Chiral bisphosphine Ph-BPE ligand: a rising star in asymmetric synthesis

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(13), P. 6735 - 6778

Published: Jan. 1, 2024

The review summarizes the increasing applications of chiral bisphosphine ligand Ph-BPE in catalytic asymmetric reactions past twenty years.

Language: Английский

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Copper-Catalyzed Diastereo-, Enantio-, and (Z)-Selective Aminoallylation of Ketones through Reductive Couplings of Azatrienes for the Synthesis of Allylic 1,2-Amino Tertiary Alcohols

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(29), P. 20270 - 20278

Published: July 16, 2024

We introduce a method for the (Z)-selective aminoallylation of range ketones to prepare allylic 1,2-amino tertiary alcohols with excellent diastereo- and enantioselectivity. Copper-catalyzed reductive couplings 2-azatrienes aryl/alkyl dialkyl proceed Ph-BPE as supporting ligand, generating anti-amino >98% (Z)-selectivity under mild conditions. The utility products is highlighted through several transformations, including those that leverage (Z)-allylic amine moiety diastereoselective reactions alkene. Calculations illustrate Curtin–Hammett control in product formation over other possible isomers origin (Z)-selectivity.

Language: Английский

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Enantioselective Synthesis of α‐Hydroxy Allyl Ketones via BINAP‐CuH‐Catalyzed Hydroacylation

Angewandte Chemie, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 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.

Language: Английский

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Enantioselective Synthesis of α‐Hydroxy Allyl Ketones via BINAP‐CuH‐Catalyzed Hydroacylation

Angewandte Chemie International Edition, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 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.

Language: Английский

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Development of regiodivergent asymmetric reductive coupling reactions of allenamides to access heteroatom-rich organic compounds

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(67), P. 10087 - 10100

Published: Jan. 1, 2023

This feature article describes the application of N -substituted allenes in regiodivergent reductive coupling strategies context new methods for synthesis heteroatom-rich organic compounds.

Language: Английский

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Enantioselective Synthesis of vic-Aminoalcohol Derivatives by Nickel-Catalyzed Reductive Coupling of Aldehydes with Protected Amino-pentadienoates

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 22, 2024

A VAPOL-derived phosphoramidite ligand is uniquely effective at reverting the regiochemical course of nickel-catalyzed reactions aldehydes with carbamate-protected 5-amino-2,4-pentadienoates as "push/pull" dienes; ensuing carbonyl α-amino-homoallylation reaction affords

Language: Английский

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