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. 2022 Apr 22;24(15):2793-2797.
doi: 10.1021/acs.orglett.2c00630. Epub 2022 Apr 11.

Ylidenenorbornadiene Carboxylates: Experimental Kinetic Analysis of a Nucleophile-Induced Fragmentation Reaction

David M Malouf  1 , Abigail D Richardson  1 , Scott J L'Heureux  1 , Elizabeth A McDonough  1 , Ava M Henry  1 , Jerry Y Sheng  1 , Erica A Medhurst  1 , Angel E Canales  1 , Cameron J Fleischer  1 , Ty B Cecil  1 , Spencer E Thurman  1 , Cameron C McMullen  1 , Philip J Costanzo  1 , Daniel A Bercovici  1
Affiliations

Ylidenenorbornadiene Carboxylates: Experimental Kinetic Analysis of a Nucleophile-Induced Fragmentation Reaction

David M Malouf et al. Org Lett. .

Abstract

Ylidenenorbornadienes (YNDs), prepared by [4 + 2] cycloadditions between fulvenes and acetylene carboxylates, react with beta-mercaptoethanol to yield a mixture of four diastereomers. These four diastereomers fragment via a retro-[4 + 2] cycloaddition at differing rates. A simulated kinetics approach extrapolated the rate constants of the diastereomers from the observed rate data. YNDs display wide variability in rate of fragmentation, dependent on the stereoelectronics of the ylidene substituents. A substrate containing one carboxylic ester proved exceptionally stable to fragmentation.

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