Gold-catalyzed addition of N-hydroxy heterocycles to alkynes and subsequent 3,3-sigmatropic rearrangement.

Kumar M, Scobie M, Mashuta MS, Hammond GB, Xu B

Org. Lett. 15 (4) 724-727 [2013-02-15; online 2013-02-04]

Gold-catalyzed intermolecular addition of hydroxybenzotriazole derivatives to alkynes at room temperature, gives vinyl ethers 3 in high yields and with excellent regioselectivity. Unlike many other vinyl ethers, 3 can easily be purified by regular silica-gel chromatography. On heating, 3,3-sigmatropic rearrangement of 3 gives access to highly functionalized benzotriazoles. This two-step sequence represents an efficient oxygen transfer protocol which incorporates a nucleophilic oxygen atom into an alkyne group. Reaction of 3 with an electrophilic fluorinating reagent (Selectfluor) gives a fluorinated ketone regioselectively and in high yield.

Affiliated researcher

PubMed 23379647

DOI 10.1021/ol4000789

Crossref 10.1021/ol4000789

Publications 9.5.0