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Updated: Jan 7, 2026

Efficient Synthesis of All-Carbon Quaternary Centers via the Conjugate Addition of Functionalized Monoorganozinc Bromides

Efficient Synthesis of All-Carbon Quaternary Centers via the Conjugate Addition of Functionalized Monoorganozinc Bromides

Published on: May 26, 2019

メカノケミカルワンポットバルビエ/シモンズ・スミス反応：逐次亜鉛活性化による

Asma A Alharthi^1,2, Benson M Kariuki¹, Louis C Morrill^1,3

¹Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Main Building, Park Place, Cardiff, CF10 3AT, UK. lcm71@bath.ac.uk.

Chemical communications (Cambridge, England)

|December 23, 2025

Abstract:

We report a mechanochemical one-pot Barbier/Simmons-Smith reaction enabled by ball-milling-mediated activation of zinc(0). This operationally simple method generates organozinc intermediates in situ and uses them sequentially in allylation and cyclopropanation without intermediate work-up. The protocol tolerates a broad range of ketones, exhibits selectivity over other carbonyl groups, and is compatible with various physical forms of zinc metal. In selected cases, the reaction proceeds with markedly enhanced diastereoselectivity under minimal-solvent milling conditions and was demonstrated on a gram scale using standard ball-milling equipment. Comparative studies show advantages over conventional solution and neat conditions, highlighting how mechanochemistry can uniquely enable tandem organometallic processes as for C-C bond construction.

キーワード:

メカノケミストリーワンポット反応バルビエ反応シモンズ・スミス反応有機亜鉛 C-C結合形成ボールミル逐次反応不斉合成

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Preparation and Use of Samarium Diiodide SmI2 in Organic Synthesis: The Mechanistic Role of HMPA and NiII Salts in the Samarium Barbier Reaction

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