Selective palladium-catalyzed hydrogenolysis of a secondary propargylic alcohol in the synthesis of vitamin D analog Ro 23-7553: Substrate and ligand control

Tetrahedron Letters

Volumn 40, Issue 51, 1999, Pages 8955-8960

  Radinov, Roumen ^a   Hutchings, Stanley D ^a  

^a HOFFMANN LA ROCHE INC   (United States)

Author keywords

Alkynes; Allenes; Hydrogenolysis; Palladium catalysis; Regiocontrol

Indexed keywords

9,10 SECOCHOLESTA 5,7,10(19),16 TETRAEN 23 YNE 1,3,25 TRIOL; ALCOHOL DERIVATIVE; ALKYNE; ALLENE DERIVATIVE; PALLADIUM; PHOSPHINE;

ARTICLE; CATALYSIS; CHEMICAL MODIFICATION; DRUG SYNTHESIS; LIGAND BINDING;

EID: 0033579622     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(99)01941-3     Document Type: Article

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20. 3P catalyst.
21. 4.
22. Better catalyst turnover was achieved in toluene, than in heptane, as a result of better catalyst solubility.
23. 3P, 1 M solution in toluene (7.2 mL, 7.2 mmol) was added. The suspension was stirred for 35 min at rt. Then, a solution of 10 (45.8 g, 90.4 mmol) in toluene (130 mL) was cannulated under nitrogen and the solution was heated for 6 h at 70°C. The solvent was evaporated in vacuum, and the residue was dissolved in hexane (100 mL) and filtered through flash (230-400 mesh) silica gel (45 g) to remove the catalyst. The products were washed out with hexane (1.5 L), and the combined filtrates and washes were concentrated to dryness under reduced pressure to give 40.2 g (96%) of a colorless oil. HPLC: 12 (8%, 1:3.4 d.r.); 11 (92%); purity >99%.
24. This mechanism is intended for illustration only and is not corroborated.
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30. Hydrogenolysis of 3-alkynols which have a terminal alkyne bond is known to give allenes exclusively (see Refs. 8 and 9). Thus, with these particular substrates the reaction is suggested to proceed via the more stable terminal σ-allenyl palladium complexes.