114646-77-4Relevant articles and documents
Ene di- and trimerization of 1-methyl-2-phenylcyclopropene
Lin, Hung-Chun,Tsai, Ru-Ting,Wu, Hsiao-Pin,Lee, Hsin-Yi,Lee, Gon-Ann
, p. 184 - 191 (2015/12/23)
1,2-Disubstituted cyclopropene, 1-methyl-2-phenylcyclopropene (18), was generated by bromo-lithium exchange of 1-bromo-2-phenylcyclopropene followed by treatment with methyl iodide. Compound 18 was oxidized by oxygen to give the α,β-unsaturated carbonyl product 25 and diketone 27 and the tautomeric, β-hydroxyl-α,β-unsaturated ketone 28. However, compound 28 reacted further with the cyclopropene 18 in a retro-Claisen-like reaction to generate adduct 26. Furthermore, compound 18 underwent ene dimerization in neat condition to form the endo-dimer 40 and exo-dimer 41 followed by oxidization with oxygen to give aldehyde 39. It is noteworthy that the endo-dimer 40 and exo-dimer 41 could be trapped with thiophenol to give adduct 42 and 43. In addition, the ene reaction of exo-dimer 41 with monomer 18 gave an exo-exo ene trimer 46 through an exo-transition state which was also trapped by thiophenol to give adducts 44 and 45.
Asymmetric synthesis of 4,4-disubstituted-2-cyclohexen-1-ones from a chiral 2-(trimethylsilyl)benzamide
Schultz, Arthur G.,Pettus, Liping
, p. 5433 - 5436 (2007/10/03)
Birch reduction-alkylation of the chiral 2-(trimethylsilyl)benzamide 4 provides 1,4-cyclohexadienes 5b-5e with diastereomer ratios of >100:1. The conversions of 5b-5e to the 4,4-disubstituted-2-cyclohexen-1-ones 8b-8e are described.