Remarkable rate acceleration of SmI3-mediated iodination of acetates of Baylis-Hillman adducts in ionic liquid: facile synthesis of (Z)-allyl iodides / 浙江大学学报（英文版）（B辑：生物医学和生物技术）

Stereoselective transformation of Baylis-Hillman acetates 1 into corresponding (Z)-allyl iodides 2 has been achieved by treatment of 1 with samarium triiodide in THF. Remarkable rate acceleration of samarium triiodide-mediated iodination of 1 was found when ionic liquid 1-n-butyl-3-methyl-imidazolium tetrafluroborate ([bmim]BF(4)) was used as reaction media in stead of THF. This novel approach proceeds readily at 50 degrees C within a few minutes to afford (Z)-allyl iodides 2 in excellent yields. A mechanism involving stereoselective iodination of the acetates of Baylis-Hillman adducts by samarium triiodide is described, in which a six-membered ring transition state played a key role in the stereoselective formation of 2.

A convenient and stereoselective synthesis of (Z)-allyl selenides via Sm/TMSCl system-promoted coupling of Baylis-Hillman adducts with diselenides / 浙江大学学报（英文版）（B辑：生物医学和生物技术）

A simple and convenient procedure for stereoselective synthesis of (Z)-allyl selenides has been developed by a one-pot reaction of diselenides with Baylis-Hillman adducts in the presence of samarium metal-trimethylsilyl chloride under mild conditions. Presumably, the diselenides are cleaved by Sm/TMSCl system to form selenide anions, which then undergo S(N)2' substitution of Baylis-Hillman adducts to produce the (Z)-allyl selenides.