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Reactions of Carbenes with Ethers: The Role of Noncovalent Interactions

✍ Scribed by Jean-Luc Mieusset; Udo H. Brinker

Publisher
John Wiley and Sons
Year
2008
Tongue
English
Weight
309 KB
Volume
2008
Category
Article
ISSN
1434-193X

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✦ Synopsis

Abstract

The influence of ethers upon carbenes has been investigated computationally by the B3LYP, MP2, and MPWB1K methods. Ylide formation is only obtained with reactive‐electrophilic carbenes like cyclopentadienylidene, whereas more nucleophilic carbenes like cyclopent‐2‐enylidene associate by interactions of lone pairs of carbon and oxygen atoms with C–H bonds. Between the stabilized‐electrophilic dichlorocarbene and the oxygen lone pairs, only weak complexes are formed. Furthermore, the mechanism of the C–H insertion of dichlorocarbene into bicyclic ethers containing a three‐membered ring has been explored. The experimental data confirm the computational results. The insertion occurs easily into the α‐position of the oxygen atom in secondary ethers but not into the methyl group of methyl ethers. In all cases, insertion into the α‐position of a cyclopropane ring is not competitive.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

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