Highly regioselective Pd-catalyzed intermolecular aminoacetoxylation of alkenes and evidence for cis-aminopalladation and SN2 C-O bond formation
Highly regioselective Pd-catalyzed intermolecular aminoacetoxylation of alkenes and evidence for cis-aminopalladation and SN2 C-O bond formation
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DOI：
10.1021/ja061706h
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发表时间：
2006-06-07
影响因子：
15
通讯作者：
Stahl, Shannon S.
中科院分区：
文献类型：
--
作者：
Liu, Guosheng;Stahl, Shannon S.
实现烯烃的氧化1，2-双官能化的合成方法在有机化学中是非常强大的。本文报道了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源，Pd催化的烯烃氨基乙酰氧基化反应的第一个实例。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，反应通过烯烃的氨基钯化进行，然后通过氧化裂解中间体Pd-C键并转化立体化学。
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)2as the stoichiometric oxidant and source of acetate. These reactions are highly regio- and diastereoselective, and mechanistic studies reveal that the reaction proceeds viacis-aminopalladation of the alkene followed by oxidative cleavage of the intermediate Pd−C bond with inversion of stereochemistry.