Selective hydrogenation of α,β-unsaturated oxosteroids with homogeneous rhodium catalysts

Rui M D Nunes, Andreia F. Peixoto, M. Rosa Axet, Mariette M. Pereira, Maria José Moreno, L. Kollár, Carmen Claver, Sergio Castillón

Research output: Contribution to journalArticle

9 Citations (Scopus)

Abstract

A comparative study of the ligand (5-10) effect on the rhodium catalytic activity and selectivity in the homogeneous hydrogenation of α,β-unsaturated oxosteroids (1-4) is reported. The highest activity for CC reduction was observed with phosphite ligands, being diphosphite 10 the most active. Furthermore, the presence of phosphite 6 significantly enhances the chemo and α-diastereoselectivity for the hydrogenation reaction. The β-methyl groups of the steroidal framework lead to a very high α-diastereoselectivity, even in the absence of phosphorous ligands. Substrate 4 is the paradigm presenting higher than 94% α- diastereoselectivity for any catalytic system studied. The catalytic system formed from rhodium and the new diphosphite 10 also revealed a remarkable tendency for the CO reduction and a noteworthy stability.

Original languageEnglish
Pages (from-to)275-282
Number of pages8
JournalJournal of Molecular Catalysis A: Chemical
Volume247
Issue number1-2
DOIs
Publication statusPublished - Mar 16 2006

Fingerprint

Ketosteroids
Rhodium
rhodium
Phosphites
Hydrogenation
hydrogenation
Ligands
catalysts
ligands
Catalysts
Catalyst selectivity
Carbon Monoxide
catalytic activity
Catalyst activity
tendencies
selectivity
Substrates

Keywords

  • Hydrogenation
  • Oxosteroid
  • Phosphine
  • Phosphite
  • Rhodium
  • Steroid

ASJC Scopus subject areas

  • Catalysis
  • Process Chemistry and Technology
  • Materials Science (miscellaneous)

Cite this

Selective hydrogenation of α,β-unsaturated oxosteroids with homogeneous rhodium catalysts. / Nunes, Rui M D; Peixoto, Andreia F.; Axet, M. Rosa; Pereira, Mariette M.; Moreno, Maria José; Kollár, L.; Claver, Carmen; Castillón, Sergio.

In: Journal of Molecular Catalysis A: Chemical, Vol. 247, No. 1-2, 16.03.2006, p. 275-282.

Research output: Contribution to journalArticle

Nunes, RMD, Peixoto, AF, Axet, MR, Pereira, MM, Moreno, MJ, Kollár, L, Claver, C & Castillón, S 2006, 'Selective hydrogenation of α,β-unsaturated oxosteroids with homogeneous rhodium catalysts', Journal of Molecular Catalysis A: Chemical, vol. 247, no. 1-2, pp. 275-282. https://doi.org/10.1016/j.molcata.2005.11.058
Nunes, Rui M D ; Peixoto, Andreia F. ; Axet, M. Rosa ; Pereira, Mariette M. ; Moreno, Maria José ; Kollár, L. ; Claver, Carmen ; Castillón, Sergio. / Selective hydrogenation of α,β-unsaturated oxosteroids with homogeneous rhodium catalysts. In: Journal of Molecular Catalysis A: Chemical. 2006 ; Vol. 247, No. 1-2. pp. 275-282.
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AU - Peixoto, Andreia F.

AU - Axet, M. Rosa

AU - Pereira, Mariette M.

AU - Moreno, Maria José

AU - Kollár, L.

AU - Claver, Carmen

AU - Castillón, Sergio

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AB - A comparative study of the ligand (5-10) effect on the rhodium catalytic activity and selectivity in the homogeneous hydrogenation of α,β-unsaturated oxosteroids (1-4) is reported. The highest activity for CC reduction was observed with phosphite ligands, being diphosphite 10 the most active. Furthermore, the presence of phosphite 6 significantly enhances the chemo and α-diastereoselectivity for the hydrogenation reaction. The β-methyl groups of the steroidal framework lead to a very high α-diastereoselectivity, even in the absence of phosphorous ligands. Substrate 4 is the paradigm presenting higher than 94% α- diastereoselectivity for any catalytic system studied. The catalytic system formed from rhodium and the new diphosphite 10 also revealed a remarkable tendency for the CO reduction and a noteworthy stability.

KW - Hydrogenation

KW - Oxosteroid

KW - Phosphine

KW - Phosphite

KW - Rhodium

KW - Steroid

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