Copper(I)-Catalyzed Asymmetric Conjugate Addition of 1,4-Dienes to β-Substituted Alkenyl Azaarenes
Copper(I)-Catalyzed Asymmetric Conjugate Addition of 1,4-Dienes to β-Substituted Alkenyl Azaarenes
复制标题
铜 (I) 催化 1,4-二烯不对称共轭加成到 β-取代的烯基氮杂芳烃
DOI：
10.1021/jacs.2c10688
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发表时间：
2023
影响因子：
15
通讯作者：
Liang Yin
中科院分区：
文献类型：
--
作者：
Zhi-Zhou Pan;Deng Pan;Jia-Heng Li;Xiao-Song Xue;Liang Yin
Chiral azaarene compounds are extremely important due to their prevalence in pharmaceutical ingredients. Herein, an array of chiral molecules bearing azaaryl groups is synthesized in moderate-to-excellent yields with moderate-to-excellentZ/Eratios, high dr, and excellent enantioselectivity by a copper(I)-catalyzed asymmetric conjugate addition of 1,4-dienes to (E)-β-substituted alkenyl azaarenes. The reaction is carried out under mild proton-transfer conditions, which enjoys very high atom economy. Moreover, the reaction features a broad substrate scope on (E)-α,β-unsaturated azaarenes as various azaarenes are well tolerated, such as benzothiazole, thiazole,N-methyl-benzimidazole, benzoxazole, quinoline, isoquinoline, pyrimidine, pyrazine, and triazine. Interestingly, the reaction with (Z)-α,β-unsaturated azaarenes affords the same products in excellent results but with a reversed absolute configuration. DFT calculations indicate that the C–C bond-forming nucleophilic addition is aZ-/E- and enantio-selectivities-determining step and provides a rationale for the origin of selectivities. At last, the synthetic utilities of the product are showcased by several transformations, including olefin metathesis, [4 + 2] cyclization, [2 + 1] cyclization, and cleavage of the benzothiazole ring.
