Diverse Reactions of Vinyl Diazo Compounds with Quinone Oxonium Ions, Quinone Imine Ketals, and Eschenmoser’s Salt
Diverse Reactions of Vinyl Diazo Compounds with Quinone Oxonium Ions, Quinone Imine Ketals, and Eschenmoser’s Salt
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DOI：
10.1021/acscatal.1c02674
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发表时间：
2021-08
期刊：
影响因子：
12.9
通讯作者：
Haifeng Zheng;Kan Wang;Isa Faghihi;W. Griffith;Hadi D Arman;M. Doyle
中科院分区：
文献类型：
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作者：
Haifeng Zheng;Kan Wang;Isa Faghihi;W. Griffith;Hadi D Arman;M. Doyle
无金属亲电试剂对乙烯基重氮化合物的加成反应揭示了高选择性的[3 + 2]环化、烯烃的1，2-双官能化和C-H官能化。这些方法的成功是基于亲电加成到乙烯基重氮化合物的乙烯基位置，形成乙烯基重氮离子中间体。通过使用不同的亲电试剂，这些高活性中间体显示出不同的反应活性，以高产率和选择性提供β-苯并氢呋喃-、β-甲氧基-β-苄基-和γ-氨基烯丙基取代的α-重氮酯。包括迁移、氧化、扩环和缀合物加成的进一步转化突出了该方法的潜在效用。
Metal-free electrophile addition to vinyl diazo compounds reveals highly selective formal [3 + 2] cyclization, 1,2-difunctionalization of alkenes, and C–H functionalization. The success of these methodologies is based on electrophilic addition to the vinylogous position of vinyl diazo compounds, forming vinyl diazonium ion intermediates. By using diverse electrophilic reagents, these highly reactive intermediates show diverse reactivities, affording β-benzohydrofuran-, β-methoxy-β-benzyl-, and γ-aminoallyl-substituted α-diazo esters in high yields and selectivities. Further transformations that include migration, oxidation, ring-expansion, and conjugate addition highlight the potential utility of this method.