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Enediolate-dilithium amide mixed aggregates in the enantioselective alkylation of arylacetic acids: structural studies and a stereochemical model.
Ma, Yun; Stivala, Craig E; Wright, Ashley M; Hayton, Trevor; Liang, Jun; Keresztes, Ivan; Lobkovsky, Emil; Collum, David B; Zakarian, Armen.
Afiliação
  • Ma Y; Department of Chemistry and Biochemistry, University of California, Santa Barbara , California 93106, United States.
J Am Chem Soc ; 135(45): 16853-64, 2013 Nov 13.
Article em En | MEDLINE | ID: mdl-23654300
ABSTRACT
A combination of X-ray crystallography, (6)Li, (15)N, and (13)C 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 C2-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.
Assuntos

Texto completo: 1 Base de dados: MEDLINE Assunto principal: Compostos Organometálicos / Amidas / Lítio / Acetatos Tipo de estudo: Prognostic_studies Idioma: En Ano de publicação: 2013 Tipo de documento: Article

Texto completo: 1 Base de dados: MEDLINE Assunto principal: Compostos Organometálicos / Amidas / Lítio / Acetatos Tipo de estudo: Prognostic_studies Idioma: En Ano de publicação: 2013 Tipo de documento: Article