Cyanogen: A Versatile Reagent for Diversity-Oriented Synthesis

Abstract

This short review summarises the synthetic applications of cyanogen. The review is divided into several parts, including transition-metal-catalysed reactions, addition reactions, and cyclisation processes.

1 Introduction

2 Addition Reactions

3 Ring-Closure Reactions

4 Transition-Metal-Catalysed Reactions

5 Conclusions

Key words

cyclization - cycloaddition - heterocycles - transition metals - addition

• References

• 1a Fray N, Bénilan Y, Cottin H, Gazeau M.-C, Crovisier J. Planet. Space Sci. 2005; 53: 1243
• 1b Kunde VG, Aikin AC, Hanel RA, Jennings DE, Maguire WC, Samuelson RE. Nature (London) 1981; 292
• 2 Conway JB, Wilson RH. Jr, Grosse AV. J. Am. Chem. Soc. 1953; 75: 499

Selected examples:
• 3a Kirley JW, Day RA, Kreishman GP. FEBS Lett. 1985; 193: 145
• 3b Karagözler AA, Ghenbot G, Day RA. Biopolymers 1993; 33: 687
• 3c Huijbreqts MA. J, Rombouts LJ. A, Ragas AM. J, van de Meent D. Integr. Environ. Assess. Manage. 2005; 1: 181
• 4 Desmarchelier FJ. M, Yonglin R, O’Brien IG. WO 1996001051, 1996 ; cyanogen fumigants and methods of fumigation using cyanogen.
• 5 Currently, cyanogen is offered by HBCChem, Inc. (http://www.hbcchem-inc.com/index.html, 22.11. 2016) and 5A Pharm (http://www.5apharm.com/ accessed 22.11. 2016).

Selected examples:
• 6a House JE, Marquardt LA. Thermochim. Acta 1989; 145: 265
• 6b Chamberlain MM, Greene AF. Jr. J. Inorg. Nucl. Chem. 1963; 25: 1471
• 7 Park DJ, Stern AG, Willer RL. Synth. Commun. 1990; 20: 2901
• 8a Brotherton TK, Lynn JW. Chem. Rev. 1959; 59: 841
• 8b Corain B. Coord. Chem. Rev. 1982; 47: 165
• 9 Vorlander D. Ber. Dtsch. Chem. Ges. 1911; 44: 2455
• 10 Woodburn HM, Lathroum LB. J. Org. Chem. 1954; 19: 285
• 11 Lynn KR. Aust. J. Chem. 1954; 7: 303
• 12 Eastham JF, Raaen VF. Proc. Chem. Soc. 1958; 149
• 13 Raaen VF, Eastham JF. J. Am. Chem. Soc. 1960; 82: 1349
• 14 Harmon CA, Streitwieser AJr. J. Org. Chem. 1973; 38: 549
• 15 Paquette LA, Burke LD. J. Org. Chem. 1987; 52: 2674
• 16 Jutzi P, Schwartzen KH, Mix A. Chem. Ber. 1990; 123: 837
• 17 Boltze KH, Dell HD, Janseii H. Justus Liebigs Ann. Chem. 1967; 709: 63
• 18 Zweifel G, Snow JT, Whitney ChC. J. Am. Chem. Soc. 1968; 90: 7139
• 19 Woodburn HM, Dolce TJ. J. Org. Chem. 1960; 25: 452
• 20 Luthman K, Orbe M, Waglund T, Claesson A. J. Org. Chem. 1987; 52: 3777
• 21 Ciganek E. J. Org. Chem. 1970; 35: 3631
• 22 Begland RW, Cairncross A, Donald DS, Hartter DR, Sheppard WA, Webster OW. J. Am. Chem. Soc. 1971; 93: 4953
• 23 Webster OW, Hartter DR, Begland RW, Sheppard WA, Cairncross A. J. Org. Chem. 1972; 37: 4133
• 24a Begland RW, Hartter DR. J. Org. Chem. 1972; 37: 4136
• 24b Hordiyenko OV, Rudenko IV, Zamkova IA, Denisenko OV, Biitseva AV, Arrault A, Tolmachev AA. Synthesis 2013; 45: 3375
• 24c Belozerova YI, Efimova SV, Korzhenevskii AB, Koifman OI. Russ. J. Gen. Chem. 2009; 79: 2678
• 24d Fukunaga T, Begland RW. J. Org. Chem. 1984; 49: 813
• 25 Sundermeyer J, Roesky HW. Chem. Ber. 1991; 124: 1517
• 26 Robson P, McLoughlin VC. R, Hynes JB, Bigelow LA. J. Am. Chem. Soc. 1961; 83: 5010
• 27 Emeléus HJ, Hurst GL. J. Chem. Soc. 1964; 1: 396
• 28 Waterfeld A, Mews R. J. Chem. Soc., Chem. Commun. 1982; 839
• 29 Mir Q, DesMarteau DD. Inorg. Chem. 1991; 30: 535
• 30 Karrer P, Ferla J. Helv. Chim. Acta 1921; 4: 203
• 31 Baxter AF, Christe KO, Haiges R. Angew. Chem. Int. Ed. 2015; 54: 14535
• 32 Keller K, Thiel A, Roesky HW. J. Fluorine Chem. 1984; 26: 313
• 33 Grützmacher H, Roesky HW. Chem. Ber. 1986; 119: 2127
• 34 Grützmacher H, Keweloh N, Roesky HW, Noltemeyer M, Sheldrick GM. J. Fluorine Chem. 1987; 37: 279
• 35 Emeleus HJ, Hurst GL. J. Chem. Soc. 1962; 3276
• 36 Mutha SC, Ketcham R. J. Org. Chem. 1969; 34: 2053
• 37 Heindel ND, Schaeffer LA. J. Heterocycl. Chem. 1975; 12: 783
• 38 Martin AR, Ketcham R. J. Org. Chem. 1966; 31: 3612
• 39 Shah VP, Lam G, Ketcham R. J. Med. Chem. 1971; 14: 456
• 40 Gay-Lussac JL. Ann. Chim. (Paris) 1815; 95: 196
• 41 Ketcham R, Schaumann E, Adiwidjaja G. Eur. J. Org. Chem. 2001; 1695

Formation of 1,3-disubstituted imidazolidine systems by reaction of N-substituted cyanoformamides with isocyanates and isocyanates was reported:
• 42a Khattak I, Ketcham R. J. Chem. Soc., Chem. Commun. 1983; 260
• 42b Khattak I, Ketcham R, Schaumann E, Adiwidjaja G. J. Org. Chem. 1985; 50: 3431
• 43 Alkorta I, Arán VJ, Dávila E, Ruiz JR, Stud M. Liebigs Ann. Chem. 1989; 1135
• 44 Arán VJ, Ruiz JR, Dávila E, Alkorta I, Stud M. Liebigs Ann. Chem. 1988; 337
• 45 Ward JS, Merritt L, Calligaro DO, Bymaster FP, Shannon HE, Mitch CH, Whitesitt C, Brunsting D, Sheardown MJ, Olesen PH, Swedberg MD. B, Jeppesen L, Sauerberg P. J. Med. Chem. 1998; 41: 379
• 46 Weinstock LM, Davis P, Handelsman B, Tull R. J. Org. Chem. 1967; 32: 2823
• 47 Roesky HW, Keller K, Bats JW. Angew. Chem. 1983; 95: 904 ; Angew. Chem., Int. Ed. Engl.; 1983, 22: 881
• 48a Parsons S, Passmore J, Schriver MJ, White PS. J. Chem. Soc., Chem. Commun. 1991; 369
• 48b Doyle PD, Parsons S, Passmore J, Wood DJ. J. Chem. Soc., Chem. Commun. 1993; 199
• 48c Brooks WV. F, Brownridge S, Parsons S, Passmore J. Phosphorus, Sulfur Silicon 1994; 93–94: 443
• 48d Cameron TS, Decken A, Grein F, Knapp C, Passmore J, Rautiainen JM, Shuvaev KV, Thompson RC, Wood DJ. Inorg. Chem. 2010; 49: 7861
• 49 Sundermeyer J, Roesky HW. Angew. Chem. Int. Ed. 1988; 27: 1372
• 50 Weidinger H, Kranz J. Chem. Ber. 1964; 97: 1599
• 51 Preparation of bis(2-hydroxypropyl) oxaldiimidate dihydrochloride was published herein: Woodburn HM, Whitehouse AB, Pautler BG. J. Org. Chem. 1959; 24: 210
• 52 Zhang L, Lo KC, Chan WK. Chem. Commun. 2014; 50: 4245
• 53 Bast K, Christl M, Huisgen R, Mack W. Chem. Ber. 1972; 105: 2825
• 54 Ried W, Fulde M. Helv. Chim. Acta 1988; 71: 1681
• 55 Crawford M.-J, Klapötke TM, Martin FA, Sabaté CM, Rusan M. Chem. Eur. J. 2011; 17: 1683
• 56 Hees U, Ledermann M, Regitz M. Synlett 1990; 401
• 57 Sundermeyer J, Roesky HW, Noltemeyer M. Z. Naturforsch., B 1990; 45: 77
• 58 Meiners F, Haase D, Koch R, Saak W, Weidenbruch M. Organometallics 2002; 21: 3990
• 59 Lim C, Choi CH. J. Chem. Phys. 2004; 121: 5445
• 60 Argento BJ, Fitton P, McKeon JE, Rick EA. J. Chem. Soc., Chem. Commun. 1969; 1427
• 61 Bressan M, Favero G, Corain B, Turco A. Inorg. Nucl. Chem. Lett. 1971; 7: 203
• 62 Corain B, Basato M, Favero G. J. Chem. Soc., Dalton Trans. 1977; 2081
• 63 Corain B, Basato M, Favero G, Rosano P. Inorg. Chim. Acta 1984; 85: L27
• 64 tom Dieck H, Diercks R, Stamp L, Bruder H, Schuld T. Chem. Ber. 1987; 120: 1943
• 65 Hanack M, Polley R, Knecht S, Schlick U. Inorg. Chem. 1995; 34: 3621
• 66 Giordano F, Panunzi B, Roviello A, Ruffo F. Inorg. Chim. Acta 1995; 239: 61
• 67 Grotjahn DB, Brewster MA, Ziurys LM. J. Am. Chem. Soc. 2002; 124: 5895
• 68 Gong Y, Andrews L, Liebov BK, Fang Z, Garner III EB, Dixon DA. Chem. Commun. 2015; 51: 3899
• 69 Von Guttenberger JF. Angew. Chem. 1967; 79: 1071
• 70 Deeming AJ, Donovan-Mtunzi S, Kabir SE, Arce AJ, De Sanctis Y. J. Chem. Soc., Dalton Trans. 1987; 1457
• 71 Siddiqui S, Henderson WW, Shepherd RE. Inorg. Chem. 1987; 26: 3101
• 72 Von Ruschke P, Dehnicke K. Z. Anorg. Allg. Chem. 1980; 466: 157
• 73 Tornieporth-Oetting IC, Klapötke TM. Inorg. Chim. Acta 1994; 215: 5
• 74 Ruiz J, Riera V, Vivanco M. Organometallics 1998; 17: 4562
• 75 Mosquera ME. G, Ruiz J, Riera V, García-Granda S, Díaz MR. Organometallics 2001; 20: 3821
• 76a Corain B, Crotti C, Del Pra A, Filira F. Inorg. Chem. 1981; 20: 2044
• 76b Corain B, Basato M, Klein H.-F. Angew. Chem. 1981; 93: 1034 ; Angew. Chem. Int. Ed. 1981, 20, 972
• 76c Basato M, Corain B, Marcomini A, Valle G, Zanotti G. J. Chem. Soc., Perkin Trans. 2 1984; 965
• 77 Corain B, Basato M, Mori E, Valle G. Inorg. Chim. Acta 1983; 76: L277
• 78 Basato M, Corain B, Veronese AC, D’Angeli F, Valle G, Zanotti G. J. Org. Chem. 1984; 49: 4696
• 79a Basato M, Campostrini R, Corain B, D’Angeli F, Veronese AC, Valle G. Inorg. Chim. Acta 1985; 98: L17
• 79b Basato M, Campostrini R, Corain B, Longato B, Sitran S, Veronese AC, Valle G. J. Chem. Soc., Perkin Trans. 2 1985; 2019
• 80 Veronese AC, Callegari R. J. Mol. Catal. 1991; 68: L1
• 81a Corain B, Del Pra A, Filira F, Zanotti G. Inorg. Chem. 1979; 18: 3523
• 81b Corain B, Basato M. J. Organomet. Chem. 1982; 232: C59
• 81c Corain B, Basato M, Del Zotto A, Zanotti G. Inorg. Chem. 1983; 22: 2744
• 81d Corain B, Basato M, Ballota C, Ahmed M. Inorg. Chim. Acta 1984; 87: 105
• 82 Corain B, Basato M, Visentin G, Zanotti G. J. Chem. Soc., Dalton Trans. 1983; 1217
• 83 Corain B, Basato M, Marcomini A, Klein H.-F. Inorg. Chim. Acta 1983; 74: 1
• 84 Basato M, Corain B, Favero G. Inorg. Chim. Acta 1989; 159: 59