Theoretical insight into the influences of alpha-substituents in aliphatic aldehydes on the enantioselectivities of aldol reactions.
Chirality. 2008 Jan; 20(1):54-61.C

Abstract

Density functional theory has been applied to study the influences of alpha-substituents in aliphatic aldehydes on the enantioselectivities of the (S)-proline-catalyzed direct aldol reactions. Reaction scenarios of three kinds of aliphatic aldehydes were investigated. Four transition states associated with the stereocontrolling step of each reaction have been obtained. They are corresponding to the syn and anti arrangements of enamine intermediates and the si and re attacks to the carbonyl group of an aldehyde. The solvent effect of DMSO was investigated using self-consistent reaction field method based on the polarizable continuum model. The computed energies of transition states explain the origin of the catalysis and enantioselectivities for these (S)-proline-catalyzed aldol reactions and reveal the influences of alpha-substituents in aliphatic aldehydes on the enantioselectivities of these reactions.

Authors+Show Affiliations

Fan JF

Key Laboratory of Organic Synthesis of Jiangsu Province, Faculty of Chemistry and Chemical Engineering, Suzhou University, Suzhou, People's Republic of China. jffan1965@163.com

He LJ

No affiliation info available

Sun YP

No affiliation info available

Pub Type(s)

Journal Article

Language

eng

PubMed ID

17999437

Citation

Fan, Jian-Fen, et al. "Theoretical Insight Into the Influences of Alpha-substituents in Aliphatic Aldehydes On the Enantioselectivities of Aldol Reactions." Chirality, vol. 20, no. 1, 2008, pp. 54-61.

Fan JF, He LJ, Sun YP. Theoretical insight into the influences of alpha-substituents in aliphatic aldehydes on the enantioselectivities of aldol reactions. Chirality. 2008;20(1):54-61.

Fan, J. F., He, L. J., & Sun, Y. P. (2008). Theoretical insight into the influences of alpha-substituents in aliphatic aldehydes on the enantioselectivities of aldol reactions. Chirality, 20(1), 54-61.

Fan JF, He LJ, Sun YP. Theoretical Insight Into the Influences of Alpha-substituents in Aliphatic Aldehydes On the Enantioselectivities of Aldol Reactions. Chirality. 2008;20(1):54-61. PubMed PMID: 17999437.

* Article titles in AMA citation format should be in sentence-case

TY - JOUR T1 - Theoretical insight into the influences of alpha-substituents in aliphatic aldehydes on the enantioselectivities of aldol reactions. AU - Fan,Jian-Fen, AU - He,Liang-Jun, AU - Sun,Yun-Peng, PY - 2007/11/14/pubmed PY - 2007/11/14/medline PY - 2007/11/14/entrez SP - 54 EP - 61 JF - Chirality JO - Chirality VL - 20 IS - 1 N2 - Density functional theory has been applied to study the influences of alpha-substituents in aliphatic aldehydes on the enantioselectivities of the (S)-proline-catalyzed direct aldol reactions. Reaction scenarios of three kinds of aliphatic aldehydes were investigated. Four transition states associated with the stereocontrolling step of each reaction have been obtained. They are corresponding to the syn and anti arrangements of enamine intermediates and the si and re attacks to the carbonyl group of an aldehyde. The solvent effect of DMSO was investigated using self-consistent reaction field method based on the polarizable continuum model. The computed energies of transition states explain the origin of the catalysis and enantioselectivities for these (S)-proline-catalyzed aldol reactions and reveal the influences of alpha-substituents in aliphatic aldehydes on the enantioselectivities of these reactions. SN - 0899-0042 UR - https://www.unboundmedicine.com/medline/citation/17999437/Theoretical_insight_into_the_influences_of_alpha_substituents_in_aliphatic_aldehydes_on_the_enantioselectivities_of_aldol_reactions_ DB - PRIME DP - Unbound Medicine ER -

Tags

Theoretical insight into the influences of alpha-substituents in aliphatic aldehydes on the enantioselectivities of aldol reactions.Chirality. 2008 Jan; 20(1):54-61.C