Synthesis of Multisubstituted Guanidines through Palladium-Catalyzed Insertion of Isonitriles

Pei-Xia Li; Xiu-Jin Meng; Li Yang; Hai-Tao Tang; Ying-Ming Pan

doi:10.1055/s-0037-1610981

Synlett, Inhaltsverzeichnis

Synlett 2018; 29(17): 2326-2330
DOI: 10.1055/s-0037-1610981

letter

Synthesis of Multisubstituted Guanidines through Palladium-Catalyzed Insertion of Isonitriles

Pei-Xia Li

^aState Key Laboratory for the Chemistry and Molecular Engineering of Medicinal Resources, School of Chemistry and Pharmaceutical Sciences of Guangxi Normal University, Guilin 541004, P. R. of China eMail: httang@gxnu.edu.cn

,

Xiu-Jin Meng

^aState Key Laboratory for the Chemistry and Molecular Engineering of Medicinal Resources, School of Chemistry and Pharmaceutical Sciences of Guangxi Normal University, Guilin 541004, P. R. of China eMail: httang@gxnu.edu.cn

,

Li Yang*

^bGuangxi Key Laboratory of Special Non-wood Forest Cultivation and Utilization, Guangxi Zhuang Autonomous Region Forestry Research Institute, Nanning, 530002, P. R. of China eMail: yangli2828@yeah.net

,

Hai-Tao Tang*

^aState Key Laboratory for the Chemistry and Molecular Engineering of Medicinal Resources, School of Chemistry and Pharmaceutical Sciences of Guangxi Normal University, Guilin 541004, P. R. of China eMail: httang@gxnu.edu.cn

,

Ying-Ming Pan

^aState Key Laboratory for the Chemistry and Molecular Engineering of Medicinal Resources, School of Chemistry and Pharmaceutical Sciences of Guangxi Normal University, Guilin 541004, P. R. of China eMail: httang@gxnu.edu.cn

› Institutsangaben

Abstract

Alle Artikel dieser Rubrik

Abstract

A new method for the synthesis of multisubstituted guanidines through tandem intermolecular insertion of isonitriles with unactivated amides has been developed. In this study, isonitriles could be used not only as reaction materials but also as the source of amines.

Key words

insertion of isonitriles - unactivated amides - cascade transformation - palladium

Volltext

Referenzen

References and Notes

1a Carbone M. Ciavatta ML. Mathieu V. Ingels A. Kiss R. Pascale P. Mollo E. Ungur N. Guo Y.-W. Gavagnin M. J. Nat. Prod. 2017; 80: 1339
1b Martins LF. Mesquita JT. Pinto EJ. Costa-Silva TA. Borborema SE. T. Junior AJ. G. Neves BJ. Andrade CH. Shuhaib ZA. Bennett EL. Black GP. Harper PM. Evans DM. Fituri HS. Leyland JP. Martin C. Roberts TD. Thornhill AJ. Vale SA. Howard-Jones A. Thomas DA. Williams HL. Overman LE. Berlinck RG. S. Murphy PJ. Tempone AG. J. Nat. Prod. 2016; 79: 2202
1c Li C. Teng P. Peng Z. Sang P. Sun X. Cai J. ChemMedChem 2018; 13: 1414
1d Teng P. Nimmagadda A. Su M. Hong Y. Shen N. Li C. Tsai L.-Y. Cao J. Li Q. Cai J. Chem. Commun. 2017; 11948
1e Pan L. Li Z. Ding T. Fang X. Zhang W. Xu H. Xu Y. J. Org. Chem. 2017; 82: 10043
1f Wang R. Guan W. Han Z.-B. Liang F. Suga T. Bi X. Nishide H. Org. Lett. 2017; 19: 2358

2 Müller F. Weitz D. Mertsch K. König J. Fromm MF. Mol. Pharmaceutics 2018; 15: 3425
3 Tapiero H. Mathe G. Couvreur P. Tew KD. Biomed. Pharmacother. 2002; 56: 439
4 Xian M. Li X. Tang X. Chen X. Zheng Z. Galligan JJ. Kreulen DL. Wang PG. Bioorg. Med. Chem. Lett. 2001; 11: 2377
5 Chen C. Yu J. Fleck BA. Hoare SR. J. Saunders J. Foster AC. J. Med. Chem. 2004; 47: 4083
6 Heinzl GA. Huang W. Yu W. Giardina BJ. Zhou Y. MacKerell AD. Wilks A. Xue F. J. Med. Chem. 2016; 59: 6929

7a Wangngae S. Pattarawarapan M. Phakhodee W. J. Org. Chem. 2017; 82: 10331
7b Zhang Z. Li Z. Fu B. Zhang Z. Chem. Commun. 2015; 16312
7c Demjén A. Angyal A. Wölfling J. Puskása LG. Kanizsai I. Org. Biomol. Chem. 2018; 16: 2143
7d Zhang Z. Huang B. Qiao G. Zhu L. Xiao F. Chen F. Fu B. Zhang Z. Angew. Chem. Int. Ed. 2017; 56: 4320
7e Zhu T.-H. Wang S.-Y. Wei T.-Q. Ji S.-J. Adv. Synth. Catal. 2015; 357: 823
7f Gu Z.-Y. Liu Y. Wang F. Bao X. Wang S.-Y. Ji S.-J. ACS Catal. 2017; 7: 3893
7g Zhang W.-X. Li D. Wang Z. Xi Z. Organometallics 2009; 28: 882
7h Zhang W.-X. Xu L. Xi Z. Chem. Commun. 2015; 254 ; and references cited therein

8a Boyarskiy VP. Bokach NA. Luzyanin KV. Kukushkin VY. Chem. Rev. 2015; 115: 2698
8b Giustiniano M. Basso A. Mercalli V. Massarotti A. Novellino E. Tron GC. Zhu J. Chem. Soc. Rev. 2017; 46: 1295
8c Ruijter E. Scheffelaar R. Orru RV. A. Angew. Chem. Int. Ed. 2011; 50: 6234
8d Zhang B. Studer A. Chem. Soc. Rev. 2015; 44: 3505
8e Song B. Xu B. Chem. Soc. Rev. 2017; 46: 1103

9 Qiu G. Ding Q. Wu J. Chem. Soc. Rev. 2013; 42: 5257

For recent examples, see:

10a Wang X. Xiong W. Huang Y. Zhu J. Hu Q. Wu W. Jiang H. Org. Lett. 2017; 19: 5818
10b Peng J. Gao Y. Hu W. Gao Y. Hu M. Wu W. Ren Y. Jiang H. Org. Lett. 2016; 18: 5924
10c Hu W. Li M. Jiang G. Wu W. Jiang H. Org. Lett. 2018; 20: 3500

11 Jiang X. Tang T. Wang J.-M. Chen Z. Zhu Y.-M. Ji S.-J. J. Org. Chem. 2014; 79: 5082
12 Tong W. Li W.-H. He Y. Mo Z.-Y. Tang H.-T. Wang H.-S. Pan Y.-M. Org. Lett. 2018; 20: 2494
13 Typical Procedure: To a round-bottom flask was added amide 1 (0.3 mmol), tert-butyl isocyanide 2 (0.72 mmol), PdCl₂, and Cs₂CO₃, and MeCN (2.0 mL) was added under air. The reaction mixture was stirred at 70 °C for ca. 2 h, and the progress of the reaction was monitored by TLC. The reaction mixture was evacuated under vacuum, and the residue was further purified by silica gel column chromatography (petroleum ether and ethyl acetate) to afford the product 3.

14a Representative Analytical Data for 3b: White solid; mp 137–139 °C. ¹H NMR (400 MHz, CDCl₃): δ = 7.94 (d, J = 7.4 Hz, 1 H), 7.25–7.14 (m, 3 H), 2.63 (s, 3 H), 1.46 (s, 18 H). ¹³C NMR (100 MHz, CDCl₃): δ = 179.55 (s), 158.43 (s), 139.81 (s), 137.54 (s), 130.84 (s), 129.46 (s), 128.83 (s), 124.86 (s), 50.92 (s), 29.87 (s), 21.39 (s). HRMS (ESI): m/z [M+H]⁺ calcd for C₁₇H₂₈N₃O: 290.2227; found: 290.2215.

Zusatzmaterial

Supporting Information