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Synthesis and Reactivity of ?-Haloglycine Esters: Hyperconjugation in Action.

ABSTRACT: A general and efficient synthesis of ?-haloglycine esters from commercially available feedstock chemicals, in a single step, is reported. The reactivity of these ?-haloglycine esters with various nucleophiles was studied as surrogates of ?-iminoesters upon activation with hydrogen-bond donor catalysts. DFT calculations on the ?-haloglycine structures (X = F, Cl, Br) accompanied by an X-ray characterization of the ?-bromoglycine ester support the existence of a "generalized" anomeric effect created by hyperconjugation. This peculiar hyperconjugative effect is proposed to be responsible for the enhanced halogen nucleofugality leading to a facile halogen abstraction by hydrogen-bond donor catalysts. This reactivity was exploited with thiourea catalysts on several catalytic transformations (aza-Friedel-Crafts and Mannich reactions) for the synthesis of several types of non-proteinogenic ?-amino esters.

SUBMITTER: Samanta SS

PROVIDER: S-EPMC7189931 | biostudies-literature | 2019 Oct

REPOSITORIES: biostudies-literature

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Synthesis and Reactivity of α-Haloglycine Esters: Hyperconjugation in Action.

Samanta Shyam S SS Roche Stéphane P SP

European journal of organic chemistry 20190824 39

A general and efficient synthesis of α-haloglycine esters from commercially available feedstock chemicals, in a single step, is reported. The reactivity of these α-haloglycine esters with various nucleophiles was studied as surrogates of α-iminoesters upon activation with hydrogen-bond donor catalysts. DFT calculations on the α-haloglycine structures (X = F, Cl, Br) accompanied by an X-ray characterization of the α-bromoglycine ester support the existence of a "generalized" anomeric effect creat ...[more]

PMID: 32351314

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