Study on the Mechanism of Ru-Catalyzed Cyclization of Aromatic Amides with Allylphosphine Oxides

被引：2

作者：

Yan, Wenxin ^{[1
]}

Cheng, Qi ^{[1
]}

Jiao, Yinchun ^{[1
,2
]}

Cao, Chao-Tun ^{[1
,2
]}

Tang, Zilong ^{[1
,2
]}

机构：

[1] Hunan Univ Sci & Technol, Sch Chem & Chem Engn, Xiangtan 411201, Peoples R China

[2] Hunan Univ Sci & Technol, Key Lab Theoret Organ Chem & Funct Mol, Hunan Prov Key Lab Controllable Preparat & Funct A, Minist Educ,Sch Chem & Chem Engn, Xiangtan 411201, Peoples R China

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2023年 / 88卷 / 21期

基金：

中国国家自然科学基金;

关键词：

EFFECTIVE CORE POTENTIALS; C-H ACTIVATION; OXIDATIVE CYCLOADDITION; MOLECULAR CALCULATIONS; BASIS-SETS; ANNULATION; CYCLOMETALATION; ISOQUINOLONES; ALKYNES; BONDS;

D O I：

10.1021/acs.joc.3c01287

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The mechanism of Ru-catalyzed cyclization of aromatic amides with allylphosphine oxides is studied by density functional theory calculation (DFT). The results show that, first, a 5-membered Ru ring intermediate is formed by N-H and C-H diprotons via the concerted metalation-deprotonation mechanism (CMD) and then the allylphosphine oxide is inserted through the ring-extending reaction to form a 7-membered ring intermediate. Next, reduction elimination is followed via intramolecular hydrogen transfer isomerization. At last, with the assistance of acetic acid, Ru (II) -> Ru (IV) -> Ru (II) complexes occur from the 7-membered Ru ring intermediate, and the final product is formed by reduction elimination and protonation reaction, while the catalyst is released to participate in the next cycle.

引用

页码：14945 / 14952

页数：8

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