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

Lookup NU author(s): Dr Tim Blackburn


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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.

Publication metadata

Author(s): Blackburn T, Kilner M, Thomas E

Publication type: Article

Publication status: Published

Journal: Tetrahedron

Year: 2015

Volume: 71

Issue: 39

Pages: 7293-7309

Print publication date: 30/09/2015

Online publication date: 10/04/2015

Acceptance date: 02/04/2015

ISSN (print): 0040-4020

Publisher: Elsevier


DOI: 10.1016/j.tet.2015.04.005


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