title: Origins of Stereoselectivity of Chiral Vicinal Diamine-Catalyzed Aldol Reactions.
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.affiliation: Department of Chemistry and Biochemistry, University of California, Los Angeles , 607 Charles E. Young Drive East, Los Angeles, California 90095-1569, United States.
authors.forename: Adam
authors.identifier: 0000-0001-6334-3359
authors.initials: A
authors.lastname: Simon
authors.affiliation: Department of Chemistry and Biochemistry, University of California, Los Angeles , 607 Charles E. Young Drive East, Los Angeles, California 90095-1569, United States.
authors.forename: Alexander J
authors.initials: AJ
authors.lastname: Yeh
authors.affiliation: Department of Chemistry and Biochemistry, University of California, Los Angeles , 607 Charles E. Young Drive East, Los Angeles, California 90095-1569, United States.
authors.forename: Yu-Hong
authors.identifier: 0000-0002-4946-1487
authors.initials: YH
authors.lastname: Lam
authors.affiliation: Department of Chemistry and Biochemistry, University of California, Los Angeles , 607 Charles E. Young Drive East, Los Angeles, California 90095-1569, United States.
authors.forename: K N
authors.initials: KN
authors.lastname: Houk
mesh_terms: D000447:Aldehydes / Q000737:chemistry*; D000473:Alkanes / Q000737:chemistry; D002384:Catalysis; D003959:Diamines / Q000737:chemistry*; D006860:Hydrogen Bonding; D008958:Models, Molecular; D011789:Quantum Theory; D013237:Stereoisomerism
chemical_list: D000447:Aldehydes; D000473:Alkanes; D003959:Diamines; C116609:3-hydroxybutanal