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Rhodium-catalyzed asymmetric hydrogenation of functionalized olefins using monodentate spiro phosphoramidite ligands.
J Org Chem. 2004 Jul 09; 69(14):4648-55.JO

Abstract

Novel chiral monodentate phosphorus ligands, SIPHOS, were conveniently synthesized from 1,1'-spirobiindane-7,7'-diol. The Rh complexes of SIPHOS can catalyze the hydrogenation of alpha-dehydroamino esters in mild conditions, providing alpha-amino acid derivatives in up to 99% ee. Enamides and beta-dehydroamino esters can also be hydrogenated in good to excellent enantioselectivities (up to 99% and 94% ee, respectively). The SIPHOS ligand with smaller alkyl groups on the N-atom afforded higher enantioselectivity. The X-ray analysis of single crystal showed that the structure of Rh/SIPHOS catalyst is [Rh(COD)((S)-SIPHOS-Me)(2)](+), which clarified the configuration of the catalyst with the monodentate chiral phosphorus ligand in Rh-catalyzed asymmetric hydrogenation. A positive nonlinear effect in the relationship of the optical purities of ligand and product was observed in the hydrogenation of dehydroamino acid derivatives. The kinetic study of hydrogenation showed that the reaction is zero order in the concentration of substrate and first order in the concentration of Rh catalyst and the hydrogenation pressure. The rate of hydrogenation decreased when the Rh/L ratio changed from 1:1 to 1:4.

Authors+Show Affiliations

State Key Laboratory and Institute of Elemento-organic Chemistry, Nankai University, Tianjin 300071, China.No affiliation info availableNo affiliation info availableNo affiliation info availableNo affiliation info availableNo affiliation info available

Pub Type(s)

Journal Article

Language

eng

PubMed ID

15230585

Citation

Fu, Yu, et al. "Rhodium-catalyzed Asymmetric Hydrogenation of Functionalized Olefins Using Monodentate Spiro Phosphoramidite Ligands." The Journal of Organic Chemistry, vol. 69, no. 14, 2004, pp. 4648-55.
Fu Y, Guo XX, Zhu SF, et al. Rhodium-catalyzed asymmetric hydrogenation of functionalized olefins using monodentate spiro phosphoramidite ligands. J Org Chem. 2004;69(14):4648-55.
Fu, Y., Guo, X. X., Zhu, S. F., Hu, A. G., Xie, J. H., & Zhou, Q. L. (2004). Rhodium-catalyzed asymmetric hydrogenation of functionalized olefins using monodentate spiro phosphoramidite ligands. The Journal of Organic Chemistry, 69(14), 4648-55.
Fu Y, et al. Rhodium-catalyzed Asymmetric Hydrogenation of Functionalized Olefins Using Monodentate Spiro Phosphoramidite Ligands. J Org Chem. 2004 Jul 9;69(14):4648-55. PubMed PMID: 15230585.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Rhodium-catalyzed asymmetric hydrogenation of functionalized olefins using monodentate spiro phosphoramidite ligands. AU - Fu,Yu, AU - Guo,Xun-Xiang, AU - Zhu,Shou-Fei, AU - Hu,Ai-Guo, AU - Xie,Jian-Hua, AU - Zhou,Qi-Lin, PY - 2004/7/3/pubmed PY - 2004/7/3/medline PY - 2004/7/3/entrez SP - 4648 EP - 55 JF - The Journal of organic chemistry JO - J Org Chem VL - 69 IS - 14 N2 - Novel chiral monodentate phosphorus ligands, SIPHOS, were conveniently synthesized from 1,1'-spirobiindane-7,7'-diol. The Rh complexes of SIPHOS can catalyze the hydrogenation of alpha-dehydroamino esters in mild conditions, providing alpha-amino acid derivatives in up to 99% ee. Enamides and beta-dehydroamino esters can also be hydrogenated in good to excellent enantioselectivities (up to 99% and 94% ee, respectively). The SIPHOS ligand with smaller alkyl groups on the N-atom afforded higher enantioselectivity. The X-ray analysis of single crystal showed that the structure of Rh/SIPHOS catalyst is [Rh(COD)((S)-SIPHOS-Me)(2)](+), which clarified the configuration of the catalyst with the monodentate chiral phosphorus ligand in Rh-catalyzed asymmetric hydrogenation. A positive nonlinear effect in the relationship of the optical purities of ligand and product was observed in the hydrogenation of dehydroamino acid derivatives. The kinetic study of hydrogenation showed that the reaction is zero order in the concentration of substrate and first order in the concentration of Rh catalyst and the hydrogenation pressure. The rate of hydrogenation decreased when the Rh/L ratio changed from 1:1 to 1:4. SN - 0022-3263 UR - https://www.unboundmedicine.com/medline/citation/15230585/Rhodium_catalyzed_asymmetric_hydrogenation_of_functionalized_olefins_using_monodentate_spiro_phosphoramidite_ligands_ L2 - https://doi.org/10.1021/jo049655z DB - PRIME DP - Unbound Medicine ER -
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