期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 135, 期 45, 页码 16853-16864出版社
AMER CHEMICAL SOC
DOI: 10.1021/ja403076u
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资金
- NIGMS NIH HHS [GM 077167, R01 GM077379, R01 GM039764, R01 GM077167, GM077379, GM39764, R37 GM039764] Funding Source: Medline
A combination of X-ray crystallography, Li-6, N-15, and C-13 NMR spectroscopies, and density functional theory computations affords insight into the structures and reactivities of intervening aggregates underlying highly selective asymmetric alkylations of carboxylic acid dianions (enediolates) mediated by the dilithium salt of a C-2-symmetric chiral tetraamine. Crystallography shows a trilithiated n-butyllithium-dilithiated amide that has dimerized to a hexalithiated form. Spectroscopic studies implicate the non-dimerized trilithiated mixed aggregate. Reaction of the dilithiated amide with the dilithium enediolate derived from phenylacetic acid affords a tetralithio aggregate comprised of the two dianions in solution and the dimerized octalithio form in the solid state. Computational studies shed light on the details of the solution structures and afford a highly predictive stereochemical model.
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