- METHOD OF HYDROBORATING ALCOHOLS AND REDUCING FUNCTIONAL GROUPS USING A RECYCLABLE FLUOROUS BORANE-SULFIDE
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A method of hydroborating an alkene or alkyne, or reducing an organic functionality, oxidizing primary and secondary alcohols using a fluorous borane-sulfide is disclosed. The method includes regeneration and recycling the fluorous borane-sulfide.
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- Fluorous dimethyl sulfide: A convenient, odorless, recyclable borane carrier
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(matrix presented) Borane gas and 2-(perfluorooctyl)ethyl methyl sulfide form a solid comprised of an approximately 1:1 mixture (fluorous BMS) of sulfide and the corresponding sulfide-borane. Fluorous BMS permits hydroboration of alkenes in a dichloromethane/perfluorinated hydrocarbon mixture with subsequent recycling of the fluorous sulfide by fluorous extraction. The use of fluorous BMS in the asymmetric reduction of ketones catalyzed by a chiral oxaborolidine catalyst, and in the reduction of other functional groups, is also reported.
- Crich, David,Neelamkavil, Santhosh
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p. 4175 - 4177
(2007/10/03)
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- Synthesis of terminally perfluorinated long-chain alkanethiols, sulfides and disulfides from the corresponding halides
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Semifluorinated n-alkanethiols, symmetrical sulfides and disulfides bearing the chain(s) F(CF2)n(CH2)m with n=4, 6, 8, 10, and m=2, 11 have been prepared by various synthetic methods, starting from the corresponding iodides or bromides. Methods based on sodium hydrogen sulfide, commonly used to accomplish this conversion, treatment of the Bunte salt obtained from sodium thiosulfate, the basic hydrolysis of isothiouronium salts, the hydrolysis under mild conditions of thiophosphorates formed from sodium thiophosphate and the basic hydrolysis of thiol acetic acid derivatives, have been investigated and compared relatively to the selective synthesis of the title compounds. The thiolacetic route yields essentially the thiols with some amounts of disulfides. Results from thiourea appears similar. Sodium thiophosphate constitutes an excellent route for the synthesis of thioethers, particularly when starting from the bromides. The two classical methods based on sodium hydrogen sulfide and sodium thiosulfate exhibit poor selectivity. It has been possible to obtain all the sulfur compounds reported in the pure state.
- Naud,Calas,Blancou,Commeyras
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p. 173 - 183
(2007/10/03)
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