Department of Chemistry and Biochemistry, University of Maryland, College Park, Maryland 20742, USA.
J Am Chem Soc. 2013 Jan 30;135(4):1244-7. doi: 10.1021/ja311392m. Epub 2013 Jan 17.
Transition-metal catalysts direct 1,2-C→C, -O→C, and -N→C migrations from β-methylene-β-silyloxy-β-amido-α-diazoacetates with high selectivity. The key to achieving this unique display of differential selectivities relies on steric and stereoelectronic control by their catalytically generated metal carbenes.
过渡金属催化剂可高选择性地引导β-亚甲基-β-硅氧基-β-酰胺-α-重氮乙酰酸盐进行 1,2-C→C、-O→C 和 -N→C 迁移。实现这种独特的差分选择性显示的关键在于其催化生成的金属卡宾的空间和立体电子控制。