Diastereoconvergent synthesis of anti -1,2-amino alcohols with N-containing quaternary stereocenters via selenium-catalyzed intermolecular C-H amination.

Autor:	Zheng T; Department of Chemistry, University of Washington Box 351700 Seattle Washington 98195-1700 USA michael@chem.washington.edu., Berman JL; Department of Chemistry, University of Washington Box 351700 Seattle Washington 98195-1700 USA michael@chem.washington.edu., Michael FE; Department of Chemistry, University of Washington Box 351700 Seattle Washington 98195-1700 USA michael@chem.washington.edu.
Jazyk:	angličtina
Zdroj:	Chemical science [Chem Sci] 2022 Aug 03; Vol. 13 (33), pp. 9685-9692. Date of Electronic Publication: 2022 Aug 03 (Print Publication: 2022).
DOI:	10.1039/d2sc02648a
Abstrakt:	We report a diastereoconvergent synthesis of anti -1,2-amino alcohols bearing N-containing quaternary stereocenters using an intermolecular direct C-H amination of homoallylic alcohol derivatives catalyzed by a phosphine selenide. Destruction of the allylic stereocenter during the selenium-catalyzed process allows selective formation of a single diastereomer of the product starting from any diastereomeric mixture of the starting homoallylic alcohol derivatives, eliminating the need for the often-challenging diastereoselective preparation of starting materials. Mechanistic studies show that the diastereoselectivity is controlled by a stereoelectronic effect (inside alkoxy effect) on the transition state of the final [2,3]-sigmatropic rearrangement, leading to the observed anti selectivity. The power of this protocol is further demonstrated on an extension to the synthesis of syn -1,4-amino alcohols from allylic alcohol derivatives, constituting a rare example of 1,4-stereoinduction. Competing Interests: There are no conflicts to declare. (This journal is © The Royal Society of Chemistry.)
Databáze:	MEDLINE
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