Cited by Two distinct electrophiles enabled sequential dual migrations of alkynyl tetracoordinate borons

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

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

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

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

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

Modular Synthesis of Chiral 1,3-Diboronates with Differentiable Boryl Groups via Cu-Catalyzed Borylalkylation of Styrenes DOI

Guoxiang Zhang,

Quan-Hong Zhao,

Xin‐Yue Chai

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 8913 - 8924

Published: May 12, 2025

Language: Английский

Citations

Application of the Horner–Wadsworth–Emmons Olefination in the Construction of E-α,β-Unsaturated β-Boryl Nitriles DOI

Kaja Gosak,

Martin Črnugelj,

Zdenko Časar

et al.

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

Published: May 21, 2025

Herein, we describe a simple transition-metal-free synthesis of E-α,β-unsaturated β-boryl nitriles by the Horner-Wadsworth-Emmons reaction starting from potassium acyltrifluoroborates. The methodology encompasses broad range alkyl and aryl substrates. conditions are simple, products in most cases isolated with good yields as pure E isomers without column chromatography.

Language: Английский

Citations

Synthesis of chiral germanium center enabled by poly-deborylative alkylation and desymmetrization DOI

Ke Wang, Xin‐Yuan Liu, Zhe Dong

et al.

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

Published: May 30, 2025

Chiral germanium centers are historically undervalued due to their extremely limited synthetic accessibility. Although shares similar chemical properties with silicon, synthesizing chiral proves significantly more challenging. To facilitate rapid access centers, we develop two strategies: deborylative alkylation of chlorides and copper-catalyzed diol desymmetrization. The α-boryl carbanion is demonstrated be an exceptional coupling partner for chloride, yielding 1,3-prochiral diols, which subsequently undergo desymmetrization afford centers. By combining these methodologies, successfully transform simple tetrachloride into a center in merely four steps, representing significant advancement main-group element chirality. Additionally, this strategy efficiently facilitates the construction silicon-stereogenic as well. Subsequent deoxygenative cross-coupling reactions products further expand scope organogermanium chemistry, revealing entirely new possibilities.

Language: Английский

Citations

Two distinct electrophiles enabled sequential dual migrations of alkynyl tetracoordinate borons DOI

Hejun An,

Wei Zhu,

Mengwei Tan

et al.

Science China Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: June 4, 2025

Language: Английский

Citations