Acta Chimica Sinica, Год журнала: 2024, Номер 82(12), С. 1274 - 1274
Опубликована: Янв. 1, 2024
Язык: Английский
ACS Catalysis, Год журнала: 2025, Номер 15(3), С. 1487 - 1513
Опубликована: Янв. 9, 2025
Due to the wide applications of resulting chiral tertiary homoallylic alcohols in organic synthesis, catalytic asymmetric ketone allylations have attracted continuous attention from synthetic chemists. Despite inherent difficulty enantiofacial differentiation and low reactivity ketones, past two decades witnessed rapid progress allylation ketones. Many efficient methods been reported, with discovery unprecedented catalysts reagents. The current Review aims give a summary achievements this area 2011 date is divided into six parts according reagents that were applied. Special paid scope application each method brief introduction corresponding mechanisms.
Язык: Английский
Процитировано
1
ACS Catalysis, Год журнала: 2025, Номер unknown, С. 5796 - 5805
Опубликована: Март 25, 2025
The transition metal-catalyzed asymmetric [n + 2] cycloaddition reaction with oxy-substituted ketene intermediates remains a synthetic challenge due to the limited availability of suitable precursors. Herein, we report visible-light-driven, palladium-catalyzed [4 vinyl benzoxazinanones siloxyketene intermediates, generating structurally diverse chiral quinolinone derivatives satisfactory diastereo- and enantioselectivities. transient generation siloxyketenes from α-ketoacylsilylanes through visible-light-induced Brook rearrangement is important for success present cycloaddition. 13C-labeling experiments reveal pathway involving [1,3]-silyl migration process. side arm effects BOX ligand silyl steric hindrance α-ketoacylsilanes play crucial roles in stereoselectivity control, theoretical calculations provide insights into stereochemical outcome reaction.
Язык: Английский
Процитировано
1
Science China Chemistry, Год журнала: 2025, Номер unknown
Опубликована: Янв. 3, 2025
Язык: Английский
Процитировано
0
Angewandte Chemie, Год журнала: 2025, Номер unknown
Опубликована: Янв. 31, 2025
Abstract Catalytic hydrocupration of unsaturated carbon‐carbon bonds to generate organometallic nucleophiles has recently become an attractive alternative conventional stoichiometric reagents in the stereoselective synthesis. Herein, we have developed efficient and economical method synthesize enantiopure α ‐hydroxy allyl ketones via a copper hydride (CuH)‐catalyzed hydroacylation alkoxyallenes, significant advancement given scarcity reports on such scaffolds literature. DFT calculations reveal that this reaction proceeds through nucleophilic attack kinetically favourable Z ‐selective allyl‐copper intermediate acid anhydrides six‐membered chair‐like transition state, stabilized by strongly non‐covalent interactions ultimately leads high level enantioselectivities using simple BINAP ligand. This successfully overcomes challenges over‐reduction carbonyl functionality presence CuH‐complex, olefin isomerization highly enolizable ‐stereocenter, which can lead erosion enantioselectivities, making our strategy desirable. The exhibits wide range substrate scope including symmetrical as well carbonic with both aromatic, aliphatic substitutions. In addition, ‐substituted provide exclusive syn α,α′ ‐disubstituted excellent enantiomeric ratios, where allylation occurs one carbonyls containing matched α‐ stereocenter, confirmed mechanistic studies.
Язык: Английский
Процитировано
0
Angewandte Chemie International Edition, Год журнала: 2025, Номер unknown
Опубликована: Янв. 31, 2025
Abstract Catalytic hydrocupration of unsaturated carbon‐carbon bonds to generate organometallic nucleophiles has recently become an attractive alternative conventional stoichiometric reagents in the stereoselective synthesis. Herein, we have developed efficient and economical method synthesize enantiopure α ‐hydroxy allyl ketones via a copper hydride (CuH)‐catalyzed hydroacylation alkoxyallenes, significant advancement given scarcity reports on such scaffolds literature. DFT calculations reveal that this reaction proceeds through nucleophilic attack kinetically favourable Z ‐selective allyl‐copper intermediate acid anhydrides six‐membered chair‐like transition state, stabilized by strongly non‐covalent interactions ultimately leads high level enantioselectivities using simple BINAP ligand. This successfully overcomes challenges over‐reduction carbonyl functionality presence CuH‐complex, olefin isomerization highly enolizable ‐stereocenter, which can lead erosion enantioselectivities, making our strategy desirable. The exhibits wide range substrate scope including symmetrical as well carbonic with both aromatic, aliphatic substitutions. In addition, ‐substituted provide exclusive syn α,α′ ‐disubstituted excellent enantiomeric ratios, where allylation occurs one carbonyls containing matched α‐ stereocenter, confirmed mechanistic studies.
Язык: Английский
Процитировано
0
Chemical Science, Год журнала: 2024, Номер unknown
Опубликована: Янв. 1, 2024
An economical method for highly enantioselective and diastereoselective synthesis of 1,2- syn-tert , sec -diols via Cu-BINAP-catalysed reductive coupling alkoxyallenes with ketones.
Язык: Английский
Процитировано
2
Chinese Journal of Organic Chemistry, Год журнала: 2024, Номер 44(7), С. 2391 - 2391
Опубликована: Янв. 1, 2024
Язык: Английский
Процитировано
0
Acta Chimica Sinica, Год журнала: 2024, Номер 82(12), С. 1274 - 1274
Опубликована: Янв. 1, 2024
Язык: Английский
Процитировано
0