Utilization of Borane-Catalyzed Hydrosilylation as a Dearomatizing Tool: Six-Membered Cyclic Amidine Synthesis from Isoquinolines and Pyridines

Vinh Do Cao; Dong Geun Jo; Huiae Kim; Changeun Kim; Seula Yun; Seewon Joung

doi:10.1055/s-0040-1707323

Synthesis, Inhaltsverzeichnis

Synthesis 2021; 53(04): 754-764
DOI: 10.1055/s-0040-1707323

paper

Utilization of Borane-Catalyzed Hydrosilylation as a Dearomatizing Tool: Six-Membered Cyclic Amidine Synthesis from Isoquinolines and Pyridines

Vinh Do Cao‡

,

Dong Geun Jo‡

,

Huiae Kim

,

Changeun Kim

,

Seula Yun

,

Seewon Joung∗

Abstract

Alle Artikel dieser Rubrik

Abstract

In this study, a convenient strategy to synthesize six-membered cyclic amidines from isoquinolines and pyridines has been developed. Borane-catalyzed hydrosilylation of each N-heteroarene was utilized as a dearomatizing tool. Substrate scope is broad with respect to both isoquinolines and pyridines, with various reaction pathways depending on the substitution pattern of the N-heteroarenes. The reaction mechanism and reactivity of each class of N-heteroarenes has been discussed. The resulting six-membered (Z)-sulfonyl amidine products are rarely reported and are mostly unprecedented. The scalability of this method and versatility of the cyclic amidine products are also presented.

Key words

cyclic amidine - hydrosilylation - N-heteroarenes - dearomatization - [3+2] cycloaddition - B(C₆F₅)₃

Volltext

Referenzen

References

1a Becquart C, Le Roch M, Azoulay S, Uriac P, Di Giorgio A, Duca M. ACS Omega 2018; 3: 16500
1b Rasmussen CR, Gardocki JF, Plampin JN, Twardzik BL, Reynolds BE, Molinari AJ, Schwartz N, Bennetts WW, Price BE, Marakowski J. J. Med. Chem. 1978; 21: 1044
1c Jaroch S, Hölscher P, Rehwinkel H, Sülzle D, Burton G, Hillmann M, McDonald FM. Bioorg. Med. Chem. Lett. 2002; 12: 2561
1d Diana GD, Hinshaw WB, Lape HE. J. Med. Chem. 1977; 20: 449
1e Calas M, Ouattara M, Piquet G, Ziora Z, Bordat Y, Ancelin ML, Escale R, Vial H. J. Med. Chem. 2007; 50: 6307
1f Penning TD, Khilevich A, Chen BB, Russell MA, Boys ML, Wang Y, Duffin T, Engleman VW, Finn MB, Freeman SK, Hanneke ML, Keene JL, Klover JA, Nickols GA, Nickols MA, Rader RK, Settle SL, Shannon KE, Steininger CN, Westlin MM, Westlin WF. Bioorg. Med. Chem. Lett. 2006; 16: 3156
1g Blériot Y, Dintinger T, Genre-Grandpierre A, Padrines M, Tellier C. Bioorg. Med. Chem. Lett. 1995; 5: 2655
1h Christoff JJ, Bradley L, Miller DD, Lei L, Rodriguez F, Fraundorfer P, Romstedt K, Shams G, Feller DR. J. Med. Chem. 1997; 40: 85
1i Webber RK, Metz S, Moore WM, Connor JR, Currie MG, Fok KF, Hagen TJ, Hansen DW, Jerome GM, Manning PT, Pitzele BS, Toth MV, Trivedi M, Zupec ME, Tjoeng FS. J. Med. Chem. 1998; 41: 96

2a Guthikonda RN, Shah SK, Pacholok SG, Humes JL, Mumford RA, Grant SK, Chabin RM, Green BG, Tsou N, Ball R, Fletcher DS, Luell S, MacIntyre DE, MacCoss M. Bioorg. Med. Chem. Lett. 2005; 15: 1997
2b Delcros J.-G, Tomasi S, Duhieu S, Foucault M, Martin B, Le Roch M, Eifler-Lima V, Renault J, Uriac P. J. Med. Chem. 2006; 49: 232
2c Lee E, Han S, Jin GH, Lee HJ, Kim W.-Y, Ryu J.-H, Jeon R. Bioorg. Med. Chem. Lett. 2013; 23: 3976
2d Glushkov VA, Anikina LV, Vikharev YB, Feshina EV, Shklyaev YV. Pharm. Chem. J. 2005; 39: 533
2e Al-Khawaja A, Petersen JG, Damgaard M, Jensen MH, Vogensen SB, Lie ME. K, Kragholm B, Bräuner-Osborne H, Clausen RP, Frølund B, Wellendorph P. Neurochem. Res. 2014; 39: 1988
2f Schweinitz A, Dönnecke D, Ludwig A, Steinmetzer P, Schulze A, Kotthaus J, Wein S, Clement B, Steinmetzer T. Bioorg. Med. Chem. Lett. 2009; 19: 1960

3a Chen J, Long W, Yang Y, Wan X. Org. Lett. 2018; 20: 2663
3b Tsuritani T, Yamamoto Y, Kawasaki M, Mase T. Org. Lett. 2009; 11: 1043
3c Chang S, Lee M, Jung DY, Yoo EJ, Cho SH, Han SK. J. Am. Chem. Soc. 2006; 128: 12366
3d Golovko TV, Solov’eva NP, Anisimova OS, Granik VG. Chem. Heterocycl. Compd. 2003; 39: 344
3e Xu Y, Zhu S. Tetrahedron 2001; 57: 4337

4 Cao VD, Mun SH, Kim SH, Kim GU, Kim HG, Joung S. Org. Lett. 2020; 22: 515

5a Gandhamsetty N, Joung S, Park S.-W, Park S, Chang S. J. Am. Chem. Soc. 2014; 136: 16780
5b Gandhamsetty N, Park S, Chang S. J. Am. Chem. Soc. 2015; 137: 15176
5c Park S, Chang S. Angew. Chem. Int. Ed. 2017; 56: 7720

6 Bakulev VA, Beryozkina T, Thomas J, Dehaen W. Eur. J. Org. Chem. 2018; 262
7 Xu Y, Wang Y, Zhu S, Zhu G, Jia Y, Huang Q. J. Fluorine Chem. 2000; 106: 133
8 See the Supporting Information for details.
9 Curless LD, Ingleson MJ. Organometallics 2014; 33: 7241
10 Gandhamsetty N, Park S, Chang S. Synlett 2017; 28: 2396
11 See the Supporting Information for details.
12 We observed double hydrosilylation as well as [3+2] cycloaddition of the 2-methylenamine.
13 See the Supporting Information for a detailed mechanism describing the stereoselectivity.
14 CCDC 1987424 contains the supplementary crystallographic data for this paper. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/getstructures.

15a Rendler S, Oestreich M. Angew. Chem. Int. Ed. 2008; 47: 5997
15b Sakata K, Fujimoto H. J. Org. Chem. 2013; 78: 12505

16 Similar hydrolysis of the cyclic amidine product from quinoline was also described in the Supporting Information.

17a Mortelmans C, Van Binst G. Tetrahedron 1978; 34: 363
17b Wang J.-J, Hu W.-P. J. Org. Chem. 1999; 64: 5725
17c Scott JD, Miller MW, Li SW, Lin S.-I, Vaccaro HA, Hong L, Mullins DE, Guzzi M, Weinstein J, Hodgson RA, Varty GB, Stamford AW, Chan T.-Y, McKittrick BA, Greenlee WJ, Priestley T, Parker EM. Bioorg. Med. Chem. Lett. 2009; 19: 6018
17d Akkarasamiyo S, Sawadjoon S, Orthaber A, Samec JS. M. Chem. Eur. J. 2018; 24: 3488

Zusatzmaterial

Supporting Information