Department of Applied Chemistry, Graduate School of Engineering, Tokyo University of Agriculture and Technology, Koganei, Tokyo 184-8588, Japan.
J Am Chem Soc. 2010 Jun 16;132(23):7896-8. doi: 10.1021/ja102418h.
A cationic rhodium(I) complex, [Rh(cod)(2)]SbF(6), catalyzes the [3 + 2] cycloaddition of propargyl esters with dialkyl acetylenedicarboxylates in good yields, presumably through carbonyl-stabilized cationic rhodium(I) alkenylcarbene intermediates. The same rhodium(I) complex also catalyzes the [2 + 1] cycloaddition (cyclopropanation) of propargyl esters with N,N-disubstituted acrylamides in good yields with perfect diastereoselectivity.
一种阳离子铑(I)配合物,[Rh(cod)(2)]SbF(6),可以催化炔丙酯与二烷基丙二酸盐的[3 + 2]环加成反应,产率良好,可能是通过羰基稳定的阳离子铑(I)烯基卡宾中间体。同样的铑(I)配合物也可以催化炔丙酯与 N,N-二取代丙烯酰胺的[2 + 1]环加成(环丙烷化)反应,产率良好,具有完美的非对映选择性。