Iron-Catalyzed Radical Activation Mechanism for Denitrogenative Rearrangement Over C(sp3)-H Amination

被引:40
作者
Roy, Satyajit [1 ,2 ]
Das, Sandip Kumar [1 ]
Khatua, Hillol [1 ]
Das, Subrata [1 ]
Singh, Krishna Nand [2 ]
Chattopadhyay, Buddhadeb [1 ]
机构
[1] Ctr Biomed Res CBMR, Div Mol Synth & Drug Discovery, SGPGIMS Campus,Raebareli Rd, Lucknow 226014, UP, India
[2] Banaras Hindu Univ, Inst Sci, Dept Chem, Varanasi 221005, Uttar Pradesh, India
关键词
homogeneous catalysis; denitrogenative annulation; Fe-nitrene; metalloradicals; nitrogen heterocycles;
D O I
10.1002/anie.202014950
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
An iron-catalyzed denitrogenative rearrangement of 1,2,3,4-tetrazole is developed over the competitive C(sp(3))-H amination. This catalytic rearrangement reaction follows an unprecedented metalloradical activation mechanism. Employing the developed method, a wide number of complex-N-heterocyclic product classes have been accessed. The synthetic utility of this radical activation method is showcased with the short synthesis of a bioactive molecule. Collectively, this discovery underlines the progress of radical activation strategy that should find wide application in the perspective of medicinal chemistry, drug discovery and natural product synthesis research.
引用
收藏
页码:8772 / 8780
页数:9
相关论文
共 63 条
[1]   Iron-Catalyzed Intramolecular Aminations of C(sp3)-H Bonds in Alkylaryl Azides [J].
Alt, Isabel T. ;
Guttroff, Claudia ;
Plietker, Bernd .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2017, 56 (35) :10582-10586
[2]   Iron-Catalyzed Intramolecular C(sp2)-H Amination [J].
Alt, Isabel T. ;
Plietker, Bernd .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2016, 55 (04) :1519-1522
[3]   Aziridination of alkenes and amidation of alkanes by bis(tosylimido)ruthenium(VI) porphyrins. A mechanistic study [J].
Au, SM ;
Huang, JS ;
Yu, WY ;
Fung, WH ;
Che, CM .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1999, 121 (39) :9120-9132
[4]   Catalytic Synthesis of N-Heterocycles via Direct C(sp3)-H Amination Using an Air-Stable Iron(III) Species with a Redox-Active Ligand [J].
Bagh, Bidraha ;
Broere, Daniel L. J. ;
Sinha, Vivek ;
Kuijpers, Petrus F. ;
van Leest, Nicolaas P. ;
de Bruin, Bas ;
Demeshko, Serhiy ;
Siegler, Maxime A. ;
van der Vlugt, Jan Ivar .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2017, 139 (14) :5117-5124
[5]   REARRANGEMENT OF SUITABLY CONSTITUTED ARYL, ALKYL, OR VINYL RADICALS BY ACYL OR CYANO GROUP MIGRATION [J].
BECKWITH, ALJ ;
OSHEA, DM ;
WESTWOOD, SW .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1988, 110 (08) :2565-2575
[6]   Transition-Metal-Catalyzed Denitrogenative Transannulation: Converting Triazoles into Other Heterocyclic Systems [J].
Chattopadhyay, Buddhadeb ;
Gevorgyan, Vladimir .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2012, 51 (04) :862-872
[7]   Fused Tetrazoles as Azide Surrogates in Click Reaction: Efficient Synthesis of N-Heterocycle-Substituted 1,2,3-Triazoles [J].
Chattopadhyay, Buddhadeb ;
Vera, Claudia I. Rivera ;
Chuprakov, Stepan ;
Gevorgyan, Vladimir .
ORGANIC LETTERS, 2010, 12 (09) :2166-2169
[8]   Substrate-controlled Rh(II)-catalyzed single-electron-transfer (SET): divergent synthesis of fused indoles [J].
Chen, Kai ;
Zhu, Zi-Zhong ;
Liu, Jia-Xin ;
Tang, Xiang-Ying ;
Wei, Yin ;
Shi, Min .
CHEMICAL COMMUNICATIONS, 2016, 52 (02) :350-353
[9]   Rhodium(II)-Catalyzed Intramolecular Cycloisomerizations of Methylenecyclopropanes with N-Sulfonyl 1,2,3-Triazoles [J].
Chen, Kai ;
Zhu, Zi-Zhong ;
Zhang, Yong-Sheng ;
Tang, Xiang-Ying ;
Shi, Min .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2014, 53 (26) :6645-6649
[10]   Manganese-catalysed benzylic C(sp3)-H amination for late-stage functionalization [J].
Clark, Joseph R. ;
Feng, Kaibo ;
Sookezian, Anasheh ;
White, M. Christina .
NATURE CHEMISTRY, 2018, 10 (06) :583-591