Casey Charles P, Bikzhanova Galina A, Guzei Ilia A
Department of Chemistry, University of Wisconsin, Madison, WI 53706, USA.
J Am Chem Soc. 2006 Feb 22;128(7):2286-93. doi: 10.1021/ja056402u.
The stereochemistry of hydrogen transfer from [2,5-Ph(2)-3,4-Tol(2)(eta(5)-C(4)COD)]Ru(CO)(2)D to N-aryl imines to give amine complexes was shown to be mostly trans stereospecific. Stereospecific hydrogen transfer is proposed to generate an amine and a coordinatively unsaturated ruthenium intermediate in close proximity. Coordination of the amine is proposed to occur faster than lone pair inversion of the amine. In contrast, hydrogen transfer to N-alkyl imines is stereorandom. It is proposed that stereochemistry is lost in part due to the reversibility of the hydrogen transfer being faster than amine coordination.
从[2,5-二苯基-3,4-二甲基（η⁵-环辛二烯）]钌（Ⅱ）二羰基氢化物（[2,5-Ph(2)-3,4-Tol(2)(η⁵-C(4)COD)]Ru(CO)(2)D）到N-芳基亚胺的氢转移生成胺配合物的立体化学被证明大多是反式立体专一性的。立体专一性氢转移被认为会生成一个胺和一个紧密相邻的配位不饱和钌中间体。胺的配位被认为比胺的孤对反转发生得更快。相比之下，氢转移到N-烷基亚胺是立体随机的。据推测，立体化学部分丧失是由于氢转移的可逆性比胺的配位更快。
