Stereoselective access to highly substituted vinyl ethers via trans-difunctionalization of alkynes with alcohols and iodine(III) electrophile

A method for the regio- and stereoselective synthesis of highly substituted vinyl ethers via trans-1,2-difunctionalization of alkynes with a cyclic λ3-iodane electrophile (benziodoxole triflate) and alcohols is reported. The reaction tolerates a variety of internal and terminal alkynes as well as various alcohols, affording β-λ3-iodanyl vinyl ethers in good yields with high regio- and stereoselectivities. The benziodoxole moiety of the products can be used as a versatile linchpin for the synthesis of structurally diverse vinyl ethers that are difficult to access by other means.Ministry of Education (MOE)Accepted versionThis work was supported by the Ministry of Education(Singapore) and Nanyang Technological University(MOE2016-T2-2-043 and RG114/18). We thank Dr. Yongxin Li (Nanyang Technological University) for his assistance withthe X-ray crystallographic analysis