accelerations in the lactonization of trimethyl lock systems are due to proximity orientation and not to strain effects加速度三甲基内酯化的锁系统是由于接近取向和应变的影响.pdfVIP

Hindawi Publishing Corporation Research Letters in Organic Chemistry Volume 2009, Article ID 240253, 5 pages doi:10.1155/2009/240253 Research Letter Accelerations in the Lactonization of Trimethyl Lock Systems Are due to Proximity Orientation and not to Strain Effects Rafik Karaman Faculty of Pharmacy, Al-Quds University, P. O. Box 20002, Jerusalem, Palestinian Correspondence should be addressed to Rafik Karaman, dr karaman@ Received 18 November 2008; Accepted 20 January 2009 Recommended by Robert Flowers DFT at B3LYP/6-31G(d, p) and HF at 6-31G and AM1 semiempirical calculations of thermodynamc and kinetic parameters for the trimethyl lock system (an important enzyme model) indicate that the remarkable enhancement in the lactonizations is largely the result of a proximity orientation as opposed to the currently advanced strain effect. Copyright © 2009 Rafik Karaman. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. 1. Introduction [10– 12]. Cohen’s interpretation of his data was criticized by various researchers who claimed that the high rate The study of enzyme mechanisms is of vast importance enhancement results from relief in strain energy during the and has become central to both bioorganic chemistry and lactonization of the hydroxyhydrocinnamic acid and not computational chemistry. Studies in this field by Bruice, because of a stereopopulation control within the trimethyl Benkovic, Jencks, and Bender over the past 40 years