Substituent Effects in Samarium Diiodide-Induced 6-trig Cyclizations of γ-Arylketones to Functionalized Hexahydronaphthalene Derivatives

Mathias Berndt; Hans-Ulrich Reissig

doi:10.1055/s-2001-16051

Synlett 2001; 2001(8): 1290-1292
DOI: 10.1055/s-2001-16051

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Substituent Effects in Samarium Diiodide-Induced 6-trig Cyclizations of γ-Arylketones to Functionalized Hexahydronaphthalene Derivatives

Mathias Berndt^* , Hans-Ulrich Reissig

^*Institut für Chemie - Organische Chemie, Freie Universität Berlin, Takustr. 3, 14195 Berlin, Germany; Fax + 49(0)30/838-5 53 67; E-mail: hans.reissig@chemie.fu-berlin.de

Abstract

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The samarium diiodide-induced 6-trig cyclizations of substituted γ-arylketones 1, 4, 5, 9, 11, and 14 are strongly influenced by substituents of the aryl group. Whereas para-methoxy derivative 5 as well as ortho- and para-cyano derivatives 9 and 14 provided the expected functionalized hexahydronaphthalene derivatives 6 (together with 7), 10, and 15 in moderate to good yields, ortho-methoxy compound 1 was a poor substrate and meta-methoxy derivative 4 did not undergo cyclization at all. The behavior of meta-cyano compound 11 was exceptional since the intermediate cyclohexadienyl "carbanion" was sufficiently stable to be trapped by electrophiles furnishing adducts such as 17 and 18 in moderate yields.

samarium(II) iodide - electron transfer - ketyl - radicals - hexahydronaphthalenes

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