5532-86-5Relevant articles and documents
An expedient synthesis of cyanoformates via DAST-mediated C–C bond cleavage of α-oximino-β-ketoesters
Kim, Danhee,Lim, Hee Nam
supporting information, (2021/05/10)
A new protocol to synthesize cyanoformates was developed using simple β-ketoesters as substrates. (Diethylamino)sulfur trifluoride (DAST) was used as a dual-role reagent to activate the oxime moiety and to donate a fluoride. The key intermediates, α-oximino-β-ketoesters, were prepared by highly efficient acid-assisted oximation of β-ketoesters. Then, the deconstruction of α-oximino-β-ketoesters by the fluorinative C–C bond cleavage was demonstrated to provide cyanoformates. In this event, the fluoride addition followed by the C–C bond cleavage selectively occurred in the ketones over esters. Due to simple and mild reaction conditions, variously functionalized cyanoformates were exemplified.
Process for producing cyanoformate esters
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, (2008/06/13)
Alkyl, aralkyl or aryl cyanoformate esters having from one to 20 carbon atoms are prepared by anhydrously reacting stoichiometric amounts of the corresponding alkyl, aralkyl or aryl haloformate and an organosilyl nitrile in the presence of a catalytic amount of a tertiary amine base, preferably 1,4-diazabicyclo?2.2.2!octane, in the absence or presence of an inert solvent. The reaction is conducted at a temperature of from about -30° C. to 70° C., preferably at from about 5° C. to 30° C.
