Ligand-Controlled Enantioselective Copper-Catalyzed Hydroboration and Ring-Opening Dihydroboration of Arylidenecyclobutanes DOI
Wenrui Zheng, Yuhan Cao,

Boon Beng Tan

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: March 25, 2025

Arylidenecyclobutanes are readily accessible and versatile reagents in synthetic chemistry due to the multifaceted reactivity exhibited by their alkene strained cyclobutane moieties. However, metal-catalyzed enantioselective functionalization of arylidenecyclobutanes, particularly controllable ring-retaining ring-opening reactions, is rarely explored. Considering utility enantioenriched organoboronate compounds, herein we report ligand-controlled copper-catalyzed hydroboration dihydroboration reactions arylidenecyclobutanes that afford chiral α-cyclobutyl benzylboronate 1,5-diboronate compounds with high enantioselectivity when (S)-DTBM-Segphos (S,S)-Ph-BPE employed, respectively. Mechanistic studies reveal process via β-C elimination significantly slower than arylidenecyclopropanes presence CuOAc (S,S)-Ph-BPE. The these two protocols further demonstrated through conducting various stereospecific site-selective transformations organoboron products, including concise synthesis bioactive molecules.

Language: Английский

Anti-Markovnikov hydroallylation reaction of alkenes via scandium-catalyzed allylic C‒H activation DOI Creative Commons

Shiyu Wang,

Lichao Ning,

Tao Mao

et al.

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: Feb. 6, 2025

Compared with rare-earth (RE)…heteroatom interaction, RE…π frequently used in facilitating regio- and stereoselectivity of olefin polymerizations, is seldomly to trigger catalytic C - H functionalization. Here, we describe a direct anti-Markovnikov hydroallylation reaction styrene derivatives 1-aryl-2-alkyl alkenes α-alkenes by use interaction. This protocol provides straightforward atom-efficient route for the synthesis valuable chain elongated internal (65 examples, up 99% yield, > 19:1 E/Z ratio). The proceeds via an allylic Csp3‒H activation pathway initiated site-selective deprotonation assistance cationic imidazolin-2-iminato scandium alkyl species followed alkene insertion into resulting scandium-allyl bond. A amount Lewis base additives, such as amine tetrahydrofuran (THF) show significant effects on reactivity selectivity. mechanism elucidated experimental studies theoretical calculations.

Language: Английский

Citations

3
Silver-mediated formal [4π + 2σ] cycloaddition reactions of bicyclobutanes with nitrile imines: access to 2,3-diazobicyclo[3.1.1]heptenes DOI Creative Commons

Huijuan Liao,

Jianyang Dong,

Xuechen Zhou

et al.

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

Published: Jan. 1, 2025

We disclose a method for silver-enabled formal [4π + 2 σ ] cycloaddition reactions between bicyclobutanes and nitrile imines (generated from hydrazonyl chlorides) to furnish diverse array of 2,3-diazo-BCHepes.

Language: Английский

Citations

2
Ligand-Controlled Enantioselective Copper-Catalyzed Hydroboration and Ring-Opening Dihydroboration of Arylidenecyclobutanes DOI
Wenrui Zheng, Yuhan Cao,

Boon Beng Tan

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: March 25, 2025

Arylidenecyclobutanes are readily accessible and versatile reagents in synthetic chemistry due to the multifaceted reactivity exhibited by their alkene strained cyclobutane moieties. However, metal-catalyzed enantioselective functionalization of arylidenecyclobutanes, particularly controllable ring-retaining ring-opening reactions, is rarely explored. Considering utility enantioenriched organoboronate compounds, herein we report ligand-controlled copper-catalyzed hydroboration dihydroboration reactions arylidenecyclobutanes that afford chiral α-cyclobutyl benzylboronate 1,5-diboronate compounds with high enantioselectivity when (S)-DTBM-Segphos (S,S)-Ph-BPE employed, respectively. Mechanistic studies reveal process via β-C elimination significantly slower than arylidenecyclopropanes presence CuOAc (S,S)-Ph-BPE. The these two protocols further demonstrated through conducting various stereospecific site-selective transformations organoboron products, including concise synthesis bioactive molecules.

Language: Английский

Citations

0