Catalytic enantioselective synthesis of P-stereogenic compounds
Catalytic enantioselective strategies have become synthetically useful to access P-stereogenic phosphines. To date, enantioselective desymmetrisations and dynamic kinetic resolutions dominate the field. Desymmetrisation strategies do not necessarily require the formation of a P-carbon or P-heteroato...
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| Published in | Chemical communications (Cambridge, England) Vol. 46; no. 4; pp. 7477 - 7485 |
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| Main Authors | , |
| Format | Journal Article |
| Language | English |
| Published |
England
28.10.2010
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| Online Access | Get full text |
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| Summary: | Catalytic enantioselective strategies have become synthetically useful to access P-stereogenic phosphines. To date, enantioselective desymmetrisations and dynamic kinetic resolutions dominate the field. Desymmetrisation strategies do not necessarily require the formation of a P-carbon or P-heteroatom bond. This approach has been validated with variable levels of success using organocatalysed asymmetric deprotonation (chiral diamine) or methylation (phase transfer catalysis), enzyme-mediated esterification, rhodium catalysed [2+2+2] cycloadditions and more recently molybdenum-based ring closing metathesis. The dynamic kinetic resolution of racemic P-templates relying on a P-C bond-forming event has been the object of extensive investigations, which have culminated with the arylation and alkylation (benzylation) of equilibrating diastereomeric palladium, platinum or ruthenium phosphido complexes. Although all these routes allow access to a myriad of highly interesting P-stereogenic compounds, the level of enantiocontrol is substrate- and reactant-dependent. Pleasingly, ee's up to 98% were obtained on selected systems.
To access P-stereogenic phosphines, catalytic enantioselective desymmetrisations are advantageous as they do not necessarily require the formation of a P-C or P-X bond. DKR tactics have culminated with the arylation and benzylation of equilibrating diastereomeric metal-phosphido complexes (ee up to 98%). |
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| Bibliography: | Véronique Gouverneur is a Professor of Chemistry at the University of Oxford. Since her appointment in Oxford in 1998, she holds a Tutorial Fellowship at Merton College. After her PhD with Prof. L. Ghosez at the Université Catholique de Louvain, she left Belgium and moved to a postdoctoral position with Prof. R. A. Lerner at the Scripps Research Institute (California, USA). She returned to Europe in 1994 as a Maître de Conférence at the Université Louis Pasteur (Strasbourg, France) with Dr C. Mioskowski, then moved to Oxford. Her research on F-, P-, Si-chemistry and interest in reaction discovery have been recognised with a number of awards inclusive of the AstraZeneca Research Award in Organic Chemistry (2005) and the RSC Bader Award (2008). James Harvey graduated with both his MA (Hons) and MSci degrees from Clare College Cambridge in 2006, completing a research project with the late Dr Jonathan Spencer. He then moved to the University of Oxford where he completed his DPhil under the supervision of Prof. Véronique Gouverneur. His DPhil research was focused on the development of catalytic enantioselective approaches to P-stereogenic targets. This project involved collaborative work with Prof. A. Hoveyda (Boston College, USA). In 2010, he moved to Princeton University (USA) to conduct his post-doctoral research with Prof. David W. C. MacMillan on enantioselective organocatalytic transformations. ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 |
| ISSN: | 1359-7345 1364-548X |
| DOI: | 10.1039/c0cc01939a |