Enantiodivergent Cyclization by Inversion of the Reactivity in Ambiphilic Molecules.

Autor: Rodríguez-López J; Instituto Universitario de Bio-Orgánica Antonio González, Universidad de La Laguna, Francisco Sánchez 2, 38206, La Laguna, Tenerife, Spain., Brovetto M; Instituto Universitario de Bio-Orgánica Antonio González, Universidad de La Laguna, Francisco Sánchez 2, 38206, La Laguna, Tenerife, Spain., Martín VS; Instituto Universitario de Bio-Orgánica Antonio González, Universidad de La Laguna, Francisco Sánchez 2, 38206, La Laguna, Tenerife, Spain.; Departamento de Química Orgánica, Universidad de La Laguna, Francisco Sánchez s/n. Facultad de Farmacia, 38200, La Laguna, Tenerife, Spain., Martín T; Instituto Universitario de Bio-Orgánica Antonio González, Universidad de La Laguna, Francisco Sánchez 2, 38206, La Laguna, Tenerife, Spain.; Instituto de Productos Naturales y Agrobiología, CSIC, Francisco Sánchez 3, 38206, La Laguna, Tenerife, Spain.
Jazyk: angličtina
Zdroj: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2020 Sep 21; Vol. 59 (39), pp. 17077-17083. Date of Electronic Publication: 2020 Jul 29.
DOI: 10.1002/anie.202006650
Abstrakt: Inverting the reactivity of the functional groups in ambiphilic molecules provides a new synthetic strategy to perform late-stage enantiodivergence. Both enantiomers of the final compound can be obtained from a common chiral precursor. As a proof of concept, the synthesis of substituted five- and six-membered oxacycles is described. The key step is the cyclization of an ambiphilic linear precursor bearing a propargylic alcohol and an epoxide linked through an alkyl chain. Through a slight modification of these linear precursors and employing different reaction conditions, these functional groups can inverse their chemical reactivity, producing one enantiomer or another of the final product. This enantiodivergent cyclization involves three stereogenic centers that can undergo fully controlled retention or inversion of their configuration depending on the cyclization pathway that is activated. The cyclization provides late-stage enantiodivergence, enabling the synthesis of either enantiomers of the oxacycles from a common chiral substrate with total transfer of the enantiomeric purity.
(© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)
Databáze: MEDLINE
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