In:
European Journal of Organic Chemistry, Wiley, Vol. 2008, No. 19 ( 2008-07), p. 3363-3368
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)
Type of Medium:
Online Resource
ISSN:
1434-193X
,
1099-0690
DOI:
10.1002/ejoc.v2008:19
DOI:
10.1002/ejoc.200800256
Language:
English
Publisher:
Wiley
Publication Date:
2008
detail.hit.zdb_id:
1475010-7
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