In:
Bulletin of the Chemical Society of Japan, Oxford University Press (OUP), Vol. 74, No. 2 ( 2001-02-01), p. 245-254
Abstract:
Structures and reactions of CH3OCH2M (M = Li, Na, K) were investigated in a theoretical manner. CH3OCH2M has the acute bond angle of ∠M-C-O due to a strong coordination of the oxygen to the alkali metals. The nucleophilic substitution reaction of the substrate CH3OCH2Li by the nucleophile CH3OCH2Li is more preferred than the carbene generation by α-elimination and a nucleophilic substitution of CH3OCH2Li by CH3Li. The resulting 2-methoxyethyllithium readily liberated lithium methoxide to afford ethylene, which added to the anion species to give an ethylated product. Among the CH3OCH2M (M = Li, Na, K), CH3OCH2K is the most nucleophilic, due to the high σC–K level, while CH3OCH2Li is the most nucleophilic because of the lowest σ*C–O level. This supports a previously proposed mechanism for the ethylation of indole derivatives by methyl ethers in the presence of BuLi - t-BuOK.
Type of Medium:
Online Resource
ISSN:
0009-2673
,
1348-0634
Language:
English
Publisher:
Oxford University Press (OUP)
Publication Date:
2001
detail.hit.zdb_id:
2041163-7
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