A Theoretical Study on the Alkylation of the Ambident Enolate from a Methyl Glycinate Schiff Base

Title
A Theoretical Study on the Alkylation of the Ambident Enolate from a Methyl Glycinate Schiff Base
Author(s)
남기평이승민
Keywords
PHASE-TRANSFER CATALYSIS; DENSITY-FUNCTIONAL THEORY; LITHIUM ENOLATE; AGGREGATION; REACTIVITY; ION
Issue Date
201208
Publisher
KOREAN CHEMICAL SOC
Citation
BULLETIN OF THE KOREAN CHEMICAL SOCIETY, v.33, no.8, pp.2711 - 2718
Abstract
The alkylation of the ambident enolates of a methyl glycinate Schiff base with ethyl chloride was studied at B3LYP and MP2 levels with 6-31+G* basis set. The free (E)-enolates and (Z)-enolate are similar in energy and geometry. The transition states for the alkylation of the free (E)/(Z)-enolate with ethyl chloride have similar energy barriers of similar to 13 kcal/mol. However, with a lithium ion, the (E)-enolate behaves as an ambident enolate and makes a cyclic lithium-complex in bidentate pattern which is more stable by 11-23 kcal/mol than the (Z)-enolate-lithium complexes. And the TS for the alkylation of (E)-enolate-lithium complex coordinated with one methyl ether is lower in energy than those from (Z)-enolate-lithium complexes by 4.3-7.3 kcal/mol. Further solvation model (SCRF-CPCM) and reaction coordinate (IRC) were studied. This theoretical study suggests that the alkylation of ambident enolates proceeds with stable cyclic bidentate complexes in the presence of metal ion and solvent.
URI
http://hdl.handle.net/YU.REPOSITORY/27484http://dx.doi.org/10.5012/bkcs.2012.33.8.2711
ISSN
0253-2964
Appears in Collections:
이과대학 > 화학생화학부 > Articles
문과대학 > 중국언어문화학과 > Articles
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