Copper(I)‐Catalyzed Asymmetric Vinylogous Aldol‐Type Reaction of Allylazaarenes
Copper(I)‐Catalyzed Asymmetric Vinylogous Aldol‐Type Reaction of Allylazaarenes
复制标题
铜(I)催化烯丙基氮杂芳烃的不对称乙烯基醇醛型反应
DOI：
10.1002/anie.202013207
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发表时间：
2021
期刊：
影响因子：
--
通讯作者：
Liang Yin
中科院分区：
文献类型：
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作者：
Si‐Qing Wang;Zong‐Ci Liu;Wen‐Jun Yue;Liang Yin
公开了烯丙基氮杂芳烃和醛的乙烯基羟醛缩合型反应，其以中等至优异的产率和高至优异的区域选择性和对映选择性提供一系列手性γ-羟基-α，β-不饱和氮杂芳烃。以（R，RP）-TANIAPHOS和（R，R）-QUINOXP* 为配体，产物中的碳-碳双键以（E）-形式生成。以（R）-DTBM-SEGPHOS为配体，在主要产物中形成（Z）-型碳-碳双键。在该乙烯基化反应中，芳香族、α，β-不饱和和脂肪族醛是合适的底物。此外，各种氮杂芳烃，如嘧啶、吡啶、吡嗪、喹啉、喹喔啉、喹唑啉和苯并[d]咪唑耐受良好。最后，手性乙烯基醚产物被证明是一个合适的迈克尔受体对CuI催化的亲核加成与有机镁试剂。
A vinylogous aldol‐type reaction of allylazaarenes and aldehydes is disclosed that 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.