Asymmetric Catalytic 1,6-Conjugate Addition/Aromatization of para-Quinone Methides: Enantioselective Introduction of Functionalized Diarylmethine Stereogenic Centers
Asymmetric Catalytic 1,6-Conjugate Addition/Aromatization of para-Quinone Methides: Enantioselective Introduction of Functionalized Diarylmethine Stereogenic Centers
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DOI：
10.1002/anie.201303928
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发表时间：
2013-08-26
影响因子：
16.6
通讯作者：
Fan, Chun-An
中科院分区：
文献类型：
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作者：
Chu, Wen-Dao;Zhang, Le-Fen;Fan, Chun-An
Wen-Dao Chu，Le-Fen Zhang，Xu Bao，Xian-He Zhao，Chao Zeng，Ji-Yuan Du，Guo-Biao Zhang，Fang-Xin Wang，Xiao-Yan Ma，and Chun-An Fan (1)]，[1]，其结构特征在于羰基和烯属部分的独特组装，并且化学上被定义为中性和两性离子共振实体，在有机化学中已经已知超过世纪。[2]在自然界中，p-QM单元存在于各种天然产物中，如真菌代谢产物、萜烯和植物色素。[3]由于p-QM的固有亲电反应性，原位产生的高反应性瞬时p-QM物质涉及许多化学、医学和生物过程，如木质素生物合成、酶抑制和DNA烷基化和交联。[1，4]在合成上，邻醌甲基化物（o-QMs），p-QMs的结构异构体，已被广泛研究用于开发不对称方法，如1，4-共轭加成，[4+ 2]-环加成和6π电环化。[5]但令人惊讶的是，很少有对映选择性添加的p-QMs已被记录，特别是在催化不对称的方式。[1，6-8]因此，开发有效的催化对映选择性加成p-QM仍然是现代有机合成中的一个重要挑战。
Wen-Dao Chu, Le-Fen Zhang, Xu Bao, Xian-He Zhao, Chao Zeng, Ji-Yuan Du, Guo-Biao Zhang, Fang-Xin Wang, Xiao-Yan Ma, and Chun-An Fan* para-Quinone methides [p-QMs; Eq.(1)],[1] which are structurally characterized by the unique assembly of carbonyl and olefinic moieties, and chemically defined as neutral and zwitterionic resonance entities, have been already known for more than one century in organic chemistry.[2] In nature, p-QM units exist in a variety of natural products such as fungal metabolites, terpenes, and plant pigments.[3] As a result of the intrinsic electrophilic reactivity of p-QMs, highly reactive transient p-QM species generated in situ are implicated in many chemical, medicinal, and biological processes such as lignin biosynthesis, enzyme inhibition, and DNA alkylation and cross-linking.[1, 4] Synthetically, ortho-quinone methides (o-QMs), a structural isomer of p-QMs, have been extensively studied for the development of asymmetric methodologies such as 1, 4-conjugate addition,[4+ 2]-cycloaddition, and 6π electrocyclization.[5] But surprisingly, few enantioselective additions of p-QMs have been documented, especially in a catalytic asymmetric fashion.[1, 6–8] Therefore, the development of an effective catalytic enantioselective addition of p-QMs remains an important challenge in modern organic synthesis.