Efficient enantioselective hydrosilylation of ketones catalyzed by air stable copper fluoride-phosphine complexes

Organic Letters

Volumn 3, Issue 25, 2001, Pages 4111-4113

  Sirol, Sabine ^a   Courmarcel, James ^a   Mostefai, Naouël ^a   Riant, Olivier ^a  

^a UNIVERSITÉ CATHOLIQUE DE LOUVAIN   (Belgium)

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ARTICLE;

EID: 0000187570     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol0169170     Document Type: Article

References (27)

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21. 3)3·2EtOH] for the reduction of ketones by hydrosilanes was first reported by Mori in stoichiometric conditions: (a) Mori, A.; Fujita, A.; Nishihara, Y.; Hiyama, T. Chem. Commun. 1997, 2159-2160.
22. 3)3·2EtOH] for the reduction of ketones by hydrosilanes was first reported by Mori in stoichiometric conditions: (a) Mori, A.; Fujita, A.; Nishihara, Y.; Hiyama, T. Chem. Commun. 1997, 2159-2160.
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25. For a related work on hydrosilylation-hydroxylation of unsaturated substrates with a Mn(III) catalyst, see: (a) Magnus, P.; Payne, A. H.; Waring, M. J.; Scott, D. A.; Lynch, V. Tetrahedron Lett. 2000, 41, 9725-9730.
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27. General procedure for the hydrosilylation of ketones in air: a 25 mL round-bottomed flask was charged with copper fluoride (2 mg, 0.02 mmol, 1 mol %) and (S)-binap (13 mg, 0.02 mmol. 1 mol %), and a stirring bar was added in air. Toluene (8 mL) was added, and the mixture was stirred for 5-10 min. Phenylsilane (0.30 mL, 2.4 mmol, 1.2 equiv) and acetophenone (0.235 mL, 2 mmol) were sequentially added under vigorous stirring, and the flask was stoppered. Conversion and ee determination were followed by gas chromatography performed on aliquots. Hydrolysis of the silyl ether by 1 N HCl and workup gave the crude alcohol. Bulb-to-bulb distillation gave analytically pure product (194 mg, 79% yield). GC analysis on a chiral column gave a 78% ee.