RT Journal Article
T1 Enantioselective synthesis of allylic boronates bearing a stereodefined (E)-alkenyl chloride by Cu-catalyzed borylation of allylic gem-dichlorides
A1 Chaves Pouso, Andrea
A1 Álvarez Constantino, Andrés Manuel
A1 Gómez Roibás, Patricia
A1 Fañanás-Mastral, Martín
AB Chiral α,γ-substituted allyl boron reagents are valuable tools in organic synthesis. However, asymmetric catalytic strategies for synthesising this type of compound bearing a stereodefined alkenyl chloride are underdeveloped. Here we report a copper-catalyzed enantioselective borylation of allylic gem-dichlorides that provides optically active allylic boronates bearing an (E)-configured alkenyl chloride with high levels of enantioselectivity and E-selectivity. These enantioenriched allyl boronates serve as versatile building blocks for different stereospecific reactions, including their conversion into chiral propargyl alcohols and the diastereoselective addition to ketones to afford enantioenriched allylic chlorohydrins. DFT calculations provide mechanistic insight, revealing key noncovalent interactions that rationalize the observed stereocontrol. This study expands the synthetic utility of allylic boronates and offers a mechanistically informed approach to asymmetric catalysis involving gem-dichloride substrates.
PB Royal Society of Chemistry
YR 2026
FD 2026-02-24
LK https://hdl.handle.net/10347/46808
UL https://hdl.handle.net/10347/46808
LA eng
NO Chaves-Pouso, A., Álvarez-Constantino, A. M., Gómez-Roibás, P., & Fañanás-Mastral, M. (2026). Enantioselective synthesis of allylic boronates bearing a stereodefined (E)-alkenyl chloride by Cu-catalyzed borylation of allylic gem-dichlorides. Organic chemistry frontiers : an international journal of organic chemistry, 10.1039/d6qo00061d. Advance online publication. https://doi.org/10.1039/d6qo00061d
NO Financial support from the AEI (PID2023-151875NB-I00), European Research Council (863914), Xunta de Galicia (ED431C 2022/27; Centro de investigación do Sistema universitario de Galicia accreditation 2023–2027, ED431G 2023/03), and the European Regional Development Fund (ERDF) is gratefully acknowledged. This article is dedicated to Prof. Steven V. Ley on the occasion of his 80th birthday
DS Minerva
RD 21 may 2026