基于亚氨基内酯的不对称1,3-偶极环加成反应，由亲偶极体导向的2,5-顺式/反式吡咯烷的形式立体发散合成
Dipolarophile-Steered Formal Stereodivergent Synthesis of 2,5-cis/trans-Pyrrolidines Based on Asymmetric 1,3-Dipolar Cycloaddition of Imino Lactones.
作者信息
Furuya Shohei, Muroi Kenji, Kanemoto Kazuya, Fukuzawa Shin-Ichi
机构信息
Department of Applied Chemistry, Faculty of Science and Engineering, Chuo University, 1-13-27 Kasuga, Bunkyo-ku, Tokyo, 112-8551, Japan.
Graduate School of Pharmaceutical Sciences, Tohoku University, 6-3 Aoba, Aramaki, Aoba-ku, Sendai, 980-8578, Japan.
出版信息
Chemistry. 2023 Nov 24;29(66):e202302609. doi: 10.1002/chem.202302609. Epub 2023 Oct 13.
The stereodivergent asymmetric synthesis of 2,5-trans/cis pyrrolidines by 1,3-dipolar cycloaddition using two different types of activated alkenes is described. When ylidene-isoxazolones were employed as dipolarophiles, the Ag/(S,S )-iPr-FcPHOX-catalyzed asymmetric [3+2] cycloaddition of imino lactones proceeded with 2,5-trans selectivity. Subsequent decarboxylation of the isoxazolone rings produced pyrrolidines with 2,5-trans stereoretention. In the reaction using acyclic enones as activated alkenes, the Ag/(R,S )-ThioClickFerrophos complex-catalyzed asymmetric [3+2] cycloaddition afforded 2,5-cis substituted pyrrolidines in high yields and enantioselectivities. Therefore, these methods can be considered as a formal stereodivergent synthesis of 2,5-cis/trans pyrrolidines.
本文描述了使用两种不同类型的活化烯烃通过1,3-偶极环加成反应立体发散地不对称合成2,5-反式/顺式吡咯烷。当亚烷基异恶唑酮用作亲偶极体时，Ag/(S,S)-异丙基-二茂铁膦手性配体催化的亚氨基内酯的不对称[3+2]环加成反应以2,5-反式选择性进行。随后异恶唑酮环的脱羧反应产生具有2,5-反式立体构型保留的吡咯烷。在使用无环烯酮作为活化烯烃的反应中，Ag/(R,S)-硫代Click二茂铁膦配合物催化的不对称[3+2]环加成反应以高产率和对映选择性得到2,5-顺式取代的吡咯烷。因此，这些方法可被视为2,5-顺式/反式吡咯烷的形式上的立体发散合成。
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