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. 2024 Feb 16;14(7):1848-1853.
doi: 10.1039/d3cy01702h. eCollection 2024 Apr 2.

Formoxyboranes as hydroborane surrogates for the catalytic reduction of carbonyls through transfer hydroboration

Gabriel Durin  1 , R Martin Romero  1 , Timothé Godou  1 , Clément Chauvier  1 , Pierre Thuéry  1 , Emmanuel Nicolas  1 , Thibault Cantat  1
Affiliations

Formoxyboranes as hydroborane surrogates for the catalytic reduction of carbonyls through transfer hydroboration

Gabriel Durin et al. Catal Sci Technol. .

Abstract

A new class of Lewis base stabilized formoxyboranes demonstrates the feasibility of catalytic transfer hydroboration. In the presence of a ruthenium catalyst, they have shown broad applicability for reducing carbonyl compounds. Various borylated alcohols are obtained in high selectivity and yields up to 99%, tolerating several functional groups. Computational studies enabled to propose a mechanism for this transformation, revealing the role of the ruthenium catalyst and the absence of hydroborane intermediates.

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Conflict of interest statement

There are no conflicts to declare.

Figures

Scheme 1
Scheme 1. Examples of hydroboration and transfer hydroboration of unsaturated functional groups.
Scheme 2
Scheme 2. Synthesis of formoxyboranes from hydroboranes and formic acid.
Scheme 3
Scheme 3. Synthesis of formoxyboranes from chloroborane and sodium formate.
Scheme 4
Scheme 4. Scope of the catalytic transfer hydroboration of carbonyl compounds.
Scheme 5
Scheme 5. Plausible precatalyst pathway from 2a to 2b (top) and precatalyst test with 2b (bottom).
Scheme 6
Scheme 6. Computed mechanism for the catalytic transfer of hydroboration of acetophenone 3a with 1b catalyzed by Ia at B3LYP-D3/Def2SVP level of theory and SMD model to account for solvent effect (C6D6).
See this image and copyright information in PMC

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