Universität zu Köln

Severin, Fabian, Fusi, Giovanni M., Wartmann, Christina ORCID: 0000-0002-3275-8284, Neudoerfl, Jorg-Martin and Berkessel, Albrecht (2022). syn-Selective Epoxidation of Chiral Terminal Allylic Alcohols with a Titanium Salalen Catalyst and Hydrogen Peroxide. Angew. Chem.-Int. Edit., 61 (26). WEINHEIM: WILEY-V C H VERLAG GMBH. ISSN 1521-3773

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Abstract

In the Sharpless asymmetric epoxidation of chiral secondary allylic alcohols, one substrate enantiomer is predominantly converted to the anti-epoxy alcohol. We herein report the first highly syn-selective epoxidation of terminal allylic alcohols using a titanium salalen complex as catalyst, at room temperature, and aqueous hydrogen peroxide as oxidant. With enantiopure terminal allylic alcohols as substrates, the epoxy alcohols were obtained with up to 98 % yield and up to >99 : 1 dr (syn). Catalyst loadings as low as 1 mol % can be applied without eroding the syn-diastereoselectivity. Modification of the allylic alcohol to an ether does not affect the diastereoselectivity either [>99 : 1 dr (syn)]. Inverting the catalyst configuration leads to the anti-product, albeit at lower dr (ca. 20 : 1). The synthetic potential is demonstrated by a short, gram-scale preparation of a tetrahydrofuran building block with three stereocenters, involving two titanium salalen catalyzed epoxidation steps.

Item Type:	Journal Article
Creators:	Creators Email ORCID ORCID Put Code Severin, Fabian UNSPECIFIED UNSPECIFIED UNSPECIFIED Fusi, Giovanni M. UNSPECIFIED UNSPECIFIED UNSPECIFIED Wartmann, Christina UNSPECIFIED orcid.org/0000-0002-3275-8284 UNSPECIFIED Neudoerfl, Jorg-Martin UNSPECIFIED UNSPECIFIED UNSPECIFIED Berkessel, Albrecht UNSPECIFIED UNSPECIFIED UNSPECIFIED
URN:	urn:nbn:de:hbz:38-668162
DOI:	10.1002/anie.202201790
Journal or Publication Title:	Angew. Chem.-Int. Edit.
Volume:	61
Number:	26
Date:	2022
Publisher:	WILEY-V C H VERLAG GMBH
Place of Publication:	WEINHEIM
ISSN:	1521-3773
Language:	English
Faculty:	Unspecified
Divisions:	Unspecified
Subjects:	no entry
Uncontrolled Keywords:	Keywords Language DYNAMIC KINETIC RESOLUTION; ASYMMETRIC EPOXIDATION; ENANTIOSELECTIVE EPOXIDATION; DIASTEREOSELECTIVE EPOXIDATION; SECONDARY ALCOHOLS; NONCONJUGATED OLEFINS; COMPLEXES; EPOXIDES; SITES; H2O2 Multiple languages Chemistry, Multidisciplinary Multiple languages
URI:	http://kups.ub.uni-koeln.de/id/eprint/66816