Highly Stereoselective Synthesis of 1,2-Disubstituted Indanes by Pd-Catalyzed Heck/Suzuki Sequence of Diarylmethyl Carbonates
Highly Stereoselective Synthesis of 1,2-Disubstituted Indanes by Pd-Catalyzed Heck/Suzuki Sequence of Diarylmethyl Carbonates
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DOI：
10.1021/acs.orglett.0c00945
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发表时间：
2020-04-17
期刊：
影响因子：
5.2
通讯作者：
Miura, Masahiro
中科院分区：
文献类型：
--
作者：
Matsude, Akihiro;Hirano, Koji;Miura, Masahiro
已开发出一种钯催化的碳酸二芳基甲基酯与芳基硼酸衍生物的 Mizoroki-Heck 型环化/Suzuki-Miyaura 交叉偶联级联，可以以良好的产率和高非对映选择性（反式/顺式 > 20:1）生成相应的 1,2-二取代茚满。实现高化学选择性和立体选择性的关键是使用远程空间位阻的三[3,5-二(叔丁基)-4-甲氧基苯基膦(DTBMP)配体。此外，通过光学活性起始底物的对映特异性、立体反转反应可以进行不对称合成，形成具有高立体化学保真度（> 98% es）的手性茚满。
A palladium-catalyzed Mizoroki-Heck-type cyclization/Suzuki-Miyaura cross-coupling cascade of diarylmethyl carbonates with arylboronic acid derivatives has been developed to deliver the corresponding 1,2-disubstituted indanes in good yields with high diastereoselectivity (trans/cis > 20:1). The key to achieve the high chemoselectivity and stereoselectivity is the use of the tris[3,5-di(tert-butyl)-4-methoxyphenyllphosphine (DTBMP) ligand of remote steric hindrance. Moreover, the asymmetric synthesis is possible by the enantiospecific, stereoinvertive reaction of the optically active starting substrates to form the chiral indanes with high stereochemical fidelity (>98% es).