Synthetic approaches to phomactins: on the stereoselectivity of some [2,3]-Wittig rearrangements

Timothy J. Blackburn, Michael J. Kilner, Eric J. Thomas

    Research output: Contribution to journalArticlepeer-review

    Abstract

    On treatment with n-butyllithium, 4-alkoxy- and 4-silyloxy-2-(tributylstannylmethoxymethyl)-1,6-dimethyl-1-(phenylsulfonylmethyl)cyclohex-2-enes undergo tin-lithium exchange followed by [2,3]-Wittig rearrangements to give 3-alkoxy- and 3-silyloxy-2-hydroxymethyl-5,6-dimethyl-1-methylene-6-(phenylsulfonylmethyl)cyclohexanes in which the 2-hydroxymethyl and 6-phenylsulfonylmethyl residues are cis-disposed about the six-membered ring. In contrast, the corresponding 1-(phenylsulfanylmethyl)cyclohexenes give mainly methylenecyclohexanes with the 2-hydroxymethyl and 6-phenylsulfanylmethyl groups trans-disposed about the six-membered ring. This stereoselectivity is independent of the nature of the alkoxy- or silyloxy-substituent and configuration at C4. The 3-tert-butyldiphenylsilyloxy-1-methylene-6-(phenylsulfonylmethyl)cyclohexane was converted into a macrocyclic precursor of the phomactins.

    Original languageEnglish
    Article number26607
    Pages (from-to)7293-7309
    Number of pages17
    JournalTetrahedron
    Volume71
    Issue number39
    DOIs
    Publication statusPublished - 17 Aug 2015

    Keywords

    • Macrocycle
    • Natural products
    • Stereoselectivity
    • Total synthesis
    • [2,3]-Wittig rearrangements

    Fingerprint

    Dive into the research topics of 'Synthetic approaches to phomactins: on the stereoselectivity of some [2,3]-Wittig rearrangements'. Together they form a unique fingerprint.

    Cite this