On the stability of the pi-allyl intermediate in molybdenum-catalyzed asymmetric alkylations

JAR Luft, ZX Yu, DL Hughes, GC Lloyd-Jones, SW Krska, KN Houk*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

Abstract

Density functional theory calculations were performed on the apparent eta(3)-pi-allyl molybdenum intermediate that is observed during molybdenum-catalyzed asymmetric allylation [Proc. Natl. Acad Sci. U.S.A. 2004, 101, 5379]. The relative stabilities of geometric isomers, diastereoisomers, and pi-allyl rotamers of the pi-allyl molybdenum intermediate were investigated. Calculations show that the observed intermediate is the most stable because of two factors: (1) the observed pi-allyl molybdenum intermediate maximizes the bonding and back-bonding interactions between molybdenum and the pi-allyl ligand; and (2) the observed pi-allyl molybdenum intermediate minimizes the steric interactions between the chiral ligand and the pi-allyl group. (c) 2006 Elsevier Ltd. All rights reserved.

Original languageEnglish
Pages (from-to)716-724
Number of pages9
JournalTetrahedron: Asymmetry
Volume17
Issue number4
DOIs
Publication statusPublished - 20 Feb 2006

Keywords

  • MOLECULAR-ORBITAL METHODS
  • GAUSSIAN-TYPE BASIS
  • CRYSTAL-STRUCTURE
  • ETA-3-ALLYL COMPLEXES
  • SUBSTITUTED CARBONYLS
  • ORGANIC-MOLECULES
  • DYNAMIC-BEHAVIOR
  • LIGANDS
  • HYDROGENATION
  • STEREOSELECTIVITY

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