Enabling CO Insertion into o-Nitrostyrenes beyond Reduction for Selective Access to Indolin-2-one and Dihydroquinolin-2-one Derivatives | |
Department | OSSO国家重点实验室 |
Yang, Li1,2; Shi, Lijun1; Xing, Qi1; Huang, Guowei3; Xia, Chungu1; Li, Fuwei1 | |
2018 | |
Source Publication | ACS Catalysis |
Volume | 8Issue:11Pages:10340–10348 |
Abstract | The transition metal-catalyzed reductive cyclization of o-nitrostyrene in the presence of carbon monoxide (CO) has been developed to be a general synthetic route to an indole skeleton, wherein CO was used as a reductant to deoxidize nitroarene into nitrosoarene and/or nitrene with CO2 release, but the selective insertion of CO into the heterocyclic product with higher atom economy has not yet been realized. Herein, the Pd-catalyzed reduction of o-nitrostyrene by CO and its regioselective insertion were efficiently achieved to produce synthetically useful five- and six-membered benzo-fused lactams. Detailed investigations revealed that the chemoselectivity to indole or lactam was sensitive to the nature of the counteranions of Pd2+ precursors, whereas ligands significantly decided the carbonylative regioselectivity by different reaction pathways. Using PdCl2/PPh3/B(OH)3 (condition A), an olefin hydrocarboxylation was primarily initiated followed by partial reduction of the NO2 moiety and cyclization reaction to give N-hydroxyl indolin-2-one, which was further catalytically reduced by CO to afford the indolin-2-one as the final product with up to 95% yield. When the reaction was conducted under the Pd(TFA)2/BINAP/TsOH·H2O system (condition B), complete deoxygenation and carbonylation of the NO2 group occurred initially to yield the corresponding isocyanate followed by internal hydrocyclization to generate 3,4-dihydroquinolin-2-one with up to 98% yield. Importantly, the methodology could be efficiently applied in the synthesis of marketed drug Aripiprazole. |
Keyword | Carbonylation Cascade Reaction Heterocycle O-nitrostyrene Selectivity |
DOI | 10.1021/acscatal.8b02863 |
If | 11.384 |
compositor | 第一作者单位 |
Citation statistics | |
Document Type | 期刊论文 |
Identifier | http://ir.licp.cn/handle/362003/24399 |
Collection | 羰基合成与选择氧化国家重点实验室(OSSO) 苏州研究院 |
Corresponding Author | Li, Fuwei |
Affiliation | 1.State Key Laboratory for Oxo Synthesis and Selective Oxidation, Suzhou Research Institute of LICP, Lanzhou Institute of Chemical Physics (LICP), Chinese Academy of Sciences, Lanzhou 730000, P. R. China 2.University of Chinese Academy of Sciences, Beijing 100049, P. R. China 3.KAUST Catalysis Center and Division of Physical Sciences and Engineering, King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Saudi Arabia |
Recommended Citation GB/T 7714 | Yang, Li,Shi, Lijun,Xing, Qi,et al. Enabling CO Insertion into o-Nitrostyrenes beyond Reduction for Selective Access to Indolin-2-one and Dihydroquinolin-2-one Derivatives[J]. ACS Catalysis,2018,8(11):10340–10348. |
APA | Yang, Li,Shi, Lijun,Xing, Qi,Huang, Guowei,Xia, Chungu,&Li, Fuwei.(2018).Enabling CO Insertion into o-Nitrostyrenes beyond Reduction for Selective Access to Indolin-2-one and Dihydroquinolin-2-one Derivatives.ACS Catalysis,8(11),10340–10348. |
MLA | Yang, Li,et al."Enabling CO Insertion into o-Nitrostyrenes beyond Reduction for Selective Access to Indolin-2-one and Dihydroquinolin-2-one Derivatives".ACS Catalysis 8.11(2018):10340–10348. |
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