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Dimerization Behavior of Substituted Bicyclo[3.1.0]hex‐1‐ene Derivatives
Author(s) -
Zheng JunCheng,
Liu Huaqing,
Lee NamKyu,
Lee Daesung
Publication year - 2014
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201301575
Subject(s) - alkene , chemistry , bicyclic molecule , ene reaction , moiety , substituent , lithium (medication) , stereochemistry , concerted reaction , medicinal chemistry , organic chemistry , catalysis , medicine , endocrinology
The different reaction profiles of lithium trimethylsilyldiazomethane with various 4‐alkenyl ketones are described. It was found that the individual steps along the reaction pathway including a Brook rearrangement, elimination of lithium trimethylsilanolate to form alkylidene carbenes, and their addition to an alkene to form strained bicyclo[3.1.0]hex‐1‐ene derivatives were significantly affected by the substituents near or on the alkene moiety. Especially, the dimerization of bicyclo[3.1.0]hex‐1‐enes depends critically on the substituent pattern of the alkene, which controls the reaction to proceed in a concerted or a stepwise manner. On the basis of X‐ray diffraction analysis, the dimers, which are of unprecedented structural complexity, were unambiguously elucidated.