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

и другие.

ACS Catalysis, Год журнала: 2024, Номер 14(24), С. 18841 - 18850

Опубликована: Дек. 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.

Язык: Английский

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

Long‐Yi Xi,

R. Panner Selvam,

Chen Xu

и другие.

Chinese Journal of Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Апрель 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.

Язык: Английский

Процитировано

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

и другие.

ACS Catalysis, Год журнала: 2024, Номер 14(14), С. 11113 - 11120

Опубликована: Июль 10, 2024

Язык: Английский

Процитировано

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

Carter R. Kuehn

и другие.

Organic Letters, Год журнала: 2024, Номер 26(34), С. 7196 - 7201

Опубликована: Авг. 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.

Язык: Английский

Процитировано

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

и другие.

ACS Catalysis, Год журнала: 2024, Номер 14(24), С. 18841 - 18850

Опубликована: Дек. 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.

Язык: Английский

Процитировано

0