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Vinylogous Nicholas reactions in the synthesis of bi- and tricyclic cycloheptynedicobalt complexes†
Izabela Kolodziej,James R. Green
Organic & Biomolecular Chemistry Pub Date : 09/07/2015 00:00:00 , DOI:10.1039/C5OB01684C
Abstract

The Lewis acid mediated intramolecular Nicholas reactions of allylic acetate enyne-Co2(CO)6 complexes afford cycloheptenyne-Co2(CO)6 complexes in three manifestations. Electron rich aryl substituted alkyne complexes give tricyclic 6,7,x-benzocycloheptenyne complexes, with x = 5, 6, or 7. Allylsilane substituted complexes afford exo methylene bicyclic x,7-cycloheptenyne complexes (x = 6,7). The allyl acetate function may also be replaced by a benzylic acetate, to afford dibenzocycloheptyne-Co2(CO)6 complexes. Following reductive complexation, the methodology may be applied to the synthesis of the icetexane diterpene carbon framework.

Graphical abstract: Vinylogous Nicholas reactions in the synthesis of bi- and tricyclic cycloheptynedicobalt complexes
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