Electrooxidative Activation of B−B Bond in B₂cat₂: Access to gem‐Diborylalkanes via Paired Electrolysis

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(14)

Published: Feb. 1, 2023

This report describes the unprecedented electrooxidation of a solvent (e.g., DMF)-ligated B2 cat2 complex, whereby solvent-stabilized boryl radical is formed via quasi-homolytic cleavage B-B bond in DMF-ligated cation. Cyclic voltammetry and density functional theory provide evidence to support this novel activation strategy. Furthermore, strategy for electrochemical gem-diborylation gem-bromides paired electrolysis developed first time, affording range versatile gem-diborylalkanes, which are widely used synthetic society. Notably, reaction approach scalable, transition-metal-free, requires no external activator.

Language: Английский

---

Stereoselective Access to Tetra‐ and Tri‐Substituted Fluoro‐ and Chloro‐Borylalkenes via Boron‐Wittig Reaction

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(41)

Published: Aug. 23, 2022

Reported herein is the efficient synthesis of tetra- and tri-substituted (Z)-fluoro- (Z)-chloro-borylalkenes by Boron-Wittig reaction ketones aldehydes with bench-top stable halo-diborylmethanes. The substrate scope broad proceeds from a diverse range including biologically relevant molecules fluoro- or chloro-diborylmethanes, providing in good yields high stereoselectivity. utilities obtained are highlighted further modifications to afford fluoroalkene derivatives all-carbon substituted alkene.

Language: Английский

---

Selective Formal Carbene Insertion into Carbon‐Boron Bonds of Diboronates byN‐Trisylhydrazones

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 62(9)

Published: Dec. 28, 2022

Bisborylalkanes play important roles in organic synthesis as versatile bifunctional reagents. The two boron moieties these compounds can be selectively converted into other functional groups through cross-coupling, oxidation or radical reactions. Thus, the development of efficient methods for synthesizing bisborylalkanes is highly demanded. Herein we report a new strategy to access reaction N-trisylhydrazones with diboronate, which bis(boryl) methane transformed 1,2-bis(boronates) via formal carbene insertion. Since readily derived from corresponding aldehydes, this represents practical 1,2-diboronates broad substrate scope. Mechanistic studies reveal an unusual neighboring group effect 1,1-bis(boronates), accounts observed regioselectivity when unsymmetric 1,1-diboronates are applied.

Language: Английский

---

Electrooxidative Activation of B−B Bond in B₂cat₂: Access to gem‐Diborylalkanes via Paired Electrolysis

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 135(14)

Published: Feb. 1, 2023

Abstract This report describes the unprecedented electrooxidation of a solvent (e.g., DMF)‐ligated B 2 cat complex, whereby solvent‐stabilized boryl radical is formed via quasi‐homolytic cleavage B−B bond in DMF‐ligated cation. Cyclic voltammetry and density functional theory provide evidence to support this novel activation strategy. Furthermore, strategy for electrochemical gem ‐diborylation ‐bromides paired electrolysis developed first time, affording range versatile ‐diborylalkanes, which are widely used synthetic society. Notably, reaction approach scalable, transition‐metal‐free, requires no external activator.

Language: Английский

---

Stereoselective Access to Tetra‐ and Tri‐Substituted Fluoro‐ and Chloro‐Borylalkenes via Boron‐Wittig Reaction

Angewandte Chemie, Journal Year: 2022, Volume and Issue: 134(41)

Published: Aug. 23, 2022

Abstract Reported herein is the efficient synthesis of tetra‐ and tri‐substituted ( Z )‐fluoro‐ )‐chloro‐borylalkenes by Boron–Wittig reaction ketones aldehydes with bench‐top stable halo‐diborylmethanes. The substrate scope broad proceeds from a diverse range including biologically relevant molecules fluoro‐ or chloro‐diborylmethanes, providing in good yields high stereoselectivity. utilities obtained are highlighted further modifications to afford fluoroalkene derivatives all‐carbon substituted alkene.

Language: Английский

---

Selective Formal Carbene Insertion into Carbon‐Boron Bonds of Diboronates byN‐Trisylhydrazones

Angewandte Chemie, Journal Year: 2022, Volume and Issue: 135(9)

Published: Dec. 28, 2022

Abstract Bisborylalkanes play important roles in organic synthesis as versatile bifunctional reagents. The two boron moieties these compounds can be selectively converted into other functional groups through cross‐coupling, oxidation or radical reactions. Thus, the development of efficient methods for synthesizing bisborylalkanes is highly demanded. Herein we report a new strategy to access reaction N ‐trisylhydrazones with diboronate, which bis(boryl) methane transformed 1,2‐bis(boronates) via formal carbene insertion. Since readily derived from corresponding aldehydes, this represents practical 1,2‐diboronates broad substrate scope. Mechanistic studies reveal an unusual neighboring group effect 1,1‐bis(boronates), accounts observed regioselectivity when unsymmetric 1,1‐diboronates are applied.

Language: Английский

---