Tags

Type your tag names separated by a space and hit enter

Origins of Stereoselectivity of Chiral Vicinal Diamine-Catalyzed Aldol Reactions.
J Org Chem. 2016 12 16; 81(24):12408-12415.JO

Abstract

The sources of asymmetric induction in aldol reactions catalyzed by cinchona alkaloid-derived amines, and chiral vicinal diamines in general, have been determined by density functional theory calculations. Four vicinal diamine-catalyzed aldol reactions were examined. The cyclic transition states of these reactions involve nine-membered hydrogen-bonded rings in distinct conformations. Using nomenclature from eight-membered cycloalkanes, the heavy atoms of the low-energy transition states are in crown (chair-chair) and chair-boat conformations. The factors that control which of these are favored have been identified.

Authors+Show Affiliations

Simon A
Department of Chemistry and Biochemistry, University of California, Los Angeles , 607 Charles E. Young Drive East, Los Angeles, California 90095-1569, United States.
Yeh AJ
Department of Chemistry and Biochemistry, University of California, Los Angeles , 607 Charles E. Young Drive East, Los Angeles, California 90095-1569, United States.
Lam YH
Department of Chemistry and Biochemistry, University of California, Los Angeles , 607 Charles E. Young Drive East, Los Angeles, California 90095-1569, United States.
Houk KN
Department of Chemistry and Biochemistry, University of California, Los Angeles , 607 Charles E. Young Drive East, Los Angeles, California 90095-1569, United States.

MeSH

AldehydesAlkanesCatalysisDiaminesHydrogen BondingModels, MolecularQuantum TheoryStereoisomerism

Pub Type(s)

Journal Article
Research Support, N.I.H., Extramural
Research Support, Non-U.S. Gov't
Research Support, U.S. Gov't, Non-P.H.S.

Language

eng

PubMed ID

27978746

Citation

Simon, Adam, et al. "Origins of Stereoselectivity of Chiral Vicinal Diamine-Catalyzed Aldol Reactions." The Journal of Organic Chemistry, vol. 81, no. 24, 2016, pp. 12408-12415.
Simon A, Yeh AJ, Lam YH, et al. Origins of Stereoselectivity of Chiral Vicinal Diamine-Catalyzed Aldol Reactions. J Org Chem. 2016;81(24):12408-12415.
Simon, A., Yeh, A. J., Lam, Y. H., & Houk, K. N. (2016). Origins of Stereoselectivity of Chiral Vicinal Diamine-Catalyzed Aldol Reactions. The Journal of Organic Chemistry, 81(24), 12408-12415.
Simon A, et al. Origins of Stereoselectivity of Chiral Vicinal Diamine-Catalyzed Aldol Reactions. J Org Chem. 2016 12 16;81(24):12408-12415. PubMed PMID: 27978746.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Origins of Stereoselectivity of Chiral Vicinal Diamine-Catalyzed Aldol Reactions. AU - Simon,Adam, AU - Yeh,Alexander J, AU - Lam,Yu-Hong, AU - Houk,K N, Y1 - 2016/11/28/ PY - 2016/12/17/entrez PY - 2016/12/17/pubmed PY - 2018/5/31/medline SP - 12408 EP - 12415 JF - The Journal of organic chemistry JO - J Org Chem VL - 81 IS - 24 N2 - The sources of asymmetric induction in aldol reactions catalyzed by cinchona alkaloid-derived amines, and chiral vicinal diamines in general, have been determined by density functional theory calculations. Four vicinal diamine-catalyzed aldol reactions were examined. The cyclic transition states of these reactions involve nine-membered hydrogen-bonded rings in distinct conformations. Using nomenclature from eight-membered cycloalkanes, the heavy atoms of the low-energy transition states are in crown (chair-chair) and chair-boat conformations. The factors that control which of these are favored have been identified. SN - 1520-6904 UR - https://www.unboundmedicine.com/medline/citation/27978746/Origins_of_Stereoselectivity_of_Chiral_Vicinal_Diamine_Catalyzed_Aldol_Reactions_ DB - PRIME DP - Unbound Medicine ER -