Stereoinvertive C－C Bond Formation at the Boron‐Bound Stereogenic Centers via Copper-Bipyridine‐Catalyzed Intramolecular Coupling of α‐Aminobenzylboronic Esters
Stereoinvertive C－C Bond Formation at the Boron‐Bound Stereogenic Centers via Copper-Bipyridine‐Catalyzed Intramolecular Coupling of α‐Aminobenzylboronic Esters
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通过铜联吡啶催化 α-氨基苄基硼酯的分子内偶联在硼键立构中心形成立体反转 C-C 键
DOI：
10.1002/anie.201914864
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发表时间：
2020
期刊：
影响因子：
--
通讯作者：
M.
中科院分区：
文献类型：
--
作者：
Yoshinaga;Y.; Yamamoto;T.; Suginome;M.
在铜催化剂作用下，2，2 ′-联吡啶类非手性配体与α-（2-卤代苯甲酰氨基）苄基硼酸酯发生Suzuki-Miyaura-型分子内偶联反应，合成了3-取代异吲哚啉酮.对映体富集的α-氨基苄基硼反应物在硼键合的立体碳上带有一个氢原子，在具有高对映体特异性的6-苯基-2，2 ′-联吡啶配体的存在下进行立体转化偶联。在简单的2，2 ′-联吡啶配体存在下，具有完全取代的硼键立体异构中心的α-氨基苄基硼酸酯也可得到具有立体定向立体化学反转的3，3-二取代异吲哚啉酮。
Enantiospecific intramolecular Suzuki–Miyaura‐type coupling with α‐(2‐halobenzoylamino)benzylboronic esters to give 3‐substituted isoindolinones is achieved by using copper catalysts with 2,2′‐bipyridine‐based achiral ligands. Enantioenriched α‐aminobenzylboron reactants bearing a hydrogen atom at the boron‐bound stereogenic carbons undergo stereoinvertive coupling in the presence of a 6‐phenyl‐2,2′‐bipyridine ligand with high enantiospecificity. α‐Aminobenzylboronates bearing fully substituted boron‐bound stereogenic centers also gave the 3,3‐disubstituted isoindolinones with stereospecific stereochemical inversion in the presence of simple 2,2′‐bipyridine as a ligand.