Acid/Base-Tuned Asymmetric Reductive Heck and Denitrogenative Heck Reactions of In Situ-Formed α,β-Unsaturated Hydrazone DOI

Shuling Yu,

Xiaoyu Zhou, Xiaofeng Tong

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 15(1), P. 72 - 80

Published: Dec. 13, 2024

Despite significant progress in the catalytic asymmetric 1,4-additions between various Michael donors and acceptors, exploration of organohalide remains elusive. Herein, we report Pd(0)-catalyzed intramolecular vinyl/aryl iodides to α,β-unsaturated hydrazones, featuring situ-formed hydrazone acid/base-tuned reaction pathways. Due its strong coordination ability, is capable steering C–C bond formation follow 1,4-addition mechanism instead conventional alkene insertion, thus enabling generation vinylhydrazinyl–Pd2+ species via Zimmerman–Traxler chairlike transition state. Notably, this preferentially undergoes protonation under acidic conditions, furnishing a reductive Heck with aid native hydrazine reductant, while it susceptible β-HN elimination basic conditions achieve denitrogenative reaction. The protocol affords highly enantioselective access diverse heterocycles, groups poised for further chemical manipulations.

Language: Английский

Palladium-Catalyzed Domino Heck/Decarboxylative Cyanomethylation of Indoles and Alkenes with Cyanoacetate Salts DOI

Ping‐Xin Zhou,

Yang Liu, Mengjuan Li

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: April 10, 2025

A palladium-catalyzed reaction of indoles with cyanoacetate salts enables the synthesis 2,6-disubstituted indolines via tandem dearomatization/decarboxylative cyanomethylation. Remarkably, this is first example indole difunctionalization at C2 and C6 positions. Moreover, methodology extends to cyclization/decarboxylative cyanomethylation aryl halide-tethered alkenes.

Language: Английский

Citations

0
Palladium-Catalyzed Dearomative Heck/C(sp2)–H Activation/Decarboxylative Cyclization of C2-Tethered Indoles DOI
Shuyi Guo,

Wenbo Deng,

Xiaochang Xiao

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(43), P. 9389 - 9394

Published: Oct. 21, 2024

Until now, palladium-catalyzed dearomative Heck reactions of indoles were largely limited to β-H elimination and nucleophilic capture the transient alkyl-Pd(II) species. Herein, we disclose a novel Heck/C(sp

Language: Английский

Citations

2
A Mechanistic Study of Chiral Manganese Porphyrin-Catalyzed Enantioselective C−H Hydroxylation Reaction DOI

Jing-Kun Gao,

Wan-Dong Chen,

Junjie Tai

et al.

Dalton Transactions, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

This study uses DFT to explain the enantioselectivity of C–H hydroxylation by a chiral manganese porphyrin. A two-point hydrogen bonding favors pro -( S ) bond abstraction 1.9 kcal mol −1 , leading ( )-hydroxylated products.

Language: Английский

Citations

1
Acid/Base-Tuned Asymmetric Reductive Heck and Denitrogenative Heck Reactions of In Situ-Formed α,β-Unsaturated Hydrazone DOI

Shuling Yu,

Xiaoyu Zhou, Xiaofeng Tong

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 15(1), P. 72 - 80

Published: Dec. 13, 2024

Despite significant progress in the catalytic asymmetric 1,4-additions between various Michael donors and acceptors, exploration of organohalide remains elusive. Herein, we report Pd(0)-catalyzed intramolecular vinyl/aryl iodides to α,β-unsaturated hydrazones, featuring situ-formed hydrazone acid/base-tuned reaction pathways. Due its strong coordination ability, is capable steering C–C bond formation follow 1,4-addition mechanism instead conventional alkene insertion, thus enabling generation vinylhydrazinyl–Pd2+ species via Zimmerman–Traxler chairlike transition state. Notably, this preferentially undergoes protonation under acidic conditions, furnishing a reductive Heck with aid native hydrazine reductant, while it susceptible β-HN elimination basic conditions achieve denitrogenative reaction. The protocol affords highly enantioselective access diverse heterocycles, groups poised for further chemical manipulations.

Language: Английский

Citations

0