Palladium‐Catalyzed Intramolecular Mizoroki‐Heck‐Type Reaction of Diarylmethyl Carbonates
Palladium‐Catalyzed Intramolecular Mizoroki‐Heck‐Type Reaction of Diarylmethyl Carbonates
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DOI：
10.1002/adsc.201901398
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发表时间：
2020-02
影响因子：
5.4
通讯作者：
Akihiro Matsude;K. Hirano;M. Miura
中科院分区：
文献类型：
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作者：
Akihiro Matsude;K. Hirano;M. Miura
发展了钯催化的碳酸二芳甲基叔丁酯的分子内Mizoroki-Heck-type反应。该反应在外部无碱、中性条件下进行，以良好的产率形成相应的亚甲基茚满，仅释放CO2和tBuOH。所得的exo-methylene部分是反应性的，因此是用于进一步操作的良好合成手柄。此外，通过Pd/手性Mandyphos配体介导的动力学拆分也可以进行不对称合成。据我们所知，这是第一个成功的例子，催化对映选择性Mizoroki-Heck-型反应的仲苄基亲电试剂。
A palladium‐catalyzed intramolecular Mizoroki‐Heck‐type reaction of diarylmethyltert‐butyl carbonates has been developed. The reaction proceeds under external base‐free, neutral conditions to form the corresponding methyleneindanes in good yields only with liberation of CO2andtBuOH. The resultingexo‐methylene moiety is reactive and thus a good synthetic handle for further manipulations. Additionally, the asymmetric synthesis is also possible through a Pd/chiral Mandyphos ligand‐mediated kinetic resolution. To the best of our knowledge, this is the first successful example of catalytic enantioselective Mizoroki‐Heck‐type reaction of secondary benzyl electrophiles.