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双功能有机催化剂促进的不对称 spirooxindole 环氧化反应的合成。

Asymmetric Synthesis of Spirooxindoles via Nucleophilic Epoxidation Promoted by Bifunctional Organocatalysts.

机构信息

Dipartimento di Scienze- Sezione di Nanoscienze e Nanotecnologie, Università degli Studi di Roma Tre, V.le G. Marconi 446, I-00146 Rome, Italy.

Dipartimento di Medicina Molecolare e Traslazionale (DMMT), Università di Brescia, viale Europa 11, 25123 Brescia, Italy.

出版信息

Molecules. 2018 Feb 16;23(2):438. doi: 10.3390/molecules23020438.

DOI:10.3390/molecules23020438
PMID:29462935
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC6017607/
Abstract

Taking into account the postulated reaction mechanism for the organocatalytic epoxidation of electron-poor olefins developed by our laboratory, we have investigated the key factors able to positively influence the H-bond network installed inside the substrate/catalyst/oxidizing agent. With this aim, we have: (i) tested a few catalysts displaying various effects that noticeably differ in terms of steric hindrance and electron demand; (ii) employed α-alkylidene oxindoles decorated with different substituents on the aromatic ring (-), the exocylic double bond (-), and the amide moiety (-). The observed results suggest that the modification of the electron-withdrawing group (EWG) weakly conditions the overall outcomes, and conversely a strong influence is unambiguously ascribable to either the -protected or -unprotected lactam framework. Specifically, when the NH free substrates (-) are employed, an inversion of the stereochemical control is observed, while the introduction of a Boc protecting group affords the desired product in excellent enantioselectivity (97:3 ).

摘要

考虑到我们实验室提出的用于缺电子烯烃的有机催化环氧化反应机理，我们研究了能够积极影响底物/催化剂/氧化剂内部氢键网络的关键因素。为此，我们：(i) 测试了几种显示出在空间位阻和电子需求方面明显不同的效果的催化剂；(ii) 采用了α-亚烷基氧化吲哚，其在芳环(-)、外双键(-)和酰胺部分(-)上具有不同的取代基。观察到的结果表明，吸电子基团 (EWG) 的修饰对整体结果的影响较弱，而保护或非保护的内酰胺骨架的强烈影响则是明确的。具体来说，当使用 NH 游离的底物 (-) 时，观察到立体化学控制的反转，而 Boc 保护基的引入则以优异的对映选择性（97:3 ）得到所需产物。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/67a7/6017607/68cb75d0eb90/molecules-23-00438-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/67a7/6017607/c09e5655f4bd/molecules-23-00438-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/67a7/6017607/2fc9c2fc886b/molecules-23-00438-sch001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/67a7/6017607/fbf2273827c5/molecules-23-00438-sch002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/67a7/6017607/f8da891dcfd9/molecules-23-00438-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/67a7/6017607/210ab8742b06/molecules-23-00438-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/67a7/6017607/68cb75d0eb90/molecules-23-00438-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/67a7/6017607/c09e5655f4bd/molecules-23-00438-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/67a7/6017607/2fc9c2fc886b/molecules-23-00438-sch001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/67a7/6017607/fbf2273827c5/molecules-23-00438-sch002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/67a7/6017607/f8da891dcfd9/molecules-23-00438-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/67a7/6017607/210ab8742b06/molecules-23-00438-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/67a7/6017607/68cb75d0eb90/molecules-23-00438-g004.jpg

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