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Application of chiral mixed phosphorus/sulfur ligands to enantioselective rhodium-catalyzed dehydroamino acid hydrogenation and ketone hydrosilylation processes.
J Am Chem Soc. 2003 Mar 26; 125(12):3534-43.JA

Abstract

Chiral mixed phosphorus/sulfur ligands 1-3 have been shown to be effective in enantioselective Rh-catalyzed dehydroamino acid hydrogenation and ketone hydrosilylation reactions (eqs 1, 2). After assaying the influence of the substituents at sulfur, the substituents on the ligand backbone, the relative stereochemistry within the ligand backbone, and the substituents at phosphorus, ligands 2c (R = 3,5-dimethylphenyl) and 3 were found to be optimal in the Rh-catalyzed hydrogenation of a variety of alpha-acylaminoacrylates in high enantioselectivity (89-97% ee). A similar optimization of the catalyst for the Rh-catalyzed hydrosilylation of ketones showed that ligand 3 afforded the highest enantioselectivities for a wide variety of aryl alkyl and dialkyl ketones (up to 99% ee). A model for asymmetric induction in the hydrogenation reaction is discussed in the context of existing models, based on the absolute stereochemistry of the products and the X-ray crystal structures of catalyst precursors and intermediates.

Authors+Show Affiliations

Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, USA. evans@chemistry.harvard.eduNo affiliation info availableNo affiliation info availableNo affiliation info available

Pub Type(s)

Journal Article
Research Support, Non-U.S. Gov't
Research Support, U.S. Gov't, Non-P.H.S.
Research Support, U.S. Gov't, P.H.S.

Language

eng

PubMed ID

12643715

Citation

Evans, David A., et al. "Application of Chiral Mixed Phosphorus/sulfur Ligands to Enantioselective Rhodium-catalyzed Dehydroamino Acid Hydrogenation and Ketone Hydrosilylation Processes." Journal of the American Chemical Society, vol. 125, no. 12, 2003, pp. 3534-43.
Evans DA, Michael FE, Tedrow JS, et al. Application of chiral mixed phosphorus/sulfur ligands to enantioselective rhodium-catalyzed dehydroamino acid hydrogenation and ketone hydrosilylation processes. J Am Chem Soc. 2003;125(12):3534-43.
Evans, D. A., Michael, F. E., Tedrow, J. S., & Campos, K. R. (2003). Application of chiral mixed phosphorus/sulfur ligands to enantioselective rhodium-catalyzed dehydroamino acid hydrogenation and ketone hydrosilylation processes. Journal of the American Chemical Society, 125(12), 3534-43.
Evans DA, et al. Application of Chiral Mixed Phosphorus/sulfur Ligands to Enantioselective Rhodium-catalyzed Dehydroamino Acid Hydrogenation and Ketone Hydrosilylation Processes. J Am Chem Soc. 2003 Mar 26;125(12):3534-43. PubMed PMID: 12643715.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Application of chiral mixed phosphorus/sulfur ligands to enantioselective rhodium-catalyzed dehydroamino acid hydrogenation and ketone hydrosilylation processes. AU - Evans,David A, AU - Michael,Forrest E, AU - Tedrow,Jason S, AU - Campos,Kevin R, PY - 2003/3/20/pubmed PY - 2003/5/7/medline PY - 2003/3/20/entrez SP - 3534 EP - 43 JF - Journal of the American Chemical Society JO - J Am Chem Soc VL - 125 IS - 12 N2 - Chiral mixed phosphorus/sulfur ligands 1-3 have been shown to be effective in enantioselective Rh-catalyzed dehydroamino acid hydrogenation and ketone hydrosilylation reactions (eqs 1, 2). After assaying the influence of the substituents at sulfur, the substituents on the ligand backbone, the relative stereochemistry within the ligand backbone, and the substituents at phosphorus, ligands 2c (R = 3,5-dimethylphenyl) and 3 were found to be optimal in the Rh-catalyzed hydrogenation of a variety of alpha-acylaminoacrylates in high enantioselectivity (89-97% ee). A similar optimization of the catalyst for the Rh-catalyzed hydrosilylation of ketones showed that ligand 3 afforded the highest enantioselectivities for a wide variety of aryl alkyl and dialkyl ketones (up to 99% ee). A model for asymmetric induction in the hydrogenation reaction is discussed in the context of existing models, based on the absolute stereochemistry of the products and the X-ray crystal structures of catalyst precursors and intermediates. SN - 0002-7863 UR - https://www.unboundmedicine.com/medline/citation/12643715/Application_of_chiral_mixed_phosphorus/sulfur_ligands_to_enantioselective_rhodium_catalyzed_dehydroamino_acid_hydrogenation_and_ketone_hydrosilylation_processes_ L2 - https://doi.org/10.1021/ja012639o DB - PRIME DP - Unbound Medicine ER -