Chemo-, Regio-, and Diastereoselective Hydrogenation of Oxopromegestone into Trimegestone over Supported Platinoids: Effects of the Transition Metal, Support Nature, Tin Additives, and Modifiers Full article
Journal |
Journal of Catalysis
ISSN: 0021-9517 , E-ISSN: 1090-2694 |
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Output data | Year: 2000, Volume: 190, Number: 2, Pages: 364-373 Pages count : 10 DOI: 10.1006/jcat.1999.2760 | ||||||
Tags | Chemoselective hydrogenation, Diastereoselective hydrogenation, Hydro(-)cinchonidine modifier, Oxopromegestone, Platinum-tin catalyst, Trimegestone | ||||||
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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.
Cite:
Ryndin Y.A.
, Santini C.C.
, Prat D.
, Basset J.M.
Chemo-, Regio-, and Diastereoselective Hydrogenation of Oxopromegestone into Trimegestone over Supported Platinoids: Effects of the Transition Metal, Support Nature, Tin Additives, and Modifiers
Journal of Catalysis. 2000. V.190. N2. P.364-373. DOI: 10.1006/jcat.1999.2760 WOS Scopus РИНЦ
Chemo-, Regio-, and Diastereoselective Hydrogenation of Oxopromegestone into Trimegestone over Supported Platinoids: Effects of the Transition Metal, Support Nature, Tin Additives, and Modifiers
Journal of Catalysis. 2000. V.190. N2. P.364-373. DOI: 10.1006/jcat.1999.2760 WOS Scopus РИНЦ
Dates:
Submitted: | Jul 30, 1999 |
Accepted: | Nov 12, 1999 |
Published print: | Mar 10, 2000 |
Published online: | May 25, 2002 |
Identifiers:
Web of science | WOS:000086023900015 |
Scopus | 2-s2.0-0001464522 |
Elibrary | 13339569 |
Chemical Abstracts | 2000:153521 |
Chemical Abstracts (print) | 132:347786 |
OpenAlex | W2037666470 |