Zhang Wen-Xiong, Hou Zhaomin
Organometallic Chemistry Laboratory, RIKEN (The Institute of Physical and Chemical Research), Hirosawa 2-1, Wako, Saitama 351-0198, Japan.
Org Biomol Chem. 2008 May 21;6(10):1720-30. doi: 10.1039/b800135a. Epub 2008 Apr 3.
Various metal complexes (e.g., lanthanides, early transition metals, and alkali metals) can serve as catalyst precursors for the catalytic addition of alkyne C-H, amine N-H, and phosphine P-H bonds to carbodiimides, to give a new family of propiolamidines, guanidines, and phosphaguanidines, some of which were difficult to prepare previously. The catalytic reaction proceeds generally through nucleophilic addition of an M-ER (E=CR(1)R(2), NR(1), PR(1)) bond, which is formed by an acid-base reaction between a catalyst precursor and a RE-H bond, to a carbodiimide compound, followed by protonolysis of the resultant amidinate-(phospha)guanidinate species "{R'NC(ER)NR'}M" with RE-H.
各种金属配合物（例如镧系元素、早期过渡金属和碱金属）可作为催化剂前体，用于催化炔烃的C-H键、胺的N-H键和膦的P-H键与碳二亚胺加成，生成一类新型的丙炔脒、胍和磷胍，其中一些以前难以制备。催化反应通常通过M-ER（E=CR(1)R(2)、NR(1)、PR(1)）键的亲核加成进行，该键由催化剂前体与RE-H键之间的酸碱反应形成，加成到碳二亚胺化合物上，随后所得脒基-（磷）胍基物种“{R'NC(ER)NR'}M”与RE-H发生质子解反应。
