Elucidating Latent Mechanistic Complexity in Competing Acid-Catalyzed Reactions of Salicylaldehyde-Derived Baylis–Hillman Adducts
- 14 December 2015
- journal article
- research article
- Published by American Chemical Society (ACS) in The Journal of Organic Chemistry
- Vol. 81 (1), 109-120
- https://doi.org/10.1021/acs.joc.5b02372
Abstract
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 insi...Funding Information
- National Research Foundation (IFR2011032500034)
- Rhodes University
This publication has 42 references indexed in Scilit:
- Intramolecular Morita–Baylis–Hillman and Rauhut–Currier reactions. A catalytic and atom economic route for carbocycles and heterocyclesRSC Advances, 2015
- Morita–Baylis–Hillman adduct derivatives (MBHADs): versatile reactivity in Lewis base-promoted annulationOrganic & Biomolecular Chemistry, 2015
- Enatioselective Chalcogeno‐Baylis‐Hillman Reaction of Arylaldehydes with MVK and Acrylates Catalyzed by Chiral Thiepin‐TiCl4 ComplexChinese Journal of Chemistry, 2014
- Baylis–Hillman Reaction as a Versatile Platform for the Synthesis of Diverse Functionalized Polymers by Chain and Step PolymerizationMacromolecules, 2014
- The mechanism of the NHC catalyzed aza-Morita–Baylis–Hillman reaction: insights into a new substrate-catalyzed bimolecular pathwayOrganic & Biomolecular Chemistry, 2014
- Ketones as electrophiles in two component Baylis–Hillman reaction: a facile one-pot synthesis of substituted indolizinesOrganic & Biomolecular Chemistry, 2013
- P-chirogenic organocatalysts: application to the aza-Morita–Baylis–Hillman (aza-MBH) reaction of ketiminesChemical Communications, 2013
- Advances in the Baylis–Hillman reaction-assisted synthesis of cyclic frameworksTetrahedron, 2008
- The Baylis–Hillman reaction: a novel source of attraction, opportunities, and challenges in synthetic chemistryChemical Society Reviews, 2007
- A Tertiary Phosphine-catalyzed Reaction of Acrylic Compounds with AldehydesBulletin of the Chemical Society of Japan, 1968