Hypervalent Iodine-Based Activation of Triphenylphosphine for the Functionalization of AlcoholsThis work was supported by the University of Waterloo and the Natural Sciences and Engineering Research Council (NSERC) of Canada (Discovery Grant 418602-2013).
Received: 18 April 2017
Accepted after revision: 06 June 2017
12 July 2017 (eFirst)
Dedicated to Professor Victor Snieckus on the occasion of his 80th birthday
The use of hypervalent iodine reagents as a general tool for the activation of PPh3 and its application to the functionalization of alcohols is reported. Combination of PPh3 with PhICl2 or TolIF2 gives dihalophosphoranes that are characterized by 31P NMR, however, with PhIOAc2, PhI(OTFA)2, or the cyclic chloro(benzoyloxy)iodane, no phosphoranes were observed. Reaction of these iodanes with PPh3 in the presence of primary, secondary, or tertiary alcohols results in either halogenation or acyl-transfer products in moderate to high yield.