Ruthenium-Catalyzed Nucleophilic Allylic Substitution Reactions from β-Silylated Allylic Carbonates
作者:Hui-Jun Zhang、Bernard Demerseman、Loïc Toupet、Zhenfeng Xi、Christian Bruneau
DOI:10.1021/om900437m
日期:2009.9.14
propargylic ethyl carbonates catalyzed by the ruthenium complex [Ru(C5Me5)(MeCN)3][PF6], 1, leads to H2C═C(SiEt3)CH(R)OCO2Et (R = H, Me, Prn, or Ph) derivatives as allylic substrates for subsequent ruthenium-catalyzed nucleophilic allylic substitution reactions. Ruthenium catalysts based on a [Ru(C5Me5)(2-quinolinecarboxylato)] or [Ru(C5Me5)(2,2′-bipyridine)]+ fragment are more efficient than 1 for access
的反式加成HSiEt的3至炔乙基碳酸盐催化由钌络合物的[Ru(C 5我5)(MeCN中)3 ] [PF 6 ],1,引线至H 2 C = C(SIET 3)CH(R) OCO 2的Et(R = H,Me中,镨ñ,或pH)衍生物作为用于随后的钌催化的亲核烯丙基取代反应的烯丙基底物。基于[Ru(C 5 Me 5)(2-喹啉羧基羧酸)]或[Ru(C 5 Me 5)(2,2'-联吡啶)] +片段的钌催化剂比1用于访问各种ħ 2 C = C(SIET 3)CH(R)的Nu-官能乙烯基硅烷(R = H,甲基;新加坡国立大学医院=仲胺,苯酚,丙二酸二甲酯,甲醇)。新的[Ru(C 5我5)(2-quinolinecarboxylato)(η 3 -烯丙基)] +的阳离子钌(IV)的中间体的特征在于,使用氘标记的烯丙基碳酸酯实验用于从存在引起的区域选择性提供证据2-喹啉羧基(N,O)-螯合物。