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Density functional study of organocatalytic cross-aldol reactions between two aliphatic aldehydes: insight into their functional differentiation and origins of chemo- and stereoselectivities.
J Phys Chem A. 2013 Apr 04; 117(13):2862-72.JP

Abstract

The chemo-, diastereo-, and enantioselectivities in proline and axially chiral amino sulfonamide-catalyzed direct aldol reactions between two enolizable aldehydes with different electronic nature have been studied with the aid of density functional theory (DFT) method. The potential energy profiles for the enamine formation between each aliphatic aldehyde and the catalyst confirm that two subject catalysts can successfully differentiate between 3-methylbutanal as an enamine component and α-chloroaldehydes as a carbonyl component. Transition states associated with the stereochemistry-determining C-C bond-forming step with the enamine intermediate addition to the aldehyde acceptor for proline and chiral amino sulfonamide-promoted aldol reactions are reported. DFT calculations not only provide a good explanation for the formation of the sole cross-aldol product between two aliphatic aldehydes both bearing α-methylene protons but also well reproduce the opposite syn vs anti diastereoselectivities in the chiral amino sulfonamide and proline-catalyzed aldol reactions.

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Publisher Full Text (DOI)

Authors+Show Affiliations

Fu A
Institute for Computational Science and Engineering, Laboratory of New Fiber Materials and Modern Textile, The Growing Base for State Key Laboratory, Qingdao University, Qingdao 266071, China. apfu@qdu.edu.cn
Zhao C
No affiliation info available
Li H
No affiliation info available
Tian F
No affiliation info available
Yuan S
No affiliation info available
Duan Y
No affiliation info available
Wang Z
No affiliation info available

MeSH

AldehydesAminesCatalysisComputer SimulationModels, MolecularProlineQuantum TheoryStereoisomerismThermodynamics

Pub Type(s)

Journal Article
Research Support, Non-U.S. Gov't

Language

eng

PubMed ID

23442005

Citation

Fu, Aiping, et al. "Density Functional Study of Organocatalytic Cross-aldol Reactions Between Two Aliphatic Aldehydes: Insight Into Their Functional Differentiation and Origins of Chemo- and Stereoselectivities." The Journal of Physical Chemistry. A, vol. 117, no. 13, 2013, pp. 2862-72.
Fu A, Zhao C, Li H, et al. Density functional study of organocatalytic cross-aldol reactions between two aliphatic aldehydes: insight into their functional differentiation and origins of chemo- and stereoselectivities. J Phys Chem A. 2013;117(13):2862-72.
Fu, A., Zhao, C., Li, H., Tian, F., Yuan, S., Duan, Y., & Wang, Z. (2013). Density functional study of organocatalytic cross-aldol reactions between two aliphatic aldehydes: insight into their functional differentiation and origins of chemo- and stereoselectivities. The Journal of Physical Chemistry. A, 117(13), 2862-72. https://doi.org/10.1021/jp3126363
Fu A, et al. Density Functional Study of Organocatalytic Cross-aldol Reactions Between Two Aliphatic Aldehydes: Insight Into Their Functional Differentiation and Origins of Chemo- and Stereoselectivities. J Phys Chem A. 2013 Apr 4;117(13):2862-72. PubMed PMID: 23442005.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Density functional study of organocatalytic cross-aldol reactions between two aliphatic aldehydes: insight into their functional differentiation and origins of chemo- and stereoselectivities. AU - Fu,Aiping, AU - Zhao,Chengyan, AU - Li,Hongliang, AU - Tian,Fenghui, AU - Yuan,Shuping, AU - Duan,Yunbo, AU - Wang,Zonghua, Y1 - 2013/03/21/ PY - 2013/2/28/entrez PY - 2013/2/28/pubmed PY - 2013/9/14/medline SP - 2862 EP - 72 JF - The journal of physical chemistry. A JO - J Phys Chem A VL - 117 IS - 13 N2 - The chemo-, diastereo-, and enantioselectivities in proline and axially chiral amino sulfonamide-catalyzed direct aldol reactions between two enolizable aldehydes with different electronic nature have been studied with the aid of density functional theory (DFT) method. The potential energy profiles for the enamine formation between each aliphatic aldehyde and the catalyst confirm that two subject catalysts can successfully differentiate between 3-methylbutanal as an enamine component and α-chloroaldehydes as a carbonyl component. Transition states associated with the stereochemistry-determining C-C bond-forming step with the enamine intermediate addition to the aldehyde acceptor for proline and chiral amino sulfonamide-promoted aldol reactions are reported. DFT calculations not only provide a good explanation for the formation of the sole cross-aldol product between two aliphatic aldehydes both bearing α-methylene protons but also well reproduce the opposite syn vs anti diastereoselectivities in the chiral amino sulfonamide and proline-catalyzed aldol reactions. SN - 1520-5215 UR - https://www.unboundmedicine.com/medline/citation/23442005/Density_functional_study_of_organocatalytic_cross_aldol_reactions_between_two_aliphatic_aldehydes:_insight_into_their_functional_differentiation_and_origins_of_chemo__and_stereoselectivities_ L2 - https://doi.org/10.1021/jp3126363 DB - PRIME DP - Unbound Medicine ER -