ゴールド(Z)-エンチオラートの立体選択的合成とその反応

抄録

We reported stereoselective synthesis and reaction of silver (Z)-alkylenethiolates, which serve as a stabilized (Z)-enethiol storage. We report herein synthesis of gold (Z)-alkylenethiolates, and their alkylations and Michael additions. Exposure of (Z)-S-(vinyl)thioimidonium salts, prepared by vinylic SN2 reaction of (E)-1-alkenyliodanes(III), to AuCl(THT) (THT = tetrahydrothiophene) and 5% aqueous Na2CO3 in THF at room temperature afforded gold (Z)-enethiolates stereoselectively. Whereas (Z)-enethiols are labile and their isolation is difficult because of their high tendency to dimerize to dithiohemiacetals, the gold (Z)-enethiolates are easily isolated and stored in a refrigerator. Alkylation of the gold (Z)-enethiolates with alkyl halides yielding vinyl sulfides was remarkably accelerated by the addition of PPh3 or NHC (N-heterocyclic carbenes).