Hydroalkoxylation of Terminal and Internal Alkynes Catalyzed by Dinuclear Gold(I) Complexes with Bridging Di(N-Heterocyclic Carbene) Ligands
Abstract
:1. Introduction
2. Results and Discussion
2.1. Screening of the Reaction Conditions
2.2. Catalyst Screening
2.3. X-ray Structure Analysis
2.4. Substrates Scope and Analysis of the Selectivity in the Hydroalkoxylation of Alkynes
2.5. Comparison of The Catalytic Performances of Au2Br2L4 with Mononuclear Catalysts
3. Materials and Methods
3.1. Synthesis of the Mononuclear Gold(I) Complex {1-(2,6-Diisopropylphenyl)-3-Methyl Imidazol-2-Ylidene}Iodogold(I) AuIL7
3.2. X-ray Crystal Structure Determination of Au2Br2L4
3.3. Catalytic Tests on the Alkyne Hydroalkoxylation Reaction
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Conflicts of Interest
References
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Entry | Solvent | Cat | Co-Cat | T (°C) | t (h) | Alkyne Conversion (%) a |
---|---|---|---|---|---|---|
1 | neat | Au2Br2L5 | AgSbF6 | rt | 22 | nr |
2 | neat | Au2Br2L5 | AgSbF6 | 40 | 1 | 100 |
3 | neat | Au2Br2L3 | AgOTf | rt | 22 | nr |
4 | neat | Au2Br2L5 | AgOTf | 40 | 1.5 18.5 | 86 89 |
5 | neat | Au2Br2L3 | AgOTf | 40 | 1 6.5 22 | 62 86 87 |
6 | CHCl3 | Au2Br2L5 | AgOTf | 40 | 1 | 100 |
7 | CH3CN b | Au2Br2L3 | AgOTf | 40 | 1 22 | <1 12 |
8 | neat | - | AgOTf | 40 | 22 | nr |
Entry | Cat (mol%) | t (h) | Alkyne Conversion (%) a |
---|---|---|---|
1 | Au2Br2L1 | 1.5 6.5 22 | 67 91 92 |
2 | Au2Br2L2 | 1.5 6.5 | 78 90 |
3 | Au2Br2L3 | 1.5 6.5 22 | 62 86 87 |
4 | Au2Br2L4 | 1 18.5 | 100 100 |
5 | Au2Br2L5 | 1 18.5 | 86 89 |
6 | Au2Br2L6 | 1 23 | 72 100 |
Entry | Alkyne | Alcohol | t (h) | Alkyne Conversion (%) a | Yield (%) a |
---|---|---|---|---|---|
1 | PhC≡CCO2Et | MeOH | 1 18.5 | 100 100 | (E)-3aa (33); 5a (67) 5a (100) |
2 | PhC≡CCO2Et | n-BuOH | 1 18.5 | 92 100 | (Z)-3ab (21); (E)-3ab (16); 5a (55) 5a (100) |
3 b | PhC≡CCO2Et | PhOH | 1 18.5 | 66 100 | (Z)-3ac (37); 5a (29) (Z)-3ac (31); 5a (69) |
4 | PhC≡CH | MeOH | 1 18.5 | 66 99 | 5b (66) 5b (99) |
5 | HC≡CCO2Et | MeOH | 1 18.5 | 50 100 | (Z)-3ca (15); (E)-3ca (19); 3ca’ (10); 4ca (6) (E)-3ca (26); 4ca (50); 5c (14) |
6 | EtC≡CEt | MeOH | 1 18.5 | 58 89 | 5d (58) 5d (89) |
7 | PhC≡CPh | MeOH | 1 18.5 | 11 63 | 5e (11) 5e (63) |
8 | PhC≡CCO2H | MeOH | 1 18.5 | 25 50 | 5b (14); 5g (6); 1g (5) 5b (37); 5g (3); 1g (10) |
9 c | PhC≡CPh | MeOH | 1 18.5 | 25 83 | (Z)-3ea (21); 5e (4) 5e (83) |
Entry | Alkyne | Alcohol | Cat (mol%) | Co-Cat (mol%) | T (°C) | T (h) | Alkyne Conversion (%) a |
---|---|---|---|---|---|---|---|
1 | EtC≡CEt | MeOH | IPrAuCl (2) | AgOTf (2) | 40 | 1 | 100 |
2 | EtC≡CEt | MeOH | AuIL7 (2) | AgOTf (2) | 40 | 1 18.5 | nr nr |
3 | PhC≡CCO2Et | MeOH | AuIL7 (2) | AgOTf (2) | 40 | 1 18.5 | nr nr |
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Marcheggiani, E.; Tubaro, C.; Biffis, A.; Graiff, C.; Baron, M. Hydroalkoxylation of Terminal and Internal Alkynes Catalyzed by Dinuclear Gold(I) Complexes with Bridging Di(N-Heterocyclic Carbene) Ligands. Catalysts 2020, 10, 1. https://doi.org/10.3390/catal10010001
Marcheggiani E, Tubaro C, Biffis A, Graiff C, Baron M. Hydroalkoxylation of Terminal and Internal Alkynes Catalyzed by Dinuclear Gold(I) Complexes with Bridging Di(N-Heterocyclic Carbene) Ligands. Catalysts. 2020; 10(1):1. https://doi.org/10.3390/catal10010001
Chicago/Turabian StyleMarcheggiani, Elena, Cristina Tubaro, Andrea Biffis, Claudia Graiff, and Marco Baron. 2020. "Hydroalkoxylation of Terminal and Internal Alkynes Catalyzed by Dinuclear Gold(I) Complexes with Bridging Di(N-Heterocyclic Carbene) Ligands" Catalysts 10, no. 1: 1. https://doi.org/10.3390/catal10010001