Enantioselective homoallyl-cyclopropanation of dibenzylideneacetone by modified allylindium halide reagents--rapid access to enantioenriched 1-styryl-norcarene

GC Lloyd-Jones, PD Wall, JL Slaughter, AJ Parker, DP Laffan

Research output: Contribution to journalArticle (Academic Journal)peer-review

19 Citations (Scopus)

Abstract

Dibenzylideneacetone (8) reacts with in situ-generated allylindium halide reagents to yield the product of a homoallyl-cyclopropanation reaction: 2-(3''-butenyl)-1,1-bis[(E)-2'-phenylethenyl]cyclopropane (9), which proceeds via step-wise cleavage of the CO bond and delivery of two allyl fragments from the reagent. A range of enantiomerically enriched ligands have been tested as stoichiometric asymmetric modifiers for this process. Enantiopure compounds such as cinchona alkaloids, ephedra, aminoalcohols and tartaric acid derivatives, which have proven of utility as asymmetric modifiers for the indium-mediated allylation of aldehydes and ketones, were very inefficient in the process 8-->9. However, mandelic acid derivatives, in particular mandelates, were found to be of significant potential. The absolute stereochemistry of the cyclopropane 9 has been determined by degradation to 1,1-dicarboxymethyl-2-butylcyclopropane, converging with an independent enantioselective synthesis starting from hexene. Under optimised conditions, viz. using allylindium iodide reagents and working-up with aqueous Na2SO3 to avoid iodine-mediated polymerisation, (S)-9 can be generated in 86% yield and with (S)-methyl mandelate as modifier useful enantiopurity (94/6 er) was observed. The cyclopropane product ((S)-9) undergoes RCM using standard conditions to afford a norcarene unit ((1S,6S)-1-(E)-2'-(phenylethenyl)-bicyclo[4.1.0]hept-2-ene) without loss of enantiopurity.
Translated title of the contributionEnantioselective homoallyl-cyclopropanation of dibenzylideneacetone by modified allylindium halide reagents--rapid access to enantioenriched 1-styryl-norcarene
Original languageEnglish
Pages (from-to)11402 - 11412
Number of pages11
JournalTetrahedron
Volume62 (49)
DOIs
Publication statusPublished - Dec 2006

Bibliographical note

Publisher: Elsevier

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