Can relief of ring-strain in a cyclopropylmethyllithium drive the Brook rearrangement?

Jonathan Clayden, David W. Watson, Mark Chambers

    Research output: Contribution to journalArticlepeer-review

    Abstract

    α-Cyclopropyl-α-trialkylsilyl alkoxides were formed either by addition of cyclopropyllithiums to acylsilanes or by addition of organolithiums to a cyclopropylformylsilane. [1,2]-Brook rearrangement led to α-silyloxy organolithiums which on warming underwent cyclopropane ring opening and [1,5]-retro-Brook rearrangement to yield γ-silyl ketones. Despite the favourability of the cyclopropane ring opening, the Brook rearrangement still required the presence of an anion stabilising group to proceed. β-Silylketones were similarly formed by Brook-retro-Brook rearrangement on warming acylsilanes with a vinyllithium. © 2004 Elsevier Ltd. All rights reserved.
    Original languageEnglish
    Pages (from-to)3195-3203
    Number of pages8
    JournalTetrahedron
    Volume61
    Issue number13
    DOIs
    Publication statusPublished - 28 Mar 2005

    Keywords

    • Anion
    • Cyclopropane
    • Organolithium
    • Rearrrangement
    • Silicon

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