Silver(I)-Catalyzed Atroposelective Desymmetrization of N-Arylmaleimide via 1,3-Dipolar Cycloaddition of Azomethine Ylides: Access to Octahydropyrrolo[3,4-c]pyrrole Derivatives
Silver(I)-Catalyzed Atroposelective Desymmetrization of N-Arylmaleimide via 1,3-Dipolar Cycloaddition of Azomethine Ylides: Access to Octahydropyrrolo[3,4-c]pyrrole Derivatives
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银 (I) 催化的 N-芳基马来酰亚胺通过甲亚胺叶立德的 1,3-偶极环加成进行的对位选择性去对称化：获得八氢吡咯并[3,4-c]吡咯衍生物
DOI：
10.1021/acs.joc.6b00396
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发表时间：
2016-05-06
影响因子：
3.6
通讯作者：
Wang, Chun-Jiang
中科院分区：
文献类型：
--
作者：
Liu, Hua-Chao;Tao, Hai-Yan;Wang, Chun-Jiang
一种高效的Ag（I）催化的N-（2-叔丁基苯基）马来酰亚胺通过原位生成的偶氮甲碱叶立德的1，3-偶极环加成反应已经成功建立，提供了一系列生物学上重要的和对映体富集的八氢吡咯并[3，4-C]吡咯衍生物，产率高（高达99%），具有优异的非对映体/对映体选择性（高达99%ee，>20：1dr）。随后的转换导致迷人的2 H-吡咯和多取代吡咯化合物的立体选择性没有损失。通过单晶X射线衍射分析，所产生的手性轴的绝对构型已明确地确定为（M）。此外，综合的实验结果和环加合物的绝对构型的基础上，立体选择性的起源被认为是由庞大的PPh 2基团的手性配体和N-（2-叔丁基苯基）马来酰亚胺的叔丁基所施加的空间拥挤。手性配体的NH 2基团和N-（2-叔丁基苯基）马来酰亚胺的羰基之一之间可能的氢键相互作用被认为有助于稳定过渡态。
A highly efficient Ag(I)-catalyzed atroposelective desymmetrization of N-(2-t-butylphenyl)maleimide via 1,3-dipolar cycloaddition of in situ generated azomethine ylides has been established successfully, affording a facile access to a series of biologically important and enantioenriched octahydropyrrolo[3,4-c]pyrrole derivatives in generally high yields (up to 99%) with excellent levels of diastereo-/enantioselectivities (up to 99% ee, >20:1 dr). Subsequent transformations led to fascinating 2H-pyrrole and polysubstituted pyrrole compounds without loss of stereoselectivity. The absolute configuration of the generated chiral axis has been unambiguously identified as (M) through single-crystal X-ray diffraction analysis. Furthermore, on the basis of the comprehensive experimental results and the absolute configuration of one of the cycloadducts, the origin of the stereoselectivity was proposed to be attributed to the steric congestion imposed by the bulky PPh2 group of the chiral ligand and the tert-butyl group of N-(2-t-butylphenyl)maleimide. The possible hydrogen bond interaction between the NH2 group of the chiral ligand and one of the carbonyl groups of N-(2-t-butylphenyl)maleimide is considered to facilitate stabilizing the transition state.