Premium
Transition Metal‐Catalyzed Reactions of Methylenecyclopropanes
Author(s) -
Nakamura Itaru,
Yamamoto Yoshinori
Publication year - 2002
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/1615-4169(200202)344:2<111::aid-adsc111>3.0.co;2-0
Subject(s) - hydroamination , chemistry , hydrosilylation , cycloaddition , reductive elimination , allylic rearrangement , catalysis , transition metal , hydride , medicinal chemistry , bimetallic strip , palladium , metal , organic chemistry
Abstract The transition metal‐catalyzed formal [3+2] cycloaddition of methylenecyclopropanes with unsaturated compounds X=Y, such as alkenes, aldehydes, and imines, gives five‐membered carbocycles or heterocycles. The Heck‐type reaction of R‐Pd‐X with the exomethylene part of methylenecyclopropanes gives the corresponding cyclopropylcarbinylpalladium complexes which undergo further transformations through typical palladium reactions such as β‐hydride elimination or reductive elimination of Pd(0). Hydrostannation, hydrosilylation, hydrocarbonation, hydroamination, and hydroalkoxylation of methylenecyclopropanes proceed through the addition of the metal hydrides (H‐M) and pronucleophiles (H‐Nu) to the olefinic part, and the resulting intermediates are converted to the allylic products in which the homologation by three carbon atoms takes place from M and Nu, respectively. Bismetallation produces 1,3‐bimetallic derivatives through metallacyclobutane intermediates.