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Synthesis and application of phosphinoferrocenylaminophosphine ligands for asymmetric catalysis.
J Org Chem. 2005 Mar 04; 70(5):1872-80.JO

Abstract

A new class of bidentate ligands utilizing a phosphine-aminophosphine structure has been prepared on a ferrocenylethyl backbone in a straightforward and scalable fashion from acetylferrocene. The unique property of the alpha-ferrocenyl carbonium ion that allows the replacement of a variety of "leaving groups" with retention of configuration greatly facilitates the synthesis, and a number of ligands have been prepared by varying the nitrogen and phosphorus substituents on the aminophosphine. These readily prepared phosphinoferrocenylaminophosphines, known as BoPhoz ligands, show surprising hydrolytic and air stability, with no degradation after 3 years open to the air. The rhodium complexes of these ligands show exceedingly high enantioselectivities (generally >95% ee) and activities often in excess of 50,000 catalyst turnovers per hour for the asymmetric hydrogenation of a wide variety of dehydro-alpha-amino acid and itaconic acid derivatives. They also show high activity and good to excellent enantioselectivity for the hydrogenation of a number of alpha-ketoesters.

Authors+Show Affiliations

Research Laboratories, Eastman Chemical Company, P.O. Box 1972, Kingsport, Tennessee 37662, USA. nwboaz@eastman.comNo affiliation info availableNo affiliation info availableNo affiliation info availableNo affiliation info available

Pub Type(s)

Journal Article

Language

eng

PubMed ID

15730312

Citation

Boaz, Neil W., et al. "Synthesis and Application of Phosphinoferrocenylaminophosphine Ligands for Asymmetric Catalysis." The Journal of Organic Chemistry, vol. 70, no. 5, 2005, pp. 1872-80.
Boaz NW, Mackenzie EB, Debenham SD, et al. Synthesis and application of phosphinoferrocenylaminophosphine ligands for asymmetric catalysis. J Org Chem. 2005;70(5):1872-80.
Boaz, N. W., Mackenzie, E. B., Debenham, S. D., Large, S. E., & Ponasik, J. A. (2005). Synthesis and application of phosphinoferrocenylaminophosphine ligands for asymmetric catalysis. The Journal of Organic Chemistry, 70(5), 1872-80.
Boaz NW, et al. Synthesis and Application of Phosphinoferrocenylaminophosphine Ligands for Asymmetric Catalysis. J Org Chem. 2005 Mar 4;70(5):1872-80. PubMed PMID: 15730312.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Synthesis and application of phosphinoferrocenylaminophosphine ligands for asymmetric catalysis. AU - Boaz,Neil W, AU - Mackenzie,Elaine B, AU - Debenham,Sheryl D, AU - Large,Shannon E, AU - Ponasik,James A,Jr PY - 2005/2/26/pubmed PY - 2005/4/23/medline PY - 2005/2/26/entrez SP - 1872 EP - 80 JF - The Journal of organic chemistry JO - J Org Chem VL - 70 IS - 5 N2 - A new class of bidentate ligands utilizing a phosphine-aminophosphine structure has been prepared on a ferrocenylethyl backbone in a straightforward and scalable fashion from acetylferrocene. The unique property of the alpha-ferrocenyl carbonium ion that allows the replacement of a variety of "leaving groups" with retention of configuration greatly facilitates the synthesis, and a number of ligands have been prepared by varying the nitrogen and phosphorus substituents on the aminophosphine. These readily prepared phosphinoferrocenylaminophosphines, known as BoPhoz ligands, show surprising hydrolytic and air stability, with no degradation after 3 years open to the air. The rhodium complexes of these ligands show exceedingly high enantioselectivities (generally >95% ee) and activities often in excess of 50,000 catalyst turnovers per hour for the asymmetric hydrogenation of a wide variety of dehydro-alpha-amino acid and itaconic acid derivatives. They also show high activity and good to excellent enantioselectivity for the hydrogenation of a number of alpha-ketoesters. SN - 0022-3263 UR - https://www.unboundmedicine.com/medline/citation/15730312/Synthesis_and_application_of_phosphinoferrocenylaminophosphine_ligands_for_asymmetric_catalysis_ L2 - https://doi.org/10.1021/jo048312y DB - PRIME DP - Unbound Medicine ER -