Intramolecular Asymmetric Cyclopropanation Using Air-Stable Alkylboronic Esters

Luca Vedani; Manuel Gnägi-Lux; Fabrice Dénès; Philippe Renaud

doi:10.1055/a-2158-8752

Synlett, Table of Contents

Synlett 2023; 34(18): 2232-2238
DOI: 10.1055/a-2158-8752

cluster

Modern Boron Chemistry: 60 Years of the Matteson Reaction

Intramolecular Asymmetric Cyclopropanation Using Air-Stable Alkylboronic Esters

Luca Vedani‡

,

Manuel Gnägi-Lux‡

,

Fabrice Dénès ∗

,

Philippe Renaud ∗

Abstract

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Abstract

The preparation of polysubstituted bicyclo[3.1.0]hexanes starting from air-stable substituted pent-4-en-1-ylboronic acid esters has been investigated. The method involves a Matteson homologation with LiCHCl₂, leading to 1-chlorohex-5-en-1-ylboronic acid ester intermediates. The subsequent intramolecular cyclopropanation step was performed in a one-pot process. With pinacol boronic esters, the cyclopropanation step was either performed thermally at 140 °C or at 70 °C after in situ transesterification to form a catechol boronic ester. This last approach is suitable for the preparation of enantioenriched bicyclo[3.1.0]hexanes using either chiral-auxiliary control or by taking advantage of the sparteine-controlled enantioselective boroalkylation of alcohols.

Key words

cyclopropanation - boronic esters - Matteson homologation - chloroalkylboronates - bicyclo[3.1.0]hexanes - fused cyclopropanes

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References

References and Notes
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