Synthesis of Phenol‐Derived <i>cis</i>‐Vinyl Ethers Using Ethynyl Benziodoxolone
Tomoki Ura, Daisuke Shimbo, Masaharu Yudasaka, Norihiro Tada, Akichika Itoh
Abstract
The stereoselective synthesis of cis-β-phenoxyvinyl benziodoxolones (cis-β-phenol-VBXs) from an ethynyl benziodoxolone-acetonitrile complex (EBX-MeCN) and various phenols is reported herein. The reaction tolerates different phenol derivatives, including complex natural products, and can be conducted under mild conditions. The synthesis was performed in an aqueous solvent in the absence and presence of a catalytic amount of a base. Selectively mono- and di-deuterated cis-β-phenol-VBXs were also prepared. cis-β-Phenol-VBXs were stereospecifically derivatized to cis-alkynylvinyl ethers and cis-iodovinyl ethers without loss of stereoselectivity or reduction in the deuterium/hydrogen ratio.