Unprecedented E-stereoselectivity on the sigmatropic Hurd–Claisen rearrangement of Morita–Baylis–Hillman adducts: a joint experimental–theoretical study

Literature Information

Publication Date 2019-04-05
DOI 10.1039/C9OB00533A
Impact Factor 3.876
Authors

Vinicius Sobral Silva, Terezinha Alves Tolentino, Tiago Costa Alves Fontoura Rodrigues, Fernanda Ferrari Martins Santos, Daniel Francisco Scalabrini Machado, Wender Alves Silva, Heibbe Cristhian Benedito de Oliveira, Angelo Henrique Lira Machado


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Abstract

Herein we report the first systematic investigation of the tandem mercury(II) catalysed transvinylation/Hurd–Claisen rearrangement of MBH adducts derived from alkyl acrylates. This is the first report of E-selectivity for MBH adducts with alkyl side chains and is complementary to the previously reported Johnson–Claisen and Eschenmoser–Claisen rearrangements. The rearrangement products were obtained in good yields and could be readily converted to 2-alkenyl δ-valerolactones. Combined DFT and F-SAPT studies demonstrate that reaction rates are primarily governed by non-covalent interactions dictating the relative stability of the transition states. Our F-SAPT calculations revealed that the hyperconjugative effects are not so significant, but that electrostatic interactions, instead, are the driving forces for the relative E : Z stereoselectivity.

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Organic & Biomolecular Chemistry

Organic & Biomolecular Chemistry
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Organic & Biomolecular Chemistry (OBC) publishes original and high impact research and reviews in organic chemistry. We welcome research that shows new or significantly improved protocols or methodologies in total synthesis, synthetic methodology or physical and theoretical organic chemistry as well as research that shows a significant advance in the organic chemistry or molecular design aspects of chemical biology, catalysis, supramolecular and macromolecular chemistry, theoretical chemistry, mechanism-oriented physical organic chemistry, medicinal chemistry or natural products. Articles published in the journal should report new work which makes a highly-significant impact in the field. Routine and incremental work is generally not suitable for publication in the journal. More details about key areas of our scope are below. In all cases authors should include in their article clear rationale for why their research has been carried out.

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