Chemo-, Regio-, and Diastereoselective Hydrogenation of Oxopromegestone into Trimegestone over Supported Platinoids: Effects of the Transition Metal, Support Nature, Tin Additives, and Modifiers

Yurii A. Ryndin, Catherine C. Santini*, Denis Prat, Jean-Marie Maurice Basset

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

33 Scopus citations

Abstract

The selective hydrogenation of oxopromegestone (17α-methyl-17β-(1,2-dioxopropyl)-estra-4,9-dien-3-one), 1, into Trimegestone (17α-methyl-17β-(2(S)-hydroxy-1-oxopropyl)-estra-4,9-dien-3-one), 2, was carried out on various monometallic catalysts. The order of activity, Pd〉Rh〉Pt〉Ir〉Os, was almost opposite that of the chemoselectivity (selective hydrogenation of the carbonyl versus the internal olefinic double bond), Os〉Ir〉Pt=Pd〉Rh. No metal gave any required diastereoselectivity (selective formation of the 21(S)-OH alcohol). However, silica-supported rhodium, palladium, and platinum exhibited 100% diastereomer excess (d.e.) for the hydrogenation of the C3 carbonyl group. Pt/SiO2 catalyst exhibited a low chemoselectivity (24%), but its TON activity was relatively high (42×10-3 s-1). Pts(Sn)n/SiO2 catalysts, prepared by the interaction of Sn(CH3)4 with reduced Pt/SiO2 under H2 at room temperature, exhibited a significant increase of chemoselectivity compared to Pt/SiO2, but still a low diastereoselectivity to the desired 21(S)-OH unsaturated ketoalcohol, 2. In parallel, the d.e. for the hydrogenation of the C3 carbonyl group decreased from 100% to 34%. The addition of (-)cinchonidine and hydrocinchonidine on the platinum-tin catalysts sharply increased the d.e. in favor of the 21(S)-OH unsaturated ketoalcohol to 70% without changing the chemoselectivity.

Original languageEnglish (US)
Pages (from-to)364-373
Number of pages10
JournalJournal of Catalysis
Volume190
Issue number2
DOIs
StatePublished - Mar 10 2000

Keywords

  • Chemoselective hydrogenation
  • Diastereoselective hydrogenation
  • Hydro(-)cinchonidine modifier
  • Oxopromegestone
  • Platinum-tin catalyst
  • Trimegestone

ASJC Scopus subject areas

  • Catalysis
  • Physical and Theoretical Chemistry

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