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

Synthesis of α-Chloroboronic Esters via Photoredox-Catalyzed Chloro-Alkoxycarbonylation of Vinyl Boronic Esters DOI
Wen‐Duo Li, Nana Wei, Nan Feng

et al.

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

Published: March 9, 2025

α-Chloroboronic esters are a class of stable multifunctional molecules that show unique applications in pharmaceutical science and organic chemistry. Despite their apparent utility, the synthetic methods these compounds remain limited. Herein, novel strategy for efficient synthesis α-chloroboronic is developed via photoredox-catalyzed chloro-alkoxycarbonylation vinyl boronic esters. This features advantages high atom economy, environmental friendliness, excellent functional group compatibility was verified by cross-coupling variety free alcohols, oxalyl chlorides, Control experiments mechanistic studies indicate alkoxycarbonyl radical α-boryl carbocation key intermediates this transformation.

Language: Английский

Citations

0
Synthesis of 1,2-Bis- and 1,1,2-Tris-Borylalkanes under Transition Metal-Free and Solvent-Free Conditions DOI
Kiran S. Patil,

Shivakumar Reddappa,

Rakesh Kumar

et al.

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

Published: March 19, 2025

Multi(boronate) esters are useful building blocks in modern chemical synthesis. Herein, we have developed an efficient, transition metal- and solvent-free method for the regioselective boration of alkenes alkynes. The alkali metal Lewis base (NaOMe)-mediated reactions, using bis(pinacolato)diboron (B2pin2) as boron reagent, resulted diboration at room temperature triboration alkynes 60 °C to produce synthetically alkyl 1,2-bis(boronate) 1,1,2-tris(boronate) esters, respectively, excellent yields with high regioselectivity. This environmentally benign protocol demonstrates a broad substrate scope good functional group tolerance gram-scale reaction further highlights practical usefulness method. proposed pathway has been evaluated based on stoichiometric reactions DFT studies.

Language: Английский

Citations

0
Unprecedented Dual Radical Initiation in Visible-Light Photoredox-Catalyzed X–H (X = Si and B) Insertions of Sulfoxonium Ylides DOI

Mengyu Xu,

Yujing Wang, Rui Fu

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 7003 - 7014

Published: April 15, 2025

Language: Английский

Citations

0
Enantioselective Cobalt-Catalyzed Remote Hydroboration of Alkenylboronates DOI
Wenke Dong,

Zheming Liu,

Aoxuan Bai

et al.

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

Published: Feb. 14, 2025

Heteroatomic groups in alkenes typically direct thermodynamically favored chain walking of C═C bonds toward themselves, thereby facilitating C-H bond functionalization near the heteroatoms. We present herein an efficient cobalt-catalyzed contra-thermodynamic remote hydroboration alkenylboronates with pinacolborane to synthesize chiral 1,n-diboronates. This protocol features a broad substrate scope, high functional group tolerance, and excellent enantioselectivity. Mechanistic studies indicate involvement chain-walking process. Gram-scale reactions various product derivatizations further highlight its practicality.

Language: Английский

Citations

0
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