Asymmetric Bimetallic Catalysis Enabled Alkenyl Z/E Mutual Isomerization DOI
Guanlin Li,

Zheyuan Lai,

Zheng En

и другие.

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Июнь 5, 2025

Olefins are fundamental functional groups present in numerous molecules, and the geometrical configuration of C═C bonds often plays a critical role determining properties these compounds. Alkenyl isomerization is, principle, one most efficient approaches for accessing stereodefined olefins. While some progress has been made achieving unidirectional Z → E or conversion via olefin isomerization, there remains strong demand controllable, bidirectional bonds. Herein, we method Z/E mutual alkenyl by using Pd/Cu catalytic system. This process involves Pd-mediated π-σ-π interconversion followed selective trapping π-allyl-Pd intermediates with N-metalated azomethine ylides generated chiral Cu-catalyst. The reaction enables synthesis non-natural amino acid derivatives bearing Z- E-alkenyl an enantio- Z/E-divergent manner, yields up to 92%, > 20:1 E/Z, >99% ee. Furthermore, is scalable gram quantities, resulting products can be transformed into valuable molecules adorned groups. Computational studies show that bimetallic system better distinguishes among eight stereoisomers than monometallic system, which results exceptional Z/E-selectivity products. offers robust protocol synthesizing E-trisubstituted olefins motif utilizing readily available Z/E-mixture substrates.

Язык: Английский

Pd-Catalyzed Allylic Substitution of Azo-Ene Adducts Enables Net Allylic C–H Alkylation of Allylic Alcohols DOI
Yusuke Kuroda, Takashi Chiba,

Moe Kawajiri

и другие.

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Фев. 3, 2025

We present a protocol for regioselective allylic C-H alkylation of alcohols, consisting sequential azo-ene reaction and attendant Pd-catalyzed substitution with Grignard reagents. Notable features this work include: (1) C(sp3)-C(sp3) bond formation is achieved under Pd-catalysis, (2) the proceeds retention configuration at electrophilic carbon as well olefin geometry.

Язык: Английский

Процитировано

0
α,α-Difluorinated Allylsulfones: gem-Difluoroethylenyl Reagents for Synthesis of Fluorinated Chiral α-Quaternary Amino Acids DOI
Xiang Huang, Dongmei Fang, Xihong Wang

и другие.

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Март 25, 2025

Among numerous fluorine-containing molecules, chiral gem-difluoroethylenes (C═CF2) exhibited unique properties in agrochemicals, pharmaceuticals, and materials science. However, the general synthetic methods were limited to functionalization/defluorination of trifluoromethylalkenes. Here, we disclose a new type difluoroethylenyl reagent, α,α-difluoro allylsulfones, which allows highly enantioselective Cu-catalyzed desulfonylative SN2′ substitution with benzylideneamino esters. This protocol presents novel strategy for construction diversified α-quaternary amino acid derivatives containing gem-difluoroethylene moiety excellent results (up 86% yield, generally 90–98% ee). The ease synthesis applications this protocol, transformations products revealed potential utility chemistry.

Язык: Английский

Процитировано

0
Pd-Catalyzed Photoinduced Interceptive Decarboxylative Allylation DOI Creative Commons
Franz‐Lucas Haut, Filip S. Meger, Tomás G. Santiago

и другие.

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Май 12, 2025

Herein, we describe a photoinduced Pd-catalyzed interceptive decarboxylative allylation of allyl esters. Our protocol provides new gateway to enable atom pair swaps or series contractions and elongations, thus offering unconventional disconnections modular yet broadly applicable tool for rapidly reliably accessing sp3 architectures in drug discovery.

Язык: Английский

Процитировано

0
Asymmetric Bimetallic Catalysis Enabled Alkenyl Z/E Mutual Isomerization DOI
Guanlin Li,

Zheyuan Lai,

Zheng En

и другие.

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Июнь 5, 2025

Olefins are fundamental functional groups present in numerous molecules, and the geometrical configuration of C═C bonds often plays a critical role determining properties these compounds. Alkenyl isomerization is, principle, one most efficient approaches for accessing stereodefined olefins. While some progress has been made achieving unidirectional Z → E or conversion via olefin isomerization, there remains strong demand controllable, bidirectional bonds. Herein, we method Z/E mutual alkenyl by using Pd/Cu catalytic system. This process involves Pd-mediated π-σ-π interconversion followed selective trapping π-allyl-Pd intermediates with N-metalated azomethine ylides generated chiral Cu-catalyst. The reaction enables synthesis non-natural amino acid derivatives bearing Z- E-alkenyl an enantio- Z/E-divergent manner, yields up to 92%, > 20:1 E/Z, >99% ee. Furthermore, is scalable gram quantities, resulting products can be transformed into valuable molecules adorned groups. Computational studies show that bimetallic system better distinguishes among eight stereoisomers than monometallic system, which results exceptional Z/E-selectivity products. offers robust protocol synthesizing E-trisubstituted olefins motif utilizing readily available Z/E-mixture substrates.

Язык: Английский

Процитировано

0