Elucidating Latent Mechanistic Complexity in Competing Acid-Catalyzed Reactions of Salicylaldehyde-Derived Baylis–Hillman Adducts

Olomola, Temitope O; Klein, Rosalyn; Caira, Mino, R; Kaye, Perry T

Title: Elucidating Latent Mechanistic Complexity in Competing Acid-Catalyzed Reactions of Salicylaldehyde-Derived Baylis–Hillman Adducts
Creator: Olomola, Temitope O
Creator: Klein, Rosalyn
Creator: Caira, Mino, R
Creator: Kaye, Perry T
Subject: To be catalogued
Date Issued: 2016
Date: 2016
Type: text
Type: article
Identifier: http://hdl.handle.net/10962/442596
Identifier: vital:74010
Identifier: https://doi.org/10.1021/acs.joc.5b02372
Description: 1H NMR-based kinetic studies have revealed the latent mechanistic complexity of deceptively simple hydrochloric acid-catalyzed reactions of salicylaldehyde-derived Baylis–Hillman adducts. Reactions conducted at 0 °C afforded 2-(chloromethyl)cinnamic acid derivatives as the major products and the corresponding 3-(chloromethyl)coumarin derivatives as the minor products. In reactions conducted in refluxing acetic acid, however, the 3-(chloromethyl)coumarin derivatives are the sole products. Variable-temperature 1H NMR analysis permitted the determination of the rate constants and kinetic parameters involved in the pseudo-first-order formation of (Z)-2-(chloromethyl)-3-(2-hydroxyphenyl)-2-propenoic acid. The kinetic data clearly preclude the operation of classical kinetic versus thermodynamic control and indicate the operation of three independent reaction pathways. Theoretical studies of these pathways undertaken at the B3LYP/6-31G(d) level permitted rationalization of the experimental data and provided insights into the possible mechanism of the enzymic E–Z isomerization and cyclization of (E)-cinnamic acid analogues to afford coumarins.
Format: 12 pages
Format: pdf
Language: English
Relation: The Journal of Organic Chemistry
Relation: Olomola, T.O., Klein, R., Caira, M.R. and Kaye, P.T., 2016. Elucidating Latent Mechanistic Complexity in Competing Acid-Catalyzed Reactions of Salicylaldehyde-Derived Baylis–Hillman Adducts. The Journal of Organic Chemistry, 81(1), pp.109-120. https://doi.org/10.1021/acs.joc.5b02372
Relation: The Journal of Organic Chemistry volume 81 number 1 109 120 2016 1520-6904
Rights: Author
Rights: Use of this resource is governed by the ACS Chemistry of Life Terms and Conditions Statement (https://www.acs.org/terms.html)

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