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Catalysts
Special Issues
Theme Issue in Memory to Prof. Jiro Tsuji (1927–2022)
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Theme Issue in Memory to Prof. Jiro Tsuji (1927–2022)

A special issue of Catalysts (ISSN 2073-4344). This special issue belongs to the section "Catalysis in Organic and Polymer Chemistry".

Deadline for manuscript submissions: closed (30 June 2023) | Viewed by 18778

Special Issue Editors

Prof. Dr. Ewa Kowalska

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Guest Editor
Faculty of Chemistry, Jagiellonian University, Gronostajowa 2, 30-387 Krakow, Poland
Interests: heterogeneous photocatalysis; advanced oxidation processes (AOPs); environmental purification; plasmonic nanoparticles; antimicrobial properties; visible-light-responsive materials
Special Issues, Collections and Topics in MDPI journals
Prof. Dr. Yuichi Kobayashi

E-Mail Website
Guest Editor
Organization for the Strategic Coordination of Research and Intellectual Properties, Meiji University, 1-1-1, Higashimita, Tama-ku, Kawasaki, Kanagawa 214-8571, Japan
Interests: transition metal-catalyzed reaction; organic synthesis using catalytic reaction; asymmetric synthesis; carbon-carbon bond formation; allylic substitution; substitution at a secondary carbon; biologically active compounds; fatty acid metabolites; resolvins

Special Issue Information

Dear Colleagues, 

This Special Issue of Catalysts is dedicated to Professor Jiro Tsuji, who passed away on April 1st, 2022. He pioneered the discovery of many transition metal-catalyzed reactions and showed general idea of developing and applying these reactions in organic synthesis. Well-known reactions among them are several types of Pd-catalyzed reactions such as substitution of allylic substrates based on the stoichiometric reaction of π-allyl palladium with carbon nucleophiles discovered in 1965; reactions of allyl β-keto esters, resulting in allylation, olefin formation, and reduction; reactions of propargylic substrates; formation of methyl ketones from 1-olefins based on the Wacker process of ethylene. It is noteworthy that the olefin formation is used as the key step in the industrial synthesis of Jasmonate. Other reactions catalyzed by Pd, Ru, and Cu are carbonylation of olefins, dienes, acetylenes, and allyl compounds; decarbonylation of acid chloride and aldehydes; oxidative decomposition of catechol to muconic acid, etc. Tsuji focused on carbon-carbon bond forming reaction from the very beginning of his research. According to Tsuji, importance of the formation in organic synthesis was taught by Professor Gilbert Stork when he was in the doctoral program at Columbia University.

The significance of the reactions found by Tsuji has been proven by their widespread adoption in academic and industrial laboratories. Consequently, it is not surprising that Tsuji has been honored with the Chemical Society of Japan Award in 1981, the Japanese Medal of Honor with Purple Ribbon in 1994, the Japan Academy Prize in 2004, and the Tetrahedron Prize in 2014. He received Honorary Professor at Tokyo Institute of Technology.   

Jiro Tsuji was born on May 11, 1927 in Shiga, Japan. He received a Bachelor of Science degree from Kyoto University, Japan, in 1951, a Master’s degree from Baylor University, USA, in 1957, and a Ph.D. from Columbia University, USA, in 1960 under the supervision of Gilbert Stork. Tsuji returned to Japan in 1962 to work as a Research Associate at Toray Industries, where he began his career of transition-metal-catalyzed reactions. In 1974, he moved to Tokyo Institute of Technology, and served as Professor until retirement age of 60 in 1988. Thereafter, he was Professor at Okayama University of Science, Japan, from 1988 to 1996, and at Kurashiki University of Science and the Arts from 1996 to 1999.

We plan to organize a Special Issue honoring Jiro Tsuji's distinguished scientific career over the past 70 years. This Special Issue will consist of communications, original research articles, review articles, mini-reviews, perspectives, and viewpoints. Transition-metal-catalyzed reactions, application of such reactions in organic synthesis, natural product synthesis, or anecdotes on Jiro Tsuji are welcome.

Prof. Dr. Ewa Kowalska
Prof. Dr. Yuichi Kobayashi
Guest Editors

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Catalysts is an international peer-reviewed open access monthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2700 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • transition-metal complexes
  • reactions catalyzed by transition metals
  • organopalladium
  • chiral ligands
  • carbon–carbon bond formations
  • coupling reactions
  • Wacker reaction
  • allylic and propargylic systems
  • organic synthesis
  • synthesis of natural products

Published Papers (11 papers)

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Research

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6 pages, 1517 KiB  
Communication
Origins of Enhanced Enantioselectivity in the Pd-Catalyzed Decarboxylative Allylic Alkylation of N-Benzoyl Lactams
by Alexander Q. Cusumano, Tianyi Zhang, William A. Goddard III and Brian M. Stoltz
Catalysts 2023, 13(9), 1258; https://doi.org/10.3390/catal13091258 - 30 Aug 2023
Cited by 1 | Viewed by 1237
Abstract
We explore the origins of the marked improvement in enantioselectivity in the inner-sphere (PHOX)Pd-catalyzed allylic alkylation of N-benzoyl lactam nucleophiles over their carbocyclic counterparts. We employ density functional theory calculations to aid in the interpretation of experimental results. Ultimately, we propose that [...] Read more.
We explore the origins of the marked improvement in enantioselectivity in the inner-sphere (PHOX)Pd-catalyzed allylic alkylation of N-benzoyl lactam nucleophiles over their carbocyclic counterparts. We employ density functional theory calculations to aid in the interpretation of experimental results. Ultimately, we propose that the enhancement in enantioselectivity arises primarily from noncovalent interactions between the substrate and ligand rather than secondary substrate chelation, as previously hypothesized. Full article
(This article belongs to the Special Issue Theme Issue in Memory to Prof. Jiro Tsuji (1927–2022))
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Graphical abstract

14 pages, 1406 KiB  
Article
Substitution of Secondary Propargylic Phosphates Using Aryl-Lithium-Based Copper Reagents
by Yuichi Kobayashi, Takayuki Hirotsu, Yosuke Haimoto and Narihito Ogawa
Catalysts 2023, 13(7), 1084; https://doi.org/10.3390/catal13071084 - 10 Jul 2023
Viewed by 1120
Abstract
The substitution of secondary propargylic phosphates ROP(O)(OEt)2 where R = [Ph(CH2)2]C(H)(C≡CTMS)] Ph(CH2)2CH(OP(O)(OEt)2)(C≡CTMS) with copper reagents derived from PhLi and copper salts such as CuCl, CuCN, and Cu(acac)2 was studied [...] Read more.
The substitution of secondary propargylic phosphates ROP(O)(OEt)2 where R = [Ph(CH2)2]C(H)(C≡CTMS)] Ph(CH2)2CH(OP(O)(OEt)2)(C≡CTMS) with copper reagents derived from PhLi and copper salts such as CuCl, CuCN, and Cu(acac)2 was studied to establish an ArLi-based reagent system. Among the reagents prepared, PhLi/CuCl (2:1) showed 98% α regioselectivity (rs), while PhLi/Cu(acac)2 was γ selective (>99% rs). PhLi prepared in situ from PhI and PhBr by Li-halogen exchange with t-BuLi was also used for the α selective substitution. A study using the (S)-phosphate disclosed 99% enantiospecificity (es) and the inversion of the stereochemistry. The substitution of five phosphates with substituted aryl reagents produced the corresponding propargylic products with high rs and es values. Similar reactivity and selectivity were observed with 2-furyl and 2-thienyl reagents, which were prepared via direct lithiation with n-BuLi. Full article
(This article belongs to the Special Issue Theme Issue in Memory to Prof. Jiro Tsuji (1927–2022))
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Graphical abstract

10 pages, 1272 KiB  
Article
Electrochemical Thiocyanation/Cyclization Cascade to Access Thiocyanato-Containing Benzoxazines
by Jianguo Hu, Hao Wan, Shengchun Wang, Hong Yi and Aiwen Lei
Catalysts 2023, 13(3), 631; https://doi.org/10.3390/catal13030631 - 21 Mar 2023
Cited by 3 | Viewed by 1612
Abstract
Due to the importance of SCN-containing heteroarenes, developing novel and green synthetic protocols for the synthesis of SCN-containing compounds has drawn much attention over the last decades. We reported here an electrochemical oxidative cyclization of ortho-vinyl aniline to access various SCN-containing benzoxazines. [...] Read more.
Due to the importance of SCN-containing heteroarenes, developing novel and green synthetic protocols for the synthesis of SCN-containing compounds has drawn much attention over the last decades. We reported here an electrochemical oxidative cyclization of ortho-vinyl aniline to access various SCN-containing benzoxazines. Mild conditions, an extra catalyst-free and oxidant-free system, and good tolerance for air highlight the application potential of this method. Full article
(This article belongs to the Special Issue Theme Issue in Memory to Prof. Jiro Tsuji (1927–2022))
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Scheme 1

13 pages, 2936 KiB  
Article
A Second-Generation Palladacycle Architecture Bearing a N-Heterocyclic Carbene and Its Catalytic Behavior in Buchwald–Hartwig Amination Catalysis
by Sylwia Ostrowska, Lorenzo Palio, Agnieszka Czapik, Subhrajyoti Bhandary, Marcin Kwit, Kristof Van Hecke and Steven P. Nolan
Catalysts 2023, 13(3), 559; https://doi.org/10.3390/catal13030559 - 10 Mar 2023
Cited by 2 | Viewed by 2367
Abstract
Palladacyclic architectures have been shown as versatile motifs in cross-coupling reactions. NHC-ligated palladacycles possessing unique electronic and steric properties have helped to stabilize the catalytically active species and provide additional control over reaction selectivity. Here, we report on a synthetic protocol leading to [...] Read more.
Palladacyclic architectures have been shown as versatile motifs in cross-coupling reactions. NHC-ligated palladacycles possessing unique electronic and steric properties have helped to stabilize the catalytically active species and provide additional control over reaction selectivity. Here, we report on a synthetic protocol leading to palladacycle complexes using a mild base and an environmentally desirable solvent, with a focus on complexes bearing backbone-substituted N-heterocyclic carbene ligands. The readily accessible complexes exhibit high catalytic activity in the Buchwald–Hartwig amination. This is achieved using low catalyst loading and mild reaction conditions in a green solvent. Full article
(This article belongs to the Special Issue Theme Issue in Memory to Prof. Jiro Tsuji (1927–2022))
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Graphical abstract

18 pages, 2103 KiB  
Article
De Novo Synthesis of Polysubstituted 3-Hydroxypyridines Via “Anti-Wacker”-Type Cyclization
by Kazuya Ito, Takayuki Doi and Hirokazu Tsukamoto
Catalysts 2023, 13(2), 319; https://doi.org/10.3390/catal13020319 - 01 Feb 2023
Viewed by 1184
Abstract
We report an efficient method to prepare polysubstituted 3-hydroxypyridines from amino acids, propargyl alcohols, and arylboronic acids. The process involves Pd(0)-catalyzed anti-selective arylative cyclizations of N-propargyl-N-tosyl-aminoaldehydes with arylboronic acids (“anti-Wacker”-type cyclization), oxidation of the resulting 5-substituted-3-hydroxy-1,2,3,6-tetrahydropyridines to 3-oxo derivatives, [...] Read more.
We report an efficient method to prepare polysubstituted 3-hydroxypyridines from amino acids, propargyl alcohols, and arylboronic acids. The process involves Pd(0)-catalyzed anti-selective arylative cyclizations of N-propargyl-N-tosyl-aminoaldehydes with arylboronic acids (“anti-Wacker”-type cyclization), oxidation of the resulting 5-substituted-3-hydroxy-1,2,3,6-tetrahydropyridines to 3-oxo derivatives, and elimination of p-toluenesulfinic acid. This method provides diverse polysubstituted 3-hydroxypyridines, whose hydroxy group can be further substituted by a cross-coupling reaction via a triflate. Full article
(This article belongs to the Special Issue Theme Issue in Memory to Prof. Jiro Tsuji (1927–2022))
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Graphical abstract

8 pages, 1837 KiB  
Article
Palladium-Catalyzed Three-Component Coupling of Benzynes, Benzylic/Allylic Bromides and 1,1-Bis[(pinacolato)boryl]methane
by Zhicheng Bao, Chaoqiang Wu and Jianbo Wang
Catalysts 2023, 13(1), 126; https://doi.org/10.3390/catal13010126 - 05 Jan 2023
Viewed by 1455
Abstract
We report herein a palladium-catalyzed three-component cross-coupling reaction of 2-(trimethylsilyl)phenyl trifluoromethanesulfonate, benzylic/allylic bromides and 1,1-bis[(pinacolato)boryl]methane. The reaction, which affords benzyl boronates as the products, represents the first example of using 1,1-bis[(pinacolato)boryl]methane in a cross-coupling reaction involving benzyne species. Full article
(This article belongs to the Special Issue Theme Issue in Memory to Prof. Jiro Tsuji (1927–2022))
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Scheme 1

19 pages, 1694 KiB  
Article
Photocatalyzed Oxidative Decarboxylation Forming Aminovinylcysteine Containing Peptides
by Masaya Kumashiro, Kosuke Ohsawa and Takayuki Doi
Catalysts 2022, 12(12), 1615; https://doi.org/10.3390/catal12121615 - 09 Dec 2022
Viewed by 1792
Abstract
The formation of (2S,3S)-S-[(Z)-aminovinyl]-3-methyl-D-cysteine (AviMeCys) substructures was developed based on the photocatalyzed-oxidative decarboxylation of lanthionine-bearing peptides. The decarboxylative selenoetherification of the N-hydroxyphthalimide ester, generated in situ, proceeded under mild conditions at −40 °C in [...] Read more.
The formation of (2S,3S)-S-[(Z)-aminovinyl]-3-methyl-D-cysteine (AviMeCys) substructures was developed based on the photocatalyzed-oxidative decarboxylation of lanthionine-bearing peptides. The decarboxylative selenoetherification of the N-hydroxyphthalimide ester, generated in situ, proceeded under mild conditions at −40 °C in the presence of 1 mol% of eosin Y-Na2 as a photocatalyst and the Hantzsch ester. The following β-elimination of the corresponding N,Se-acetal was operated in a one-pot operation, led to AviMeCys substructures found in natural products in moderate to good yields. The sulfide-bridged motif, and also the carbamate-type protecting groups, such as Cbz, Teoc, Boc and Fmoc groups, were tolerant under the reaction conditions. Full article
(This article belongs to the Special Issue Theme Issue in Memory to Prof. Jiro Tsuji (1927–2022))
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Graphical abstract

11 pages, 3904 KiB  
Communication
Rhodium-Catalyzed Dynamic Kinetic Resolution of Racemic Internal Allenes towards Chiral Allylated Triazoles and Tetrazoles
by Simon V. Sieger, Ilja Lubins and Bernhard Breit
Catalysts 2022, 12(10), 1209; https://doi.org/10.3390/catal12101209 - 11 Oct 2022
Viewed by 1674
Abstract
A general Rh-catalyzed addition reaction of nitrogen containing heterocycles to internal allenes is reported. Starting from racemic internal allenes a dynamic kinetic resolution (DKR) provides N-allylated triazoles and tetrazoles. Simultaneous control of N1/Nx-position selectivity, enantioselectivity and olefin [...] Read more.
A general Rh-catalyzed addition reaction of nitrogen containing heterocycles to internal allenes is reported. Starting from racemic internal allenes a dynamic kinetic resolution (DKR) provides N-allylated triazoles and tetrazoles. Simultaneous control of N1/Nx-position selectivity, enantioselectivity and olefin geometry gives access to important building blocks of target-oriented synthesis. The synthetic utility is demonstrated by a gram-scale reaction and a broad substrate scope tolerating multiple functional groups. Deuterium labeling experiments and experiments with enantioenriched allenes as starting material support a plausible reaction mechanism. Full article
(This article belongs to the Special Issue Theme Issue in Memory to Prof. Jiro Tsuji (1927–2022))
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Review

Jump to: Research

23 pages, 5166 KiB  
Review
Transition-Metal-Catalyzed C–C Bond Macrocyclization via Intramolecular C–H Bond Activation
by Xiao Wang, Ming-Zhu Lu and Teck-Peng Loh
Catalysts 2023, 13(2), 438; https://doi.org/10.3390/catal13020438 - 17 Feb 2023
Cited by 3 | Viewed by 1709
Abstract
Macrocycles are commonly synthesized via late-stage macrolactamization and macrolactonization. Strategies involving C–C bond macrocyclization have been reported, and examples include the transition-metal-catalyzed ring-closing metathesis and coupling reactions. In this mini-review, we summarize the recent progress in the direct synthesis of polyketide and polypeptide [...] Read more.
Macrocycles are commonly synthesized via late-stage macrolactamization and macrolactonization. Strategies involving C–C bond macrocyclization have been reported, and examples include the transition-metal-catalyzed ring-closing metathesis and coupling reactions. In this mini-review, we summarize the recent progress in the direct synthesis of polyketide and polypeptide macrocycles using a transition-metal-catalyzed C–H bond activation strategy. In the first part, rhodium-catalyzed alkene–alkene ring-closing coupling for polyketide synthesis is described. The second part summarizes the synthesis of polypeptide macrocycles. The activation of indolyl and aryl C(sp2)–H bonds followed by coupling with various coupling partners such as aryl halides, arylates, and alkynyl bromide is then documented. Moreover, transition-metal-catalyzed C–C bond macrocyclization reactions via alkyl C(sp3)–H bond activation are also included. We hope that this mini-review will inspire more researchers to explore new and broadly applicable strategies for C–C bond macrocyclization via intramolecular C–H activation. Full article
(This article belongs to the Special Issue Theme Issue in Memory to Prof. Jiro Tsuji (1927–2022))
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Figure 1

23 pages, 7693 KiB  
Review
Coupling Reactions on Secondary Allylic, Propargylic, and Alkyl Carbons Using Organoborates/Ni and RMgX/Cu Reagents
by Yuichi Kobayashi
Catalysts 2023, 13(1), 132; https://doi.org/10.3390/catal13010132 - 06 Jan 2023
Cited by 1 | Viewed by 1574
Abstract
In the first part of this review, secondary carbon-carbon bond formation by using allylic coupling reactions with aryl and alkenyl borates is presented. Early investigations have revealed the suitability of a nickel catalyst and [RTB(OMe)3]Li (RT: transferable [...] Read more.
In the first part of this review, secondary carbon-carbon bond formation by using allylic coupling reactions with aryl and alkenyl borates is presented. Early investigations have revealed the suitability of a nickel catalyst and [RTB(OMe)3]Li (RT: transferable group). Due to their low reactivity, the borates were converted to more reactive congeners possessing an alkanediol ligand, such as 2,3-butanediol and 2,2-dimethyl-1,3-propanediol. Borates with such diol ligands were used to install aryl and alkenyl groups on the monoacetate of 4-cyclopentenyl-1,3-diol. Furthermore, alkenyl borates showed sufficient reactivity toward less reactive allylic alcohol derivatives with bromine atoms at the cis position, producing dieneyl alcohols. In the second part, copper-based and/or copper-catalyzed substitutions of secondary allylic picolinates, propargylic phosphonates, and alkyl (2-pyridine)sulfonates with RMgX are briefly summarized. The application of these reactions to the synthesis of biologically active compounds is also discussed. Full article
(This article belongs to the Special Issue Theme Issue in Memory to Prof. Jiro Tsuji (1927–2022))
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Graphical abstract

10 pages, 6796 KiB  
Review
Construction of Benzo-Fused Polycyclic Heteroaromatic Compounds through Palladium-Catalyzed Intramolecular C-H/C-H Biaryl Coupling
by Yuji Nishii and Masahiro Miura
Catalysts 2023, 13(1), 12; https://doi.org/10.3390/catal13010012 - 22 Dec 2022
Cited by 4 | Viewed by 1703
Abstract
Dibenzo-fused five-membered heteroaromatic compounds, including dibenzofuran, carbazole, and dibenzothiophene, are fundamental structural units in various important polycyclic heteroaromatic compounds. The intramolecular C-H/C-H biaryl coupling of diaryl (thio)ethers and amines based on palladium(II) catalysis under oxidative conditions is known to be one of the [...] Read more.
Dibenzo-fused five-membered heteroaromatic compounds, including dibenzofuran, carbazole, and dibenzothiophene, are fundamental structural units in various important polycyclic heteroaromatic compounds. The intramolecular C-H/C-H biaryl coupling of diaryl (thio)ethers and amines based on palladium(II) catalysis under oxidative conditions is known to be one of the most effective, step-economic methods for their construction. Representative examples for the construction of structurally intriguing π-extended polycyclic heteroaromatics through catalytic coupling reactions are briefly summarized in this mini-review. Full article
(This article belongs to the Special Issue Theme Issue in Memory to Prof. Jiro Tsuji (1927–2022))
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