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Catalytic asymmetric dipolar cycloadditions of indolyl delocalized metal-allyl species for the enantioselective synthesis of cyclopenta [ b ]indoles and pyrrolo[1,2- a ]indoles
Science China Chemistry ( IF 9.6 ) Pub Date : 2020-10-21 , DOI: 10.1007/s11426-020-9854-3
Fei Tian , Wu-Lin Yang , Tao Ni , Jian Zhang , Wei-Ping Deng

The development of novel synthons and efficient methods to synthesize chiral polycyclic indoles has been a hot topic in organic synthesis and medicinal chemistry owing to their broad applications in medicines, pesticides, and other functional molecules. Here, we disclosed novel indolyl substituted metal-allyl zwitterionic intermediates through the decarboxylation of conveniently available vinyl indoloxazolidones, which could be regarded as two types of dipolar species through the anionic delocalization. The palladium-π-allyl species tended to serve as an all-carbon 1,3-dipole in the asymmetric [3+2] cycloaddition with electron-deficient alkenes, which furnished polysubstituted cyclopenta[b]indoles with high regio- and stereoselectivities. Meanwhile, the iridium-π-allyl species was recognized as an aza-1,3-dipole in asymmetric [3+2] cycloaddition with in situ generated C1 ammonium enolates, affording pyrrolo[1,2-a]indoles with high diastereo- and enantioselectivities. In addition, the dipolar cycloadditions could be easily scaled-up and several synthetic transformations of the cycloadducts were demonstrated for the rapid synthesis of diverse chiral polycyclic indoles.



中文翻译:

吲哚基离域金属-烯丙基物种的催化不对称偶极环加成,用于对映体合成环戊[b]吲哚和吡咯并[1,2-a]吲哚

由于其在药物,农药和其他功能分子中的广泛应用,新型合成子和合成手性多环吲哚的有效方法的开发一直是有机合成和药物化学领域的热门话题。在这里,我们公开了通过方便地获得的乙烯基吲哚恶唑烷酮的脱羧作用而得到的新颖的吲哚基取代的金属-烯丙基两性离子中间体,通过阴离子离域化可以将其视为两种偶极种类。钯-π-烯丙基物种倾向于在不对称的[3 + 2]与缺电子的烯烃的加成中用作全碳的1,3-偶极子,从而提供了多取代的环戊烯[ b具有高区域选择性和立体选择性的吲哚。同时,在原位生成的C1烯醇铵不对称[3 + 2]环加成反应,铱-π-烯丙基物种被认为是aza-1,3-偶极子,提供具有高非对映异构体的吡咯并[1,2- a ]吲哚。和对映选择性。另外,偶极环加成可以容易地按比例放大,并且环加合物的几种合成转化被证明用于快速合成各种手性多环吲哚。

更新日期:2020-10-30
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