Development of Molecular Complexity through Nitrene-Transfer Reactions Catalyzed by Copper and Silver Scorpionate Complexes

Abstract

For years, metal–nitrene-transfer reactions have been mainly directed toward C=C bond aziridination or C–H bond amidation reactions. In the last decade, multiple efforts have been made to develop new synthetic approaches to expand the applicability of this powerful tool, resulting in the synthesis of complex structures from relatively simple starting materials. Here, we present our contributions to the area with several novel and, to some degree, unexpected transformations developed by our research group. The catalysts for these nitrene-transfer reactions are copper or silver complexes bearing hydrotrispyrazolyl (scorpionate) ligands. These transformations have contributed to an expansion of the scope of organic compounds accessible by nitrene-transfer reactions and to an understanding of the reactivity of metallonitrene species toward the oxidation of less-explored organic substrates.

1 Introduction

2 Synthesis of 1,2-Dihydropyridines from Furans

3 Regio- and Stereoselective Aziridination of Dienes

4 Chemoselective Synthesis of Aminimides from Amines

5 Synthesis of Sulfinamides and Isothiazoles from Alkynes

6 Formation of Azetidines and Methylene Aziridines from Allenes

7 Conclusion

Key words - nitrene transfer - C–N bond formation - copper catalysis - silver catalysis - dihydropyridines - aminimides

Publication History

Received: 29 July 2020

Accepted after revision: 06 September 2020

Article published online:
05 November 2020

• References

• 1 Kwart H, Khan AA. J. Am. Chem. Soc. 1967; 89: 1951
• 2a Dequirez G, Pons V, Dauban P. Angew. Chem. Int. Ed. 2012; 51: 7384
• 2b Degennaro L, Trinchera P, Luisi R. Chem. Rev. 2014; 114: 7881
• 2c Chang JW. W, Ton TM. U, Chan PW. H. Chem. Rec. 2011; 11: 331
• 2d Díaz-Requejo MM, Caballero A, Fructos MR, Pérez PJ. In Alkane C–H Activation by Single-Site Metal Catalysis . Pérez PJ. Springer; Dordrecht: 2012. DOI: Chap. 6, 229
• 2e Zalatan DN, Du Bois J. Top. Curr. Chem. 2010; 292: 347
• 3a Breslow DS, Sloan MF. Tetrahedron Lett. 1968; 5349
• 3b Groves JT, Takahashi T. J. Am. Chem. Soc. 1983; 105: 2073
• 3c Mansuy D, Mahy J.-P, Dureault A, Bedi G, Battioni P. J. Chem. Soc. Chem. Commun. 1984; 1161
• 3d Evans DA, Faul MM, Bilodeau MT. J. Org. Chem. 1991; 56: 6744
• 3e Breslow R, Gellman SH. J. Am. Chem. Soc. 1983; 105: 6728
• 4 Pérez PJ, Brookhart M, Templeton JL. Organometallics 1993; 12: 261
• 5 Mairena MA, Díaz-Requejo MM, Belderraín TR, Nicasio MC, Trofimenko S, Pérez PJ. Organometallics 2003; 23: 253
• 6 Díaz-Requejo MM, Belderraín TR, Nicasio MC, Trofimenko S, Pérez PJ. J. Am. Chem. Soc. 2003; 125: 12078
• 7 Fructos MR, Trofimenko S, Mar Díaz-Requejo M, Pérez PJ. J. Am. Chem. Soc. 2006; 128: 11784
• 8 Gómez-Emeterio BP, Urbano J, Díaz-Requejo MM, Pérez PJ. Organometallics 2008; 27: 4126
• 9a Novác J, Sorm F. Collect. Czech. Chem. Commun. 1958; 23: 1126
• 9b Caballero A, Díaz-Requejo MM, Trofimenko S, Belderraín TR, Pérez PJ. J. Org. Chem. 2005; 70: 6101
• 9c Kobayashi Y, Katsuno H, Sato F. Chem. Lett. 1983; 1771
• 9d Adger BM, Barrett C, Brennan J, McKervey MA, Murray RW. J. Chem. Soc., Chem. Commun. 1991; 1553
• 10a Floyd MB. J. Org. Chem. 1978; 43: 1641
• 10b Elliott BJ. D, Hetmanski M, Stoodley RJ, Palfreyman MN. J. Chem. Soc., Perkin Trans. 1 1981; 1782
• 11 Fructos MR, Álvarez E, Díaz-Requejo MM, Pérez PJ. J. Am. Chem. Soc. 2010; 132: 4600
• 12 Hogg JL, Jenks DA, Jenks WP. J. Am. Chem. Soc. 1977; 99: 4772
• 13 Maestre L, Fructos MR, Díaz-Requejo MM, Pérez PJ. Organometallics 2012; 31: 7839−7843
• 14a Llavería J, Beltrán A, Díaz-Requejo MM, Matheu MI, Castillón S, Pérez PJ. Angew. Chem. Int. Ed. 2010; 49: 7092
• 14b Llavería J, Beltrán A, Sameera WM. C, Locati A, Díaz-Requejo MM, Matheu MI, Castillón S, Maseras F, Pérez PJ. J. Am. Chem. Soc. 2014; 136: 5342
• 15a Ma L, Du D.-M, Xu J. Chirality 2006; 18: 575
• 15b Sureshkumar D, Maity S, Chandrasekaran S. J. Org. Chem. 2006; 71: 1653
• 15c Knight JG, Muldowney MP. Synlett 1995; 949
• 15d Piangiolino C, Gallo E, Caselli A, Fantauzzi S, Ragaini F, Cenini S. Eur. J. Org. Chem. 2007; 743
• 15e Nishimura M, Minakata S, Thongchant S, Ryu I, Komatsu M. Tetrahedron Lett. 2000; 41: 7089
• 16a Somfai P, Panknin O. Synlett 2007; 1190
• 16b Ohno H. In Aziridines and Epoxides in Organic Synthesis . Yudin AK. Wiley-VCH; Weinheim: 2006. DOI: Chap. 2, 37
• 16c Sweeney JB. Chem. Soc. Rev. 2002; 31: 247
• 16d McCoull W, Davis FA. Synthesis 2000; 1347
• 17a Atkinson RS, Kelly BJ. J. Chem. Soc., Chem. Commun. 1988; 624
• 17b Atkinson RS, Kelly BJ, McNicolas C. J. Chem. Soc., Chem. Commun. 1989; 562
• 17c Atkinson RS, Williams PJ. J. Chem. Soc., Perkin Trans. 1 1996; 1951
• 17d Atkinson RS, Ulukanli S, Williams PJ. J. Chem. Soc., Perkin Trans. 1 1999; 2121
• 17e Cakici M, Karabuga S, Kilic H, Ulukanli S, Şahin E, Sevin F. J. Org. Chem. 2009; 74: 9452
• 18 Maestre L, Sameera WM. C, Díaz-Requejo MM, Maseras F, Pérez PJ. J. Am. Chem. Soc. 2013; 135: 1338−1348
• 19 Maestre L, Dorel R, Pablo Ó, Escofet I, Sameera WM. C, Álvarez E, Maseras F, Díaz-Requejo MM, Echavarren AM, Pérez PJ. J. Am. Chem. Soc. 2017; 139: 2216
• 20a Jain SL, Sharma VB, Sain B. Tetrahedron Lett. 2003; 44: 4385
• 20b Ochiai M, Kawano Y, Kaneaki T, Tada N, Miyamoto K. Org. Lett. 2009; 11: 281
• 20c Ochiai M, Miyamoto K, Hayashi S, Nakanishi W. Chem. Commun. 2010; 46: 511
• 20d Pujari SA, Guénée L, Lacour J. Org. Lett. 2013; 15: 3930
• 21a McKillip WJ, Sedor EA, Culbertson BM, Wawzonek S. Chem. Rev. 1973; 73: 255
• 21b Rademacher P. In Science of Synthesis, Vol. 40b. Enders D, Schaumann E. Thieme; Stuttgart: 2009. DOI: Chap. 40.7, 1133

For examples, see:
• 22a Peisach E, Casbier D, Gallion SL, Furth P, Petsko G, Hogan JC. Jr, Ringe D. Science 1995; 269: 66
• 22b Gangapuram M, Redda KK. J. Heterocycl. Chem. 2009; 46: 309
• 23 Rodríguez MR, Beltrán A, Mudarra AL, Alvarez E, Maseras F, Díaz-Requejo MM, Pérez PJ. Angew. Chem. Int. Ed. 2017; 56: 12842
• 24a Thornton AR, Blakey SB. J. Am. Chem. Soc. 2008; 130: 5020
• 24b Li C, Zhang L. Org. Lett. 2011; 13: 1738
• 25 Ram VJ, Sethi A, Nath M, Pratap R. The Chemistry of Heterocycles: Nomenclature and Chemistry of Three-to-Five-Membered Heterocycles. Elsevier; Amsterdam: 2019
• 26 Buchner E, Curtius T. Ber. Dtsch. Chem. Ges. 1885; 18: 2377
• 27 Rodríguez MR, Besora M, Molina F, Maseras F, Díaz-Requejo MM, Pérez PJ. J. Am. Chem. Soc. 2020; 142: 13062
• 28 Feast GC, Page LW, Robertson J. Chem. Commun. 2010; 46: 2835
• 29a Stoll AH, Blakey SB. J. Am. Chem. Soc. 2009; 132: 2108
• 29b Stoll AH, Blakey SB. Chem. Sci. 2011; 2: 112
• 30a Boralsky LA, Grigg RD, Marston D, Hershberger JC, Schomaker JM. Org. Lett. 2011; 13: 1924
• 30b Adams CS, Boralsky LA, Guzei IA, Schomaker JM. J. Am. Chem. Soc. 2012; 134: 10807
• 30c Burke EG, Schomaker JM. Angew. Chem. Int. Ed. 2015; 54: 12097
• 30d Schmid SC, Guzei IA, Schomaker JM. Angew. Chem. Int. Ed. 2017; 56: 12229
• 30e Grigg RD, Schomaker JM, Timokhin V. Tetrahedron 2011; 67: 4318
• 30f Weatherly CD, Rigoli JW, Schomaker JM. Org. Lett. 2012; 14: 1704
• 30g Weatherly CD, Guzei IA, Schomaker JM. Eur. J. Org. Chem. 2013; 3667
• 30h Rigoli JW, Weatherly CD, Vo BT, Neale S, Meis AR, Schomaker JM. Org. Lett. 2013; 15: 290
• 30i Rigoli JW, Weatherly CD, Alderson JM, Vo BT, Schomaker JM. J. Am. Chem. Soc. 2013; 135: 17238
• 30j Eshon J, Nicastri KA, Schmid SC, Raskopf WT, Guzei IA, Fernández I, Schomaker JM. Nat. Commun. 2020; 11: 1273
• 31 Quast H, Risler W. Angew. Chem., Int. Ed. Engl. 1973; 12: 414
• 32a Bayliffe FH, Steven A, Ando K, Shipman M. Synlett 2015; 26: 1371
• 32b Bayliffe F. Ph.D. Thesis . University of Warwick; UK: 2013