Enantioselective Synthesis of Chiral Acyclic Nitriles Containing α-All-Carbon Quaternary Stereocenters via Synergistic Palladium and Phase-Transfer Catalysis DOI
Cheng Guo, Yunpeng Dong, Yi Wang

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(24), P. 18841 - 18850

Published: Dec. 11, 2024

Herein, we present a practical strategy for the asymmetric synthesis of chiral acyclic nitriles featuring α-all-carbon quaternary stereocenters, utilizing synergistic palladium and phase-transfer catalysis from allyl 2-cyanoacetates under mild conditions. This approach offers an efficient reliable method in situ generation tertiary α-cyano carbanions through intramolecular palladium-catalyzed decarboxylative allylic alkylation. Additionally, it enables highly enantioselective control simple via ion-pairing interactions with catalysts. The synthetic utility this is further demonstrated by its scalability to gram-scale subsequent transformation into variety functionalized compounds containing all-carbon stereocenters.

Language: Английский

Sulfonated Phosphine‐Palladium/Bisguanidinium Ion Pair Catalyzed Enantioselective Allylic Amination DOI

Long‐Yi Xi,

R. Panner Selvam,

Chen Xu

et al.

Chinese Journal of Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: April 24, 2025

Comprehensive Summary In this study, we successfully developed ion pair catalysts consisting of chiral bisguanidinium (BG) cations and non‐chiral sulphonated phosphine‐palladium complexes as counterions. These pairs catalyzed allylic alkylation reactions with excellent enantioselectivities. Furthermore, these can be easily performed on a gram‐scale, demonstrating their potential for industrial applications. We were able to obtain 1 H NMR the catalyst identified 31 P complex.

Language: Английский

Citations

0
Origin of Stereoselectivity in Pd-Catalyzed Asymmetric Allylic Substitutions with Trost-Type Mixed Bidentate Phosphorus Ligands DOI

Sanghyup Seo,

Taeil Shin,

In‐Kyu Choi

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(14), P. 11113 - 11120

Published: July 10, 2024

Language: Английский

Citations

1
Relay PHOS: Ligands with Fluxional Chirality in Asymmetric Palladium-Catalyzed Allylic Alkylation DOI
Regina C. So, Hariharaputhiran Subramanian,

Carter R. Kuehn

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(34), P. 7196 - 7201

Published: Aug. 19, 2024

A modular route toward the synthesis of P,N ligands containing a fluxional group along pyrazoline ring core is described. The racemic were accessed in three steps from commercially available fluoroacetophenone overall yields ranging 18 to 76%. enantiopure obtained using semi-preparative chiral high-performance liquid chromatography and enantioselective phase-transfer catalysis. effectiveness new was assessed palladium-catalyzed allylic alkylation with diphenylpropenyl acetate dimethylpropenyl acetate. Under optimized conditions, underwent dimethyl malonate 98% yield 94% ee. In general, enantioselectivity for product correlates size ligand group; larger group, higher selectivity.

Language: Английский

Citations

1
Enantioselective Synthesis of Chiral Acyclic Nitriles Containing α-All-Carbon Quaternary Stereocenters via Synergistic Palladium and Phase-Transfer Catalysis DOI
Cheng Guo, Yunpeng Dong, Yi Wang

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(24), P. 18841 - 18850

Published: Dec. 11, 2024

Herein, we present a practical strategy for the asymmetric synthesis of chiral acyclic nitriles featuring α-all-carbon quaternary stereocenters, utilizing synergistic palladium and phase-transfer catalysis from allyl 2-cyanoacetates under mild conditions. This approach offers an efficient reliable method in situ generation tertiary α-cyano carbanions through intramolecular palladium-catalyzed decarboxylative allylic alkylation. Additionally, it enables highly enantioselective control simple via ion-pairing interactions with catalysts. The synthetic utility this is further demonstrated by its scalability to gram-scale subsequent transformation into variety functionalized compounds containing all-carbon stereocenters.

Language: Английский

Citations

0