Liu Guosheng, Stahl Shannon S
Department of Chemistry, University of Wisconsin--Madison, 1101 University Avenue, Madison, Wisconsin 53706, USA.
J Am Chem Soc. 2006 Jun 7;128(22):7179-81. doi: 10.1021/ja061706h.
Synthetic methods that achieve oxidative 1,2-difunctionalization of alkenes are very powerful in organic chemistry. Here we report the first examples of intermolecular Pd-catalyzed aminoacetoxylation of alkenes with phthalimide as the nitrogen source and PhI(OAc)2 as the stoichiometric oxidant and source of acetate. These reactions are highly regio- and diastereoselective, and mechanistic studies reveal that the reaction proceeds via cis-aminopalladation of the alkene followed by oxidative cleavage of the intermediate Pd-C bond with inversion of stereochemistry.
实现烯烃氧化1,2-双官能化的合成方法在有机化学中非常强大。在此，我们报道了首例以邻苯二甲酰亚胺为氮源、PhI(OAc)₂为化学计量氧化剂和乙酸盐来源的分子间钯催化烯烃氨基乙酰氧基化反应。这些反应具有高度的区域选择性和非对映选择性，机理研究表明该反应通过烯烃的顺式氨基钯化反应进行，随后中间体钯-碳键发生氧化裂解，立体化学发生翻转。
