Quantum mechanical investigations into the mechanism of molybdenum-catalyzed asymmetric allylations

ORGN 830

Jennifer Anne Robbins Luft, jrobbins@chem.ucla.edu1, Zhi-Xiang Yu, zhixiang@chem.ucla.edu1, David L. Hughes2, Guy C. Lloyd-Jones, guy.lloyd-jones@bristol.ac.uk3, Shane Krska2, and K. N. Houk, houk@chem.ucla.edu1. (1) Department of Chemistry and Biochemistry, University of California, Los Angeles, 405 Hilgard Ave, Los Angeles, CA 90095-1569, (2) Department of Process Research, Merck & Co, Rahway, NJ 07065, (3) School of Chemistry, University of Bristol, Cantock's Close, Bristol, BS8 1TS, United Kingdom
The details of mechanisms of molybdenum-catalyzed asymmetric allylations have been explored using density functional theory calculations. The stability of the η3-π-allyl molybdenum intermediate that is observed during molybdenum-catalyzed asymmetric allylation was investigated. The role of the π-allyl intermediate in the catalytic cycle was determined. The potential energy surface of the reaction was examined, including the regioselectivity and enantioselectivity determining steps, the role of excess CO in the reaction, and the rate differences for enantiomeric starting materials.

 

Total Synthesis, Materials, Molecular Recognition, Process R&D, and Physical Organic Chemistry
8:00 PM-10:00 PM, Wednesday, 13 September 2006 Moscone Center -- Hall D, Poster

Sci-Mix
8:00 PM-10:00 PM, Monday, 11 September 2006 Moscone Center -- Hall D, Sci-Mix

Division of Organic Chemistry

The 232nd ACS National Meeting, San Francisco, CA, September 10-14, 2006