Arthurs, Ross A., Hughes, David L. and Richards, Christopher J. ORCID: https://orcid.org/0000-0001-7899-4082 (2020) Stereoselective synthesis of all possible phosferrox ligand diastereoisomers displaying three elements of chirality: Stereochemical optimization for asymmetric catalysis. Journal of Organic Chemistry, 85 (7). pp. 4838-4847. ISSN 0022-3263
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Abstract
All four possible diastereoisomers of phosphinofer- rocenyloxazoline (Phosferrox type) ligands containing three elements of chirality were synthesized as single enantiomers. The S-c configured oxazoline moiety (R = Me, i-Pr) was used to control the generation of planar chirality by lithiation, with the alternative diastereoisomer formed by use of a deuterium blocking group. In each case subsequent addition of PhPCl2 followed by o-TolMgBr resulted in a single P-stereogenic diastereoisomer (S-c,S-p,S-phos and S-c,S-p,R-phos,R- respectively). The alternative diastereoisomers were formed selectively by addition of o-TolPCl(2) followed by PhMgBr ((S-c,S-p,R-phos and S-c,S-p,S-phos,S- respectively). Preliminary application of these four ligand diastereoisomers, together with (S-c,S-p) and (S-c,R-p) Phosferrox PPh2, to palladium catalyzed allylic alkylation of trans-1,3-diphenylallyl acetate revealed a stepwise increase/decrease in ee, with the configuration of the matched/matched diastereoisomer as S-c,S-p,S-phos (97% ee).
Item Type: | Article |
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Uncontrolled Keywords: | highly enantioselective hydrogenation,diphosphine ligands,allylic alkylation,phosphine oxides,planar chirality,phosphorus,ketones,complexes,efficient,versatile |
Faculty \ School: | Faculty of Science > School of Chemistry (former - to 2024) Faculty of Science > School of Biological Sciences |
UEA Research Groups: | Faculty of Science > Research Groups > Chemistry of Materials and Catalysis |
Related URLs: | |
Depositing User: | LivePure Connector |
Date Deposited: | 07 May 2020 00:05 |
Last Modified: | 01 Oct 2024 01:50 |
URI: | https://ueaeprints.uea.ac.uk/id/eprint/75051 |
DOI: | 10.1021/acs.joc.9b03342 |
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