A Benzoyl Peroxide/Diphenyl Diselenide Binary System for Functionalization of Alkynes Leading to Alkenyl and Alkynyl Selenides.

Binary systems consisting of benzoyl peroxide (BPO) and diorganyl diselenide are effective in the selective benzoyloxyselenation of internal alkynes to afford the corresponding β-(benzoyloxy)alkenyl selenides in good yields. In contrast to internal alkynes, terminal alkynes undergo a novel C(sp)-H substitution with the phenylseleno group of the BPO/(PhSe)2 system, providing alkynyl selenides in good yields. Both selenation reactions might proceed via benzoyloxy selenide (PhC(O)O-SeAr) as a key intermediate for electrophilic addition to alkynes. The products alkenyl and alkynyl selenides are expected to be useful synthetic intermediates in organic synthesis.