Catalytic Cyclopropanation of Alkenes via (2-Furyl)carbene Complexes from 1-Benzoyl-cis-1-buten-3-yne with Transition Metal Compounds
- 5 February 2004
- journal article
- research article
- Published by American Chemical Society (ACS) in The Journal of Organic Chemistry
- Vol. 69 (5) , 1557-1564
- https://doi.org/10.1021/jo0352732
Abstract
The reaction of alkenes with conjugated ene-yne-ketones, such as 1-benzoyl-2-ethynylcycloalkenes, with a catalytic amount of Cr(CO)(5)(THF) gave 5-phenyl-2-furylcyclopropane derivatives in good yields. The key intermediate of this cyclopropanation is a (2-furyl)carbene complex generated by a nucleophilic attack of carbonyl oxygen to an internal alkyne carbon in pi-alkyne complex or sigma-vinyl cationic complex. A wide range of late transition metal compounds, such as [RuCl(2)(CO)(3)](2), [RhCl(cod)](2), [Rh(OAc)(2)](2), PdCl(2), and PtCl(2), also catalyzes the cyclopropanation of alkenes with ene-yne-ketones effectively. When the reactions were carried out with dienes as a carbene acceptor, the more substituted or more electron-rich alkene moiety was selectively cyclopropanated with the (2-furyl)carbenoid intermediate.Keywords
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