Silver- and Base-Enabled SOMOphilic Alkynylation of Alkylboronic Acids with Bromoalkynes DOI

Wenqian Du,

Rongjie Yang,

Jian-Shan Bai

et al.

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: May 8, 2025

Alkynyl-containing molecules hold significant importance in organic synthesis, drug discovery, and materials science. Herein, we report an efficient protocol for the C(sp)-C(sp3) cross-coupling of bromoalkynes with primary, secondary, tertiary alkylboronic acids. Mechanistic experiments suggest that silver base enable generation alkyl radical intermediate from acid then undergo a cascade α-addition β-elimination alkynyl bromides, leading to construction bonds. This strategy features readily available starting materials, diverse substrates, mild easily handled reaction conditions.

Language: Английский

Photocatalytic Strategy for Decyanative Transformations Enabled by Amine-Ligated Boryl Radical DOI Creative Commons

Yuto Yoshida,

Waka Okada,

Kazutake Takada

et al.

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

Published: Jan. 10, 2025

Decyanation after α-functionalization by exploiting the inherent properties of cyano groups enables strategic assembly a carbon scaffold. Herein, we demonstrate an amine-ligated boryl radical-mediated group transfer (CGT) strategy malononitriles under photocatalytic conditions. This allows for cleavage C(sp3)–CN and formation C(sp3)–D C(sp3) to realize decyanative deuteration cyclization via radical-polar crossover. Computational studies successfully demonstrated reactivity CGT promoters can be accurately assessed.

Language: Английский

Citations

0
Cobalt-Catalyzed Remote Site-Selective Hydroboration of Unactivated Alkenes via Chain-Walking Strategy DOI
Zhiqiang Wang,

Mengjie Zhang,

Xue Li

et al.

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

Published: March 11, 2025

An expedient synthesis of α-aminoboronic acid derivatives via cobalt-catalyzed remote site-selective hydroboration unactivated alkenes is described herein. The strategy characterized by its simplicity, site-selectivity, and wide substrate scope, as both terminal internal could undergo the reaction smoothly, affording corresponding products in good yields. According to mechanism, Co-H generated from Co(acac)2 presence HBpin, which starts chain-walking a series alkene insertion β-H elimination process.

Language: Английский

Citations

0
Modular assembly of amines and diborons with photocatalysis enabled halogen atom transfer of organohalides for C(sp3)–C(sp3) bond formation DOI Creative Commons

Rong‐Bin Liang,

Tingting Miao, Xiang-Rui Li

et al.

Chemical Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

A new photocatalytic approach by using the assembly of DABCO A1 and B 2 Nep B1 has been established to enable cross-coupling organohalides alkenes for C(sp 3 )–C(sp ) bond formation.

Language: Английский

Citations

0
MeOH-Triggered Halogen-Atom Transfer of Unactivated Alkyl Bromides Enabling the Photoredox Giese Addition DOI

Xian‐Chen He,

Yanling Liu, Jie Gao

et al.

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

Published: March 18, 2025

Herein, a nickel-catalyzed, photoredox Giese addition reaction with readily accessible alkyl bromides, driven by available feedstock MeOH as the halogen-atom transfer (XAT) reagent, was successfully achieved under mild conditions. The versatility of this protocol demonstrated through range structurally varied bromides and Giese-type acceptors moderate to good yields. Mechanistic investigation highlights that formation radicals XAT tentatively prompted •CH2OH, which derived from sequential photo-oxidation/1,2-hydrogen-atom MeOH.

Language: Английский

Citations

0
Silver- and Base-Enabled SOMOphilic Alkynylation of Alkylboronic Acids with Bromoalkynes DOI

Wenqian Du,

Rongjie Yang,

Jian-Shan Bai

et al.

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: May 8, 2025

Alkynyl-containing molecules hold significant importance in organic synthesis, drug discovery, and materials science. Herein, we report an efficient protocol for the C(sp)-C(sp3) cross-coupling of bromoalkynes with primary, secondary, tertiary alkylboronic acids. Mechanistic experiments suggest that silver base enable generation alkyl radical intermediate from acid then undergo a cascade α-addition β-elimination alkynyl bromides, leading to construction bonds. This strategy features readily available starting materials, diverse substrates, mild easily handled reaction conditions.

Language: Английский

Citations

0