Stereoselective synthesis of all possible phosferrox ligand diastereoisomers displaying three elements of chirality: Stereochemical optimization for asymmetric catalysis

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

Preview

PDF (Accepted manuscript) - Accepted Version Download (583kB) | Preview

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
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 Faculty of Science > School of Biological Sciences
UEA Research Groups:	Faculty of Science > Research Groups > Chemistry of Materials and Catalysis
Related URLs:	http://www.scopus.com/inward/record.url?...
Depositing User:	LivePure Connector
Date Deposited:	07 May 2020 00:05
Last Modified:	22 Oct 2022 06:07
URI:	https://ueaeprints.uea.ac.uk/id/eprint/75051
DOI:	10.1021/acs.joc.9b03342

Downloads

Actions (login required)

View Item