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Updated: Jun 10, 2025

Enzymatic Cascade Reactions for the Synthesis of Chiral Amino Alcohols from L-lysine
Published on: February 16, 2018
Syn vs. Anti? What Controls Addition Stereochemistry in Chlorolactonization
Emily R Dzurka Camelio1, Mitchell Maday2, Aritra Sarkar2
1Department of Green Chemistry and Biochemistry, University of Michigan-Flint, Flint, MI, 48502, USA.
Abstract:
The stereochemistry of the uncatalyzed chlorolactonization of 4-phenylpent-4-enoic acid at room temperature was examined to probe the reaction's intrinsic diastereoselectivities as a function of chlorenium ion donor, solvent polarity, and reactant concentration ranges. Kinetic studies using Variable Time Normalization Analysis (VTNA) revealed differing reaction orders for the syn and anti alkene addition processes. Aided and illustrated by quantum chemical modeling, this detailed mechanistic analysis of the substrate's intrinsic chlorolactonization reactions points to concerted AdE3-type paths for both syn and anti additions. By illuminating the factors selecting for syn- vs anti-addition paths, the results provide key reference points for future studies of stereocontrol in halofunctionalization reactions.
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