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Synthesis of Hypervalent Iodonium Alkynyl Triflates for the Application of Generating Cyanocarbenes
Published on: September 8, 2013
Synthesis, Structure and Reactivity of a Cyapho-Cyanamide Salt
Doruk Ergöçmen1, Jose M Goicoechea1
1Department of Chemistry, University of Oxford, Chemistry Research Laboratory, 12 Mansfield Road, Oxford, OX1 3TA, U.K.
Abstract:
We describe a facile synthesis of the cyapho-cyanamide salt [Na(18-crown-6)][N(CN)(CP)] from reaction of [Na(18-crown-6)][PH2 ] (18-crown-6=1,4,7,10,13,16-hexaoxacyclooctadecane) with dimethyl N-cyanocarbonimidate, (MeO)2 C=N(CN). The reaction proceeds with elimination of two equivalents of methanol. Careful tuning of the reaction conditions allowed for the isolation and characterization of the N-cyano(carboximidate)phosphide intermediate [HP{C(OMe)N(CN)}]- . Due to the adverse effects of methanol in these reaction mixtures, a bulk scale synthesis of [Na(18-crown-6)][N(CN)(CP)] could be achieved by addition of a base (LiHMDS) to neutralize the resulting alcohol. Further reactivity studies of this anion reveal that functionalization at the phosphorus atom is viable to yield a new family of cyanide-functionalised phosphorus heterocycles.
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