Solvent‐Assisted Diastereoselective Tri­meth­ylsilyl Cyanide Additions to Cyclic α‐Fluoro Ketones. Issue 18 (23rd April 2013)

• Record Type: Journal Article
• Authors: Pham, Hao; Davis, Todd A.
• Is Part Of: European journal of organic chemistry. Issue 18(2013)
• Page Start: 3896
• Page End: 3900
• Publication Date: 2013-04-23
• Subjects: Fluorine -- Cyanides -- Ketones -- Nucleophilic addition -- Solvent effects; Chemistry, Organic -- Periodicals; Organic compounds -- Synthesis -- Periodicals; Bioorganic chemistry -- Periodicals; Chemistry, Physical organic -- Periodicals; 547
• DOI: 10.1002/ejoc.201201637
• Languages: English
• ISSNs: 1434-193X

Abstract

Abstract: This paper describes the solvent‐assisted addition of trimethylsilyl cyanide (TMSCN) to cyclic α‐fluorinated ketones. In DMF, this method gives TMS‐protected cyanohydrins in good yields (70–95 %) and with good selectivities ( dr up to 22:1), and the products are readily reduced to the corresponding fluorinated 1, 2‐amino alcohols. Abstract : A method for the trimethylsilyl cyanide (TMSCN) addition to α‐fluoro ketones has been developed, giving the nitrile products in high yields and with good to modest stereoselectivities. TMSCN is activated in strongly electron‐donating solvents, such as DMF, to produce the fluorinated TMS‐protected cyanohydrin in yields of up to 95 % and diastereoselectivities as high as 22:1.