5-Disubstituted-3-Oxygenated Tetrahydrofuran. Org. Biomol. Chem. 2011, 9, 2198–2208. [Google Scholar] [CrossRef] [PubMed]
  26. Haynes, P.Y.; Chow, S.; Rahm, F.; Bernhardt, P.V.; De Voss, J.J.; Kitching, W. Synthesis of the Sponge-Derived Plakortone Series of Bioactive Compounds. J. Org. Chem. 2010, 75, 6489–6501. [Google Scholar]
  27. Werness, J.B.; Tang, W. Stereoselective Total Synthesis of (−)-Kumausallene. Org. Lett. 2011, 13, 3664–3666. [Google Scholar] [CrossRef] [PubMed]
  28. Markovič, M.; Ďuranová, M.; Koóš, P.; Szolcsányi, P.; Gracza, T. Synthesis of bis-Tetrahydrofuran Subunit of (−)-Neopallavicinin. Tetrahedron 2013, 69, 4185–4189. [Google Scholar] [CrossRef]
  29. Markovič, M.; Koóš, P.; Čarný, T.; Sokoliová, S.; Bohačiková, N.; Moncol’, J.; Gracza, T. Total Synthesis, Configuration Assignment, and Cytotoxic Activity Evaluation of Protulactone A. J. Nat. Prod. 2017, 80, 1631–1638. [Google Scholar] [CrossRef]
  30. Markovič, M.; Koóš, P.; Gracza, T. A Short Asymmetric Synthesis of Sauropunols A–D. Synthesis 2017, 49, 2939–2942. [Google Scholar]
  31. Lopatka, P.; Gavenda, M.; Markovič, M.; Koóš, P.; Gracza, T. Flow Pd(II)-Catalyzed Cyclisation in the Total Synthesis of Jaspine B. Catalysts 2021, 11, 1513. [Google Scholar] [CrossRef]
  32. Kapitán, P.; Gracza, T. Asymmetric Intramolecular Pd(II)-catalyzed Oxycarbonylation of Alkene-1,3-diols. Arkivoc 2008, viii, 8–17. [Google Scholar]
  33. Doháňošová, J.; Lásikivá, A.; Toffano, M.; Gracza, T.; Vo-Thanh, G. Kinetic Resolution of Pent-4-ene-1,3-diol by Pd(II)-Catalysed Oxycarbonylation in Ionic Liquids. New J. Chem. 2012, 36, 1744–1750. [Google Scholar] [CrossRef]
  34. Babjak, M.; Markovič, K.; Kandríkova, B.; Gracza, T. Homogeneous Cyclocarbonylation of Alkenols with Iron Pentacarbonyl. Synthesis 2014, 46, 809–816. [Google Scholar] [CrossRef]
  35. Markovič, K.; Lopatka, P.; Koóš, P.; Gracza, T. Asymmetric Formal Synthesis of (+)-Pyrenolide D. Synthesis 2014, 46, 817–821. [Google Scholar]
  36. Lopatka, P.; Markovič, K.; Koóš, P.; Ley, S.V.; Gracza, T. Continuous Pd-Catalyzed Carbonylative Cyclization Using Iron Pentacarbonyl as a CO Source. J. Org. Chem. 2019, 84, 14394–14406. [Google Scholar] [CrossRef] [PubMed]
  37. Babjak, M.; Zálupský, P.; Gracza, T. Regiocontrol in the Palladium(II)-Catalysed Oxycarbonylation of Unsaturated Polyols. Arkivoc 2005, 45, 57. [Google Scholar] [CrossRef] [Green Version]
  38. Tamaru, Y.; Kobayashi, T.; Kawamura, S.; Ochiai, H.; Yoshida, Z. Stereoselective Intramolecular Aminocarbonylation of 3-Hydroxypent-4-enylamides Catalyzed by Palladium. Tetrahedron Lett. 1985, 26, 4479–4482. [Google Scholar] [CrossRef]
  39. Tamaru, Y.; Hojo, M.; Yoshida, Z. Palladium(2+)-Catalyzed Intramolecular Aminocarbonylation of 3-Hydroxy-4-pentenylamines and 4-Hydroxy-5-hexenylamines. J. Org. Chem. 1988, 53, 5731–5741. [Google Scholar] [CrossRef]
  40. Hümmer, W.; Dubois, E.; Gracza, T.; Jäger, V. Halocyclization and Palladium(II)-Catalyzed Amidocarbonylation of Unsaturated Aminopolyols. Synthesis of 1,4-Iminoglycitols as Potential Glycosidase Inhibitors. Synthesis 1997, 1997, 634–642. [Google Scholar] [CrossRef]
  41. Caletková, O.; Ďurišová, N.; Gracza, T. Aminohydroxylation of Divinylcarbinol and its Application to the Synthesis of Bicyclic hydroxypyrrolidine and Aminotetrahydrofuran Building Blocks. Chem. Pap. 2013, 67, 66–75. [Google Scholar] [CrossRef]
  42. Koóš, P.; Špánik, I.; Gracza, T. Asymmetric Intramolecular Pd(II)-Catalysed Amidocarbonylation of Unsaturated Amino Alcohols. Tetrahedron Asymm. 2009, 20, 2720–2723. [Google Scholar] [CrossRef]
  43. Shi, L.; Weng, M.; Li, F. Palladium-Catalyzed Tandem Carbonylative Aza-Wacker-Type Cyclization of Nucleophile Tethered Alkene to Access Fused N-Heterocycles. Chin. J. Chem. 2021, 39, 317–322. [Google Scholar] [CrossRef]
  44. Lee, H.-W.; Kwong, F.-Y. A Decade of Advancements in Pauson-Khand-Type Reactions. Eur. J. Org. Chem. 2010, 2010, 789–811. [Google Scholar] [CrossRef]
  45. Shibata, T. Recent Advances in the Catalytic Pauson-Khand-type Reaction. Adv. Synth. Catal. 2006, 348, 2328–2336. [Google Scholar] [CrossRef]
  46. Blanco-Urgoiti, J.; Añorbe, L.; Pérez-Serrano, L.; Domínguez, G.; Pérez-Castells, J. The Pauson–Khand Reaction, a Powerful Synthetic Tool for the Synthesis of Complex Molecules. Chem. Soc. Rev. 2004, 33, 32–42. [Google Scholar] [CrossRef] [PubMed]
  47. Heravi, M.M.; Mohammadi, L. Application of Pauson-Khand Reaction in the Total Synthesis of Terpenes. RSC Adv. 2021, 11, 38325–38373. [Google Scholar] [CrossRef]
  48. Yang, Z. Navigating the Pauson-Khand Reaction in Total Syntheses of Complex Natural Products. Acc. Chem. Res. 2021, 54, 556–568. [Google Scholar] [CrossRef]
  49. Chen, S.; Jiang, C.; Zheng, N.; Yang, Z.; Shi, L. Evolution of Pauson-Khand Reaction: Strategic Applications in Total Syntheses of Architecturally Complex Natural Products (2016–2020). Catalysts 2020, 10, 1199. [Google Scholar] [CrossRef]
  50. Keese, F.; Guidetti-Grept, R.; Herzog, B. Synthesis of [5.5.5.5]Fenestranes by Pd-Catalyzed Carbonylation-Cyclisation. Tetrahedron Lett. 1992, 33, 1207–1210. [Google Scholar] [CrossRef]
  51. Yasuhara, S.; Sasa, M.; Kusakabe, T.; Takayama, H.; Kimura, M.; Mochida, T.; Kato, K. Cyclization–Carbonylation–Cyclization Coupling Reactions of Propargyl Acetates and Amides with Palladium(II)–Bisoxazoline Catalysts. Angew. Chem. Int. Ed. 2011, 50, 3912–3915. [Google Scholar] [CrossRef] [PubMed]
  52. Shen, R.; Kusakabe, T.; Yatsu, T.; Kanno, Y.; Takahashi, K.; Nemoto, K.; Kato, K. Palladium(II) Catalyzed Cyclization-Carbonylation-Cyclization Coupling Reaction of (ortho-Alkynyl Phenyl) (Methoxymethyl) Sulfides Using Molecular Oxygen as the Terminal Oxidant. Molecules 2016, 21, 1177. [Google Scholar] [CrossRef] [Green Version]
  53. Bartish, C.M.; Drissel, G.M. Kirk-Othmer Encyclopedia of Chemical Technology, 3rd ed.; Grayson, M., Eckroth, D., Bushey, G.J., Campbell, L., Klingsberg, A., van Nes, L., Eds.; John Wiley & Sons: New York, NY, USA, 1978; Volume 4, p. 774. [Google Scholar]
  54. Kusakabe, T.; Kawaguchi, K.; Kawamura, M.; Niimura, N.; Shen, R.; Takayama, H.; Kato, K. Cyclization-Carbonylation-Cyclization Coupling Reaction of Propargyl Ureas with Palladium(II)-bisoxazoline Catalyst. Molecules 2012, 17, 9220–9230. [Google Scholar] [CrossRef] [Green Version]
  55. Kusakabe, T.; Kawai, Y.; Shen, R.; Mochida, T.; Kato, K. Cyclization–Carbonylation–Cyclization Coupling Reaction of γ-Propynyl-1,3-diketones with Palladium(II)-bisoxazoline Catalyst. Org. Biomol. Chem. 2012, 10, 3192–3194. [Google Scholar] [CrossRef]
  56. Kusakabe, T.; Sekiyama, E.; Ishino, Y.; Motodate, S.; Kato, S.; Mochida, T.; Kato, K. Cyclization–Carbonylation–Cyclization Coupling Reactions of N-Propargylanilines and o-Alkynylphenols with Palladium(II)–bisoxazoline Catalysts. Synthesis 2012, 44, 1825–1832. [Google Scholar] [CrossRef]
  57. Kusakabe, T.; Sagae, H.; Kato, K. Cyclization–Carbonylation–Cyclization Coupling reaction of α,β-Alkynic Hydrazones with Palladium(II)-bisoxazoline Catalyst. Org. Biomol. Chem. 2013, 11, 4943–4948. [Google Scholar] [CrossRef] [PubMed]
  58. Jiang, Y.; Kusakabe, T.; Takahashi, K.; Kato, K. A Cyclization–Carbonylation–Cyclization Coupling Reaction of (ortho-Alkynyl phenyl) (Methoxymethyl) Sulfides with the Palladium(II)-bisoxazoline Catalyst. Org. Biomol. Chem. 2014, 12, 3380–3385. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  59. Shen, R.; Kusakabe, T.; Takahashi, K.; Kato, K. Pd(II)-Catalyzed Ligand Controlled Synthesis of Methyl 1-benzyl-1H-indole-3-carboxylates and Bis(1-benzyl-1H-indol-3-yl)methanones. Org. Biomol. Chem. 2014, 12, 4602–4609. [Google Scholar] [CrossRef]
  60. Ariyama, T.; Kusakabe, T.; Sato, K.; Funatogawa, M.; Lee, D.; Takahashi, K.; Kato, K. Pd(II)-Catalyzed Ligand-Controlled Synthesis of 2,3-Dihydroisoxazole-4-carboxylates and Bis(2,3-dihydroisoxazol-4-yl)methanones. Heterocycles 2016, 93, 512–518. [Google Scholar]
  61. Kubasabe, T.; Mochida, T.; Ariyama, T.; Lee, D.; Ohkubo, S.; Takahashi, K.; Kato, K. PdII Catalyzed Ligand Controlled Synthesis of Bis(3-furanyl)methanones and Methyl 3-furancarboxylates. Org. Biomol. Chem. 2019, 17, 6860–6865. [Google Scholar]
  62. Gabriele, B.; Chimento, A.; Mancuso, R.; Pezzi, V.; Ziccarelli, I.; Sirianni, R. Derivati 6,6a-diidrofuro[3,2-b]furan-2-(5H)onici, loro Preparazione e Uso nel Trattamento dei Tumori. Italian Patent 102017000078586, 8 October 2019. [Google Scholar]
  63. Gabriele, B.; Chimento, A.; Mancuso, R.; Pezzi, V.; Ziccarelli, I.; Sirianni, R. 6,6a-Dihydrofuro[3,2-b]furan-2-(5H)one Derivatives, their Preparation and Use for Treating Tumors. European Patent EP3428169, 20 January 2021. [Google Scholar]
  64. Mancuso, R.; Ziccarelli, I.; Chimento, A.; Marino, N.; Della Ca’, N.; Sirianni, R.; Pezzi, V.; Gabriele, B. Catalytic Double Cyclization Process for Antitumor Agents against Breast Cancer Cell Lines. iScience 2018, 3, 279–288. [Google Scholar] [CrossRef] [PubMed]
  65. Acerbi, A.; Carfagna, C.; Costa, M.; Mancuso, R.; Gabriele, B.; Della Ca’, N. An Unprecedented Pd-Catyalyzed Carbonylative Route to Fused Furo[3,4-b]indol-1-ones. Chem. Eur. J. 2018, 24, 4835–4840. [Google Scholar] [CrossRef] [PubMed]
  66. Mancuso, R.; Della Ca’, N.; Veltri, L.; Ziccarelli, I.; Gabriele, B. PdI2–Based Catalysis for Carbonylation Reactions: A Personal Account. Catalysts 2019, 9, 610. [Google Scholar] [CrossRef] [Green Version]
  67. Gabriele, B. Recent Advances in the PdI2-Catalyzed Carbonylative Synthesis of Heterocycles from Acetylenic Substrates: A Personal Account. Targets Heterocycl. Syst. 2018, 22, 41–55. [Google Scholar]
  68. Gabriele, B.; Salerno, G. PdI2. In e-EROS (Electronic Encyclopedia of Reagents for Organic Synthesis); Crich, D., Ed.; Wiley–Interscience: New York, NY, USA, 2006. [Google Scholar]
  69. Gabriele, B.; Salerno, G.; Costa, M. PdI2-Catalyzed Synthesis of Heterocycles. Synlett 2004, 2004, 2468–2483. [Google Scholar] [CrossRef]
  70. Gabriele, B.; Salerno, G.; Costa, M.; Chiusoli, G.P. Recent Developments in the Synthesis of Heterocyclic Derivatives by PdI2-Catalyzed Oxidative Carbonylation Reactions. J. Organomet. Chem. 2003, 687, 219–228. [Google Scholar] [CrossRef]
  71. Gabriele, B.; Costa, M.; Salerno, G.; Chiusoli, G.P. An Efficient and Selective Palladium-Catalysed Oxidative Sicarbonylation of Alkynes to Alkyl- or Aryl-Maleic Esters. J. Chem. Soc. Perkin Trans. 1 1994, 1994, 83–87. [Google Scholar] [CrossRef]
  72. Mancuso, R.; Miliè, R.; Palumbo Piccionello, A.; Olivieri, D.; Della Ca’, N.; Carfagna, C.; Gabriele, B. Catalytic Carbonylative Double Cyclization of 2-(3-Hydroxy-1-yn-1-yl)phenols in Ionic Liquids Leading to Furobenzofuranone Derivatives. J. Org. Chem. 2019, 84, 7303–7311. [Google Scholar] [CrossRef]
  73. Pancrazzi, F.; Sarti, N.; Mazzeo, P.P.; Bacchi, A.; Carfagna, C.; Mancuso, R.; Gabriele, B.; Stirling, A.; Della Ca’, N. Site-Selective Double and Tetracyclization Routes to Fused Polyheterocyclic Structures by Pd-Catalyzed Carbonylation Reactions. Org. Lett. 2020, 22, 1569–1574. [Google Scholar] [CrossRef]
  74. Gabriele, B.; Salerno, G.; Mancuso, R.; Costa, M. Efficient Synthesis of Ureas by Direct Palladium-Catalyzed Oxidative Carbonylation of Amines. J. Org. Chem. 2004, 69, 4741–4750. [Google Scholar] [CrossRef]
  75. Della Ca’, N.; Bottarelli, P.; Dibenedetto, A.; Aresta, M.; Gabriele, B.; Salerno, G.; Costa, M. Palladium-Catalyzed Synthesis of Symmetrical Urea Derivatives by Oxidative Carbonylation of Primary Amines in Carbon Dioxide Medium. J. Catal. 2011, 282, 120–127. [Google Scholar]
  76. Mancuso, R.; Russo, P.; Lettieri, M.; Santandrea, M.; Cuocci, C.; Gabriele, B. Disclosing Polycyclic Heterocycles: Synthesis of Furothienopyran and Pyranothienopyran Derivatives by Palladium Iodide Catalyzed Carbonylative Double Cyclization. Adv. Synth. Catal. 2022, 364, 3917–3926. [Google Scholar] [CrossRef]
  77. Mancuso, R.; Strangis, R.; Ziccarelli, I.; Della Ca’, N.; Gabriele, B. Palladium Catalysis with Sulfurated Substrates under Aerobic Conditions: A Direct Oxidative Carbonylation Approach to Thiophene-3-carboxylic Esters. J. Catal. 2021, 393, 335–343. [Google Scholar] [CrossRef]
  78. Mancuso, R.; Cuglietta, S.; Strangis, R.; Gabriele, B. Synthesis of Benzothiophene-3-carboxylic Esters by Palladium Iodide-Catalyzed Oxidative Cyclization−Deprotection−Alkoxycarbonylation Sequence under Aerobic Conditions. J. Org. Chem. 2023, 88, 5180–5186. [Google Scholar] [CrossRef]
  79. Mancuso, R.; Russo, P.; Miliè, R.; Dell’Aera, M.; Grande, F.; Della Ca’, N.; Gabriele, B. Palladium Iodide Catalyzed Carbonylative Double Cyclization to a New Class of S,O-Bicyclic Heterocycles. Catal. Today 2022, 397–399, 631–638. [Google Scholar] [CrossRef]
  80. Chen, J.; Neumann, H.; Beller, M.; Wu, X.-F. Palladium-Catalyzed Synthesis of Isoindoloquinazolinones via Dicarbonylation of 1,2-Dibromoarenes. Org. Biomol. Chem. 2014, 12, 5835–5838. [Google Scholar] [CrossRef] [PubMed]
  81. Shen, C.; Man, N.Y.T.; Stewart, S.; Wu, X.-F. Palladium-Catalyzed Dicarbonylative Synthesis of Tetracycle Quinazolinones. Org. Biomol. Chem. 2015, 13, 4422–4425. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  82. Natte, K.; Chen, J.; Li, H.; Neumann, H.; Beller, M.; Wu, X.-F. Palladium-Catalyzed Carbonylation of 2-Bromoanilines with 2-Formylbenzoic Acid and 2-Halobenzaldehydes: Efficient Synthesis of Functionalized Isoindolinones. Chem. Eur. J. 2014, 20, 14184–14188. [Google Scholar] [CrossRef]
  83. Li, H.; Li, W.; Spannenberg, A.; Baumann, W.; Neumann, H.; Beller, M.; Wu, X.-F. A Novel Domino Synthesis of Quinazolinediones by Palladium-Catalyzed Double Carbonylation. Chem. Eur. J. 2014, 20, 8541–8544. [Google Scholar] [CrossRef]
  84. Frutos-Pedreño, R.; García-López, J.-A. 2-Arylacetamides as Versatile Precursors for 3-Aminoisocoumarin and Homophthalimide Derivatives: Palladium-Catalyzed Cascade Double Carbonylation Reactions. Adv. Synth. Catal. 2016, 358, 2692–2700. [Google Scholar] [CrossRef]
Catalysts 13 01025 sch001 550
Scheme 1. Synthesis of 3,3a,5,9b-tetrahydro-2H-furo[3,2-c]isochromen-2-ones from 1-(2-(hydroxymethyl)phenyl)prop-2-en-1-ols [7].
Scheme 1. Synthesis of 3,3a,5,9b-tetrahydro-2H-furo[3,2-c]isochromen-2-ones from 1-(2-(hydroxymethyl)phenyl)prop-2-en-1-ols [7].
Catalysts 13 01025 sch001
Catalysts 13 01025 sch002 550
Scheme 2. Synthesis of tetrahydrofuro[3,2-b]furan-2,5-diones from 3-hydroxy-4-pentenoic acids [8].
Scheme 2. Synthesis of tetrahydrofuro[3,2-b]furan-2,5-diones from 3-hydroxy-4-pentenoic acids [8].
Catalysts 13 01025 sch002
Catalysts 13 01025 sch003 550
Scheme 3. Synthesis of tetrahydrofuro[3,2-b]furan-2(3H)-ones from 4-ene-1,3-diols [9].
Scheme 3. Synthesis of tetrahydrofuro[3,2-b]furan-2(3H)-ones from 4-ene-1,3-diols [9].
Catalysts 13 01025 sch003
Catalysts 13 01025 sch004 550
Scheme 4. Kinetic resolution of (±)-pent-4-ene-1,3-diol leading to enantioenriched (3aR,6aR)-tetrahydrofuro[3,2-b]furan-2(3H)-one [32].
Scheme 4. Kinetic resolution of (±)-pent-4-ene-1,3-diol leading to enantioenriched (3aR,6aR)-tetrahydrofuro[3,2-b]furan-2(3H)-one [32].
Catalysts 13 01025 sch004
Catalysts 13 01025 sch005 550
Scheme 5. Kinetic resolution of (±)-pent-4-ene-1,3-diol in [bmim][NTf2] leading to enantioenriched (3aS,6aS)-tetrahydrofuro[3,2-b]furan-2(3H)-one [33].
Scheme 5. Kinetic resolution of (±)-pent-4-ene-1,3-diol in [bmim][NTf2] leading to enantioenriched (3aS,6aS)-tetrahydrofuro[3,2-b]furan-2(3H)-one [33].
Catalysts 13 01025 sch005
Catalysts 13 01025 sch006 550
Scheme 6. Carbonylative double cyclization of pent-4-ene-1,3-diol using [Fe(CO)5] as in situ CO source [34].
Scheme 6. Carbonylative double cyclization of pent-4-ene-1,3-diol using [Fe(CO)5] as in situ CO source [34].
Catalysts 13 01025 sch006
Catalysts 13 01025 sch007 550
Scheme 7. Carbonylative double cyclization of 4-ene-1,3-diols using [Fe(CO)5] as in situ CO source under flow conditions [36].
Scheme 7. Carbonylative double cyclization of 4-ene-1,3-diols using [Fe(CO)5] as in situ CO source under flow conditions [36].
Catalysts 13 01025 sch007
Catalysts 13 01025 sch008 550
Scheme 8. 5-exo-trig O-cyclization followed by cyclocarbonylation with 6-membered ring closure [37].
Scheme 8. 5-exo-trig O-cyclization followed by cyclocarbonylation with 6-membered ring closure [37].
Catalysts 13 01025 sch008
Catalysts 13 01025 sch009 550
Scheme 9. Formation of 6-hydroxyhexahydro-2H-furo[3,2-b]pyrrol-2-one derivatives from N-protected 5-aminopent-1-en-3-ols [39].
Scheme 9. Formation of 6-hydroxyhexahydro-2H-furo[3,2-b]pyrrol-2-one derivatives from N-protected 5-aminopent-1-en-3-ols [39].
Catalysts 13 01025 sch009
Catalysts 13 01025 sch010 550
Scheme 10. Synthesis of 2-oxo-N-phenylhexahydrofuro[3,2-b]pyridine-4(2H)-carboxamide from 1-(4-hydroxyhex-5-en-1-yl)-3-phenylurea [39].
Scheme 10. Synthesis of 2-oxo-N-phenylhexahydrofuro[3,2-b]pyridine-4(2H)-carboxamide from 1-(4-hydroxyhex-5-en-1-yl)-3-phenylurea [39].
Catalysts 13 01025 sch010
Catalysts 13 01025 sch011 550
Scheme 11. Synthesis of (a) benzyl (3aR,6R,6aS)-6-hydroxy-2-oxohexahydro-4H-furo[3,2-b]pyrrole-4-carboxylate (a precursor for the formation of glycosidase inhibitor derivatives) [40] and (b) benzyl (3aR,6S,6aS)-6-hydroxy-2-oxohexahydro-4H-furo[3,2-b]pyrrole-4-carboxylate [41].
Scheme 11. Synthesis of (a) benzyl (3aR,6R,6aS)-6-hydroxy-2-oxohexahydro-4H-furo[3,2-b]pyrrole-4-carboxylate (a precursor for the formation of glycosidase inhibitor derivatives) [40] and (b) benzyl (3aR,6S,6aS)-6-hydroxy-2-oxohexahydro-4H-furo[3,2-b]pyrrole-4-carboxylate [41].
Catalysts 13 01025 sch011
Catalysts 13 01025 sch012 550
Scheme 12. Kinetic resolution of (±)-N-(3-hydroxypent-4-en-1-yl)-4-methylbenzenesulfonamide leading to enantioenriched (3aR,6aR)-4-tosylhexahydro-2H-furo[3,2-b]pyrrol-2-one [42].
Scheme 12. Kinetic resolution of (±)-N-(3-hydroxypent-4-en-1-yl)-4-methylbenzenesulfonamide leading to enantioenriched (3aR,6aR)-4-tosylhexahydro-2H-furo[3,2-b]pyrrol-2-one [42].
Catalysts 13 01025 sch012
Catalysts 13 01025 sch013 550
Scheme 13. Carbonylative double cyclization of tert-butyl (3-hydroxypent-4-en-1-yl)carbamate using [Fe(CO)5] as in situ CO source [34].
Scheme 13. Carbonylative double cyclization of tert-butyl (3-hydroxypent-4-en-1-yl)carbamate using [Fe(CO)5] as in situ CO source [34].
Catalysts 13 01025 sch013
Catalysts 13 01025 sch014 550
Scheme 14. Carbonylative double cyclization of N-(2-aminoethyl)pent-4-enamide and N-(2-hydroxyethyl)pent-4-enamide derivatives [43].
Scheme 14. Carbonylative double cyclization of N-(2-aminoethyl)pent-4-enamide and N-(2-hydroxyethyl)pent-4-enamide derivatives [43].
Catalysts 13 01025 sch014
Catalysts 13 01025 sch015 550
Scheme 15. Synthesis of 2a-(ethoxycarbonyl)-8-oxododecahydropentaleno[1,6-cd]pentalene-1-carboxylic acid from ethyl 5-acetoxy-1-(but-3-en-1-yl)-2,3,4,5-tetrahydropentalene-3a(1H)-carboxylate by Pauson–Khand-type intramolecular reaction [50].
Scheme 15. Synthesis of 2a-(ethoxycarbonyl)-8-oxododecahydropentaleno[1,6-cd]pentalene-1-carboxylic acid from ethyl 5-acetoxy-1-(but-3-en-1-yl)-2,3,4,5-tetrahydropentalene-3a(1H)-carboxylate by Pauson–Khand-type intramolecular reaction [50].
Catalysts 13 01025 sch015
Catalysts 13 01025 sch016 550
Scheme 16. The “cyclization–carbonylation–cyclization coupling” concept leading to di(hetero)cyclic ketones [51].
Scheme 16. The “cyclization–carbonylation–cyclization coupling” concept leading to di(hetero)cyclic ketones [51].
Catalysts 13 01025 sch016
Catalysts 13 01025 sch017 550
Scheme 17. Synthesis of 6,6a-dihydrofuro[3,2-b]furan-2(5H)ones by PdI2/KI-catalyzed carbonylative double cyclization of 4-yne-1,3-diols [62,63,64].
Scheme 17. Synthesis of 6,6a-dihydrofuro[3,2-b]furan-2(5H)ones by PdI2/KI-catalyzed carbonylative double cyclization of 4-yne-1,3-diols [62,63,64].
Catalysts 13 01025 sch017
Catalysts 13 01025 sch018 550
Scheme 18. Proposed mechanism for the PdI2/KI-catalyzed carbonylative double cyclization of 4-yne-1,3-diols leading to 6,6a-dihydrofuro[3,2-b]furan-2(5H)ones [64].
Scheme 18. Proposed mechanism for the PdI2/KI-catalyzed carbonylative double cyclization of 4-yne-1,3-diols leading to 6,6a-dihydrofuro[3,2-b]furan-2(5H)ones [64].
Catalysts 13 01025 sch018
Catalysts 13 01025 sch019 550
Scheme 19. Synthesis of furo[3,4-b]benzofuran-1(3H)ones by PdI2/KI-catalyzed carbonylative double cyclization of 2-(3-hydroxy-1-yn-1-yl)phenols in ionic liquid BmimBF4 [72].
Scheme 19. Synthesis of furo[3,4-b]benzofuran-1(3H)ones by PdI2/KI-catalyzed carbonylative double cyclization of 2-(3-hydroxy-1-yn-1-yl)phenols in ionic liquid BmimBF4 [72].
Catalysts 13 01025 sch019
Catalysts 13 01025 sch020 550
Scheme 20. Synthesis of 3,4-dihydrofuro[3,4-b]indol-1-ones by PdI2/KI-catalyzed carbonylative double cyclization of 2-(hydroxyprop-1-ynyl)anilines [65].
Scheme 20. Synthesis of 3,4-dihydrofuro[3,4-b]indol-1-ones by PdI2/KI-catalyzed carbonylative double cyclization of 2-(hydroxyprop-1-ynyl)anilines [65].
Catalysts 13 01025 sch020
Catalysts 13 01025 sch021 550
Scheme 21. Synthesis of 4,6-dihydro-5H-[1,3]oxazino[5,6-c]quinolin-5-ones by PdI2/KI-catalyzed carbonylative double cyclization of N-(3-(2-aminophenyl)prop-2-yn-1-yl)acetamides [73].
Scheme 21. Synthesis of 4,6-dihydro-5H-[1,3]oxazino[5,6-c]quinolin-5-ones by PdI2/KI-catalyzed carbonylative double cyclization of N-(3-(2-aminophenyl)prop-2-yn-1-yl)acetamides [73].
Catalysts 13 01025 sch021
Catalysts 13 01025 sch022 550
Scheme 22. Synthesis of 7,7,16,16-tetramethyl-5H,14H-benzopyrido[3’’,4’’:5’,6’]pyrimido[2’,1’:2,3][1,3]oxazino[5,6-c]quinoline-6,15-diones by PdI2/KI-catalyzed carbonylative tetracyclization of 2-(3-amino-3-methylbut-1-yn-1-yl)anilines [73].
Scheme 22. Synthesis of 7,7,16,16-tetramethyl-5H,14H-benzopyrido[3’’,4’’:5’,6’]pyrimido[2’,1’:2,3][1,3]oxazino[5,6-c]quinoline-6,15-diones by PdI2/KI-catalyzed carbonylative tetracyclization of 2-(3-amino-3-methylbut-1-yn-1-yl)anilines [73].
Catalysts 13 01025 sch022
Catalysts 13 01025 sch023 550
Scheme 23. Plausible mechanism for the PdI2/KI-catalyzed carbonylative tetracyclization of 2-(3-amino-3-methylbut-1-yn-1-yl)anilines to give 7,7,16,16-tetramethyl-5H,14H-benzopyrido[3’’,4’’:5’,6’]pyrimido[2’,1’:2,3][1,3]oxazino[5,6-c]quinoline-6,15-diones [73].
Scheme 23. Plausible mechanism for the PdI2/KI-catalyzed carbonylative tetracyclization of 2-(3-amino-3-methylbut-1-yn-1-yl)anilines to give 7,7,16,16-tetramethyl-5H,14H-benzopyrido[3’’,4’’:5’,6’]pyrimido[2’,1’:2,3][1,3]oxazino[5,6-c]quinoline-6,15-diones [73].
Catalysts 13 01025 sch023
Catalysts 13 01025 sch024 550
Scheme 24. Synthesis of (a) 1H-furo[3,4-b]thieno[3,2-d]pyran-1,5(3H)-diones, (b) 4H-furo[3,4-b]thieno[2,3-d]pyran-4,8(6H)-diones, (c) 3,4-dihydro-1H,6H-pyrano[4,3-b]thieno[3,2-d]pyran-1,6-diones, and (d) 6,7-dihydro-4H,9H-pyrano[4,3-b]thieno[2,3-d]pyran-4,9-diones by PdI2/KI-catalyzed carbonylative double cyclization of thiophenecarboxylic acids bearing an ω-hydroxyalkynyl substituent in vicinal position [76].
Scheme 24. Synthesis of (a) 1H-furo[3,4-b]thieno[3,2-d]pyran-1,5(3H)-diones, (b) 4H-furo[3,4-b]thieno[2,3-d]pyran-4,8(6H)-diones, (c) 3,4-dihydro-1H,6H-pyrano[4,3-b]thieno[3,2-d]pyran-1,6-diones, and (d) 6,7-dihydro-4H,9H-pyrano[4,3-b]thieno[2,3-d]pyran-4,9-diones by PdI2/KI-catalyzed carbonylative double cyclization of thiophenecarboxylic acids bearing an ω-hydroxyalkynyl substituent in vicinal position [76].
Catalysts 13 01025 sch024
Catalysts 13 01025 sch025 550
Scheme 25. Synthesis of 6,6a-dihydrothieno[3,2-b]furan-2(5H)-ones by PdI2/KI-catalyzed carbonylative double cyclization of 5-(methylthio)-1-yn-3-ols [79].
Scheme 25. Synthesis of 6,6a-dihydrothieno[3,2-b]furan-2(5H)-ones by PdI2/KI-catalyzed carbonylative double cyclization of 5-(methylthio)-1-yn-3-ols [79].
Catalysts 13 01025 sch025
Catalysts 13 01025 sch026 550
Scheme 26. Proposed mechanism for the PdI2/KI-catalyzed carbonylative double cyclization of 5-(methylthio)-1-yn-3-ols to give 6,6a-dihydrothieno[3,2-b]furan-2(5H)-ones [79].
Scheme 26. Proposed mechanism for the PdI2/KI-catalyzed carbonylative double cyclization of 5-(methylthio)-1-yn-3-ols to give 6,6a-dihydrothieno[3,2-b]furan-2(5H)-ones [79].
Catalysts 13 01025 sch026
Catalysts 13 01025 sch027 550
Scheme 27. Carbonylative double cyclization of 1,2-dibromoarenes with 2-aminobenzyl amine to yield isoindolo[1,2-b]quinazolin-12(10H)-ones [80].
Scheme 27. Carbonylative double cyclization of 1,2-dibromoarenes with 2-aminobenzyl amine to yield isoindolo[1,2-b]quinazolin-12(10H)-ones [80].
Catalysts 13 01025 sch027
Catalysts 13 01025 sch028 550
Scheme 28. Proposed mechanism for the carbonylative double cyclization of 1,2-dibromoarenes with 2-aminobenzyl amine leading to isoindolo[1,2-b]quinazolin-12(10H)-ones [80].
Scheme 28. Proposed mechanism for the carbonylative double cyclization of 1,2-dibromoarenes with 2-aminobenzyl amine leading to isoindolo[1,2-b]quinazolin-12(10H)-ones [80].
Catalysts 13 01025 sch028
Catalysts 13 01025 sch029 550
Scheme 29. Carbonylative double cyclization of 2-bromoanilines with 2-bromobenzyl amines to yield isoindolo[1,2-b]quinazolin-10(12H)-ones [81].
Scheme 29. Carbonylative double cyclization of 2-bromoanilines with 2-bromobenzyl amines to yield isoindolo[1,2-b]quinazolin-10(12H)-ones [81].
Catalysts 13 01025 sch029
Catalysts 13 01025 sch030 550
Scheme 30. Proposed mechanism for the carbonylative double cyclization of 2-bromoanilines with 2-bromobenzyl amines to yield isoindolo[1,2-b]quinazolin-10(12H)-ones [81].
Scheme 30. Proposed mechanism for the carbonylative double cyclization of 2-bromoanilines with 2-bromobenzyl amines to yield isoindolo[1,2-b]quinazolin-10(12H)-ones [81].
Catalysts 13 01025 sch030
Catalysts 13 01025 sch031 550
Scheme 31. Carbonylative double cyclization of 2-bromoanilines with (a) 2-bromobenzaldehyde to give 5H-benzo[4,5][1,3]oxazino[2,3-a]isoindole-5,11(6aH)-diones [82] or (b) 2-bromobenzonitriles to give isoindolo[1,2-b]quinazoline-10,12-diones [83].
Scheme 31. Carbonylative double cyclization of 2-bromoanilines with (a) 2-bromobenzaldehyde to give 5H-benzo[4,5][1,3]oxazino[2,3-a]isoindole-5,11(6aH)-diones [82] or (b) 2-bromobenzonitriles to give isoindolo[1,2-b]quinazoline-10,12-diones [83].
Catalysts 13 01025 sch031
Catalysts 13 01025 sch032 550
Scheme 32. Proposed mechanism for the carbonylative double cyclization of 2-bromoanilines with 2-bromobenzaldehyde to give 5H-benzo[4,5][1,3]oxazino[2,3-a]isoindole-5,11(6aH)-diones [82].
Scheme 32. Proposed mechanism for the carbonylative double cyclization of 2-bromoanilines with 2-bromobenzaldehyde to give 5H-benzo[4,5][1,3]oxazino[2,3-a]isoindole-5,11(6aH)-diones [82].
Catalysts 13 01025 sch032
Catalysts 13 01025 sch033 550
Scheme 33. Proposed mechanism for the carbonylative double cyclization of 2-bromoanilines with 2-bromobenzonitriles to give isoindolo[1,2-b]quinazoline-10,12-diones [83].
Scheme 33. Proposed mechanism for the carbonylative double cyclization of 2-bromoanilines with 2-bromobenzonitriles to give isoindolo[1,2-b]quinazoline-10,12-diones [83].
Catalysts 13 01025 sch033
Catalysts 13 01025 sch034 550
Scheme 34. Carbonylative double cyclization of N-(2-bromophenyl)-2-(2-iodophenyl)acetamides to give 5H-isochromeno[3,4-b]quinoline-5,12(7H)-diones [84].
Scheme 34. Carbonylative double cyclization of N-(2-bromophenyl)-2-(2-iodophenyl)acetamides to give 5H-isochromeno[3,4-b]quinoline-5,12(7H)-diones [84].
Catalysts 13 01025 sch034
Catalysts 13 01025 sch035 550
Scheme 35. Proposed mechanism for the carbonylative double cyclization of N-(2-bromophenyl)-2-(2-iodophenyl)acetamides to give 5H-isochromeno[3,4-b]quinoline-5,12(7H)-diones [84].
Scheme 35. Proposed mechanism for the carbonylative double cyclization of N-(2-bromophenyl)-2-(2-iodophenyl)acetamides to give 5H-isochromeno[3,4-b]quinoline-5,12(7H)-diones [84].
Catalysts 13 01025 sch035
Table
Table 1. Representative examples of the Pd(II)-promoted carbonylative double cyclization of enediol derivatives in the synthesis of natural and bioactive products.
Table 1. Representative examples of the Pd(II)-promoted carbonylative double cyclization of enediol derivatives in the synthesis of natural and bioactive products.
EntryConditionsSubstrateProductYield (%)Refs.
1PdCl2 (10 mol%), CuCl2 (3 equiv), AcONa (3 equiv), CO (1 atm), AcOH, 25 °C, 41 hCatalysts 13 01025 i001Catalysts 13 01025 i00263[10]
2PdCl2(MeCN)2, (10 mol%), CuCl2 (2.4 equiv), CO (1 atm), THF, 25 °C, 24 hCatalysts 13 01025 i003Catalysts 13 01025 i00465[11]
3PdCl2 (10 mol%), CuCl2 (3 equiv), AcONa (3 equiv), CO (1 atm), AcOH, 25 °C, 8 hCatalysts 13 01025 i005Catalysts 13 01025 i00685[12]
4PdCl2 (10 mol%), CuCl2 (3 equiv), AcONa (4 equiv), CO (1 atm), AcOH, 25 °C, 24 hCatalysts 13 01025 i007Catalysts 13 01025 i00893[13]
5PdCl2 (10 mol%), CuCl2 (3 equiv), AcONa (3 equiv), CO (1 atm), AcOH, 25 °C, 33 hCatalysts 13 01025 i009Catalysts 13 01025 i01038[14]
6PdCl2 (10 mol%), CuCl2 (3 equiv), AcONa (3 equiv), CO (1 atm), AcOH, 25 °C, 15 hCatalysts 13 01025 i011Catalysts 13 01025 i012>80[15]
7Pd(OAc)2 (1.5 equiv), CO
(1.1 atm), THF, 23 °C, 4 h		Catalysts 13 01025 i013Catalysts 13 01025 i01487[16]
8PdCl2 (10 mol%), CuCl2 (3 equiv), AcONa (3 equiv), CO (1 atm), AcOH, 25 °C, 15 hCatalysts 13 01025 i015Catalysts 13 01025 i01681[17]
9PdCl2 (10 mol%), CuCl2 (3 equiv), AcONa (3 equiv), CO (1 atm), AcOH, 25 °CCatalysts 13 01025 i017Catalysts 13 01025 i01863[18]
10PdCl2, CuCl, AcONa, CO, AcOHCatalysts 13 01025 i019Catalysts 13 01025 i02033[19]
11PdCl2 (10 mol%), CuCl2 (3 equiv), AcONa (3 equiv), CO (1 atm), AcOH, 25 °C, 10 hCatalysts 13 01025 i021Catalysts 13 01025 i02285[20]
12PdCl2 (10 mol%), CuCl2 (3 equiv), AcONa (3 equiv), CO (1 atm), AcOH, 23 °C, 24 hCatalysts 13 01025 i023Catalysts 13 01025 i02475[21]
13Pd(OAc)2 (1.5 equiv),
N-methylmorpholine (3 equiv), CO, THF, 25 °C, 15 h		Catalysts 13 01025 i025Catalysts 13 01025 i02658[22]
14PdCl2 (10 mol%), CuCl2 (3 equiv), AcONa (3 equiv), CO (1 atm), AcOH, 25 °C, 20 hCatalysts 13 01025 i027Catalysts 13 01025 i02865[23]
15Pd(OAc)2 (10 mol%), CuCl2
(3 equiv), AcONa (3 equiv),
CO (1 atm), AcOH, 25 °C, 15 h		Catalysts 13 01025 i029Catalysts 13 01025 i03063, 70[24,25]
16PdCl2 (10 mol%), CuCl2 (3 equiv), AcONa (3 equiv), CO (1 atm), AcOH, 25 °C, 24 hCatalysts 13 01025 i031Catalysts 13 01025 i03233[26]
17PdCl2 (10 mol%), CuCl2 (3 equiv), AcONa (3 equiv), CO (1 atm), AcOH, 25 °C, 24 hCatalysts 13 01025 i033Catalysts 13 01025 i03487[27]
18PdCl2 (10 mol%), CuCl2 (3 equiv), AcONa (3 equiv), CO (1 atm), AcOH, 25 °C, 12 hCatalysts 13 01025 i035Catalysts 13 01025 i03661[28]
19PdCl2(MeCN)2 (10 mol%), CuCl2 (5 equiv), AcOLi (5 equiv), [Fe(CO)5] (0.5 equiv), AcOH, 60 °C, 1 hCatalysts 13 01025 i037Catalysts 13 01025 i03847[29]
20PdCl2(MeCN)2 (10 mol%), Cu(OAc)2 (4 equiv), LiCl
(4 equiv), [Fe(CO)5] (0.25 equiv), AcOH, 60 °C, 15 min		Catalysts 13 01025 i039Catalysts 13 01025 i04067[30]
21PdCl2(MeCN)2 (10 mol%), CuCl2 (4 equiv), AcOLi (4 equiv), [Fe(CO)5] (0.3 equiv), AcOH, 60 °C, 30 minCatalysts 13 01025 i041Catalysts 13 01025 i04275[31]
Table
Table 2. Examples of the “cyclization–carbonylation–cyclization coupling” concept leading to di(hetero)cyclic ketones.
Table 2. Examples of the “cyclization–carbonylation–cyclization coupling” concept leading to di(hetero)cyclic ketones.
EntryConditionsSubstrateProductYields (%)Refs.
1Pd(tfa)2 (5 mol%), Catalysts 13 01025 i043 (10 mol%), p-benzoquinone
(2 equiv), CO (1 atm), MeOH, 0 °C, 5–12 h		Catalysts 13 01025 i044Catalysts 13 01025 i04590–92[51]
2Pd(L)(tfa)2 (5 mol%), L = Catalysts 13 01025 i046 p-benzoquinone
(1.5 equiv), CO (1 atm), MeOH, 7 to 25 °C, 18–48 h		Catalysts 13 01025 i047Catalysts 13 01025 i04824–89[54]
3Pd(tfa)2 (5–10 mol%), Catalysts 13 01025 i049 (7.5–12 mol%),
p-benzoquinone (2 equiv), CO (1 atm), MeOH, −30 to 0 °C,
2–53 h		Catalysts 13 01025 i050Catalysts 13 01025 i05171–99[55]
4Pd(tfa)2 (5 mol%), Catalysts 13 01025 i052 (7.5 mol%), p-benzoquinone (2 equiv), CO (1 atm), MeOH, 25 °C, 1–63 hCatalysts 13 01025 i053Catalysts 13 01025 i05410–89[56]
5Pd(L)(tfa)2 (5 mol%), L = Catalysts 13 01025 i055 p-benzoquinone
(1.5 equiv), CO (1 atm), MeOH, −5 to 25 °C, 1–46 h		Catalysts 13 01025 i056Catalysts 13 01025 i05770–94[57]
6Pd(L)(tfa)2 (5 mol%), L = Catalysts 13 01025 i058 p-benzoquinone
(1.5 equiv), CO (1 atm), MeOH, −30 to 25 °C, 24–144 h		Catalysts 13 01025 i059Catalysts 13 01025 i06075–100[52,58]
7Pd(L)(tfa)2 (5 mol%), L = Catalysts 13 01025 i061 p-benzoquinone
(1.5 equiv), CO (1 atm), iPrOH, −5 to 15 °C, 47–72 h		Catalysts 13 01025 i062Catalysts 13 01025 i06373–92[59]
8Pd(L)(tfa)2 (5 mol%), L = Catalysts 13 01025 i064 p-benzoquinone
(1.5 equiv), CO (1 atm), MeOH, −20 to 0 °C, 24–76 h		Catalysts 13 01025 i065Catalysts 13 01025 i06670–94[60]
9Pd(L)(tfa)2 (5 mol%), L = Catalysts 13 01025 i067 p-benzoquinone
(1.5 equiv), CO (1 atm), MeOH, −5 to 25 °C, 24–55 h		Catalysts 13 01025 i068Catalysts 13 01025 i06912–86[61]
Disclaimer/Publisher’s Note: The statements, opinions and data contained in all publications are solely those of the individual author(s) and contributor(s) and not of MDPI and/or the editor(s). MDPI and/or the editor(s) disclaim responsibility for any injury to people or property resulting from any ideas, methods, instructions or products referred to in the content.

Share and Cite

MDPI and ACS Style

Gabriele, B.; Mancuso, R.; Della Ca’, N.; Veltri, L.; Ziccarelli, I. An Overview of Catalytic Carbonylative Double Cyclization Reactions. Catalysts 2023, 13, 1025. https://doi.org/10.3390/catal13061025

AMA Style

Gabriele B, Mancuso R, Della Ca’ N, Veltri L, Ziccarelli I. An Overview of Catalytic Carbonylative Double Cyclization Reactions. Catalysts. 2023; 13(6):1025. https://doi.org/10.3390/catal13061025

Chicago/Turabian Style

Gabriele, Bartolo, Raffaella Mancuso, Nicola Della Ca’, Lucia Veltri, and Ida Ziccarelli. 2023. "An Overview of Catalytic Carbonylative Double Cyclization Reactions" Catalysts 13, no. 6: 1025. https://doi.org/10.3390/catal13061025

Note that from the first issue of 2016, this journal uses article numbers instead of page numbers. See further details here.

Article Metrics

Back to TopTop