Authors:	Sietmann, Jan Tenberge, Marius Wahl, Johannes M.
Title:	Wacker oxidation of methylenecyclobutanes : scope and selectivity in an unusual setting
Online publication date:	1-Mar-2024
Year of first publication:	2022
Language:	english
Abstract:	Methylenecyclobutanes are found to undergo Wacker oxidation via a semi-pinacol-type rearrangement. Key to a successful process is the use of tert-butyl nitrite as oxidant, which not only enables efficient catalyst turn-over but also ensures high Markovnikov-selectivity under mild conditions. Thus, cyclopentanones (26 examples) can be accessed in an overall good yield and excellent selectivity (up to 97 % yield, generally >99 : 1 ketone:aldehyde ratio). Stereochemical analysis of the reaction sequence reveals migration aptitudes in line with related 1,2-shifts. By introducing a pyox ligand to palladium, prochiral methylenecyclobutanes can be desymmetrized, thus realizing the first enantioselective Wacker oxidation.
DDC:	540 Chemie 540 Chemistry and allied sciences
Institution:	Johannes Gutenberg-Universität Mainz
Department:	FB 09 Chemie, Pharmazie u. Geowissensch.
Place:	Mainz
ROR:	https://ror.org/023b0x485
DOI:	http://doi.org/10.25358/openscience-10141
Version:	Published version
Publication type:	Zeitschriftenaufsatz
Document type specification:	Scientific article
License:	CC BY
Information on rights of use:	https://creativecommons.org/licenses/by/4.0/
Journal:	Angewandte Chemie International Edition 62 7
Pages or article number:	e202215381
Publisher:	Wiley
Publisher place:	Weinheim
Issue date:	2022
ISSN:	1521-3773
Publisher DOI:	10.1002/anie.202215381
Relations:	is version of 10.25358/openscience-10142
Appears in collections:	DFG-491381577-H