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ChemInform Abstract: Enantiospecific Preparation of gem-Dimethylcyclopropane Fused Cycloheptanes via Valence Tautomerization of 3,4-Homotropilidene under Thermodynamic and Kinetic Control.

✍ Scribed by T. SUGIMURA; T. FUTAGAWA; T. KATAGIRI; N. NISHIYAMA; A. TAI


Publisher
John Wiley and Sons
Year
2010
Weight
35 KB
Volume
28
Category
Article
ISSN
0931-7597

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✦ Synopsis


Enantiospecific Preparation of gem-Dimethylcyclopropane Fused Cycloheptanes via Valence Tautomerization of 3,4-Homotropilidene under Thermodynamic and Kinetic Control. -Regioselective addition of dichlorocarbene to the 4-alkoxy-8,8-dimethylcycloheptatriene (I) followed by a reductive rearrangement provides an entry to the 3,4-homotropylidene derivatives (IV), (V), and (VI). Using chiral alkoxysubstituted educts such as (VII), the stereospecificity of the rearrangement allows the preparation of optically active products (XII) and (XIII).