铜(I)催化的烯丙基含氮芳香杂环的不对称插烯羟

本期文章:《德国应用化学》:Online/在线发表

中科院上海有机所的殷亮课题组在铜催化的不对称插烯羟醛型反应(Vinylogous Aldol-Type Reaction)领域取得新进展,相关论文于2020年11月20日发表于国际顶尖学术期刊《德国应用化学》上。

在该文中,研究人员描述了一种发生在烯丙基含氮芳香杂环(allylazaarenes)和醛类间的插烯羟醛型反应,该反应可以中上的产率生成一系列区位和手性选择性优良的手性γ-羟基-α,β-不饱和含氮芳香杂环化合物。以(R, Rp)‐TANIAPHOS和(R, R)‐QUINOXP*为配体时,产物中的碳碳双键为(E)‐构象;而以(R)‐DTBM‐SEGPHOS为配体时,在主产物中形成(Z)‐构象的碳碳双键。

研究人员表示,在该插烯反应中,芳香醛、α,β-不饱和醛和脂肪醛都是合适的底物。此外,该反应对各种含氮芳香杂环类化合物如嘧啶、吡啶、吡嗪、喹啉、喹恶啉、喹唑啉、苯并咪唑等均有良好的兼容性。最后,研究人员还展示了生成的手性插烯产物作为合适的Michael反应受体在CuI催化下与有机镁试剂发生亲核加成反应。

附:英文原文

Title: Copper(I)‐Catalyzed Asymmetric Vinylogous Aldol‐Type Reaction of Allylazaarenes

Author: Si-Qing Wang, Zong-Ci Liu, Wen-Jun Yue, Liang Yin

Issue&Volume: 20 November 2020

Abstract: A vinylogous aldol‐type reaction of allylazaarenes and aldehydes is disclosed, which affords a series of chiral γ‐hydroxyl‐α,β‐unsaturated azaarenes in moderate to excellent yields with high to excellent regio‐ and enantioselectivities. With (R, Rp)‐TANIAPHOS and (R, R)‐QUINOXP* as the ligand, the carbon‐carbon double bond in the products is generated in (E)‐form. With (R)‐DTBM‐SEGPHOS as the ligand, (Z)‐form carbon‐carbon double bond is formed in the major product. In this vinylogous reaction, aromatic, α,β‐unsaturated, and aliphatic aldehydes are competent substrates. Moreover, a variety of azaarenes, such as pyrimidine, pyridine, pyrazine, quinoline, quinoxaline, quinazoline, and benzo[d]imidazole are well tolerated. At last, the chiral vinylogous product is demonstrated as a suitable Michael acceptor towards CuI‐catalyzed nucleophilic addition with organomagnesium reagents.

DOI: 10.1002/anie.202013207

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202013207

期刊信息

Angewandte Chemie:《德国应用化学》,创刊于1887年。隶属于德国化学会,最新IF:12.959
官方网址:https://onlinelibrary.wiley.com/journal/15213773
投稿链接:https://www.editorialmanager.com/anie/default.aspx