Adventures in 1,3-Selenazole Chemistry

Dedicated to Priv.-Doz. Dr. Wolf-Diethard Pfeiffer

Abstract

The synthesis of 1,3-selenazoles and related compounds, including 2,4,5-trisubstituted, 2,4-disubstituted, 4,5-disubstituted, 4-substituted 1,3-selenazoles, and parent unsubstituted 1,3-selenazole, is highlighted. Emphasis is also given on 2-benzoyl-1,3-selenazoles which can be functionalized by Knoevenagel reactions or by rearrangements via their corresponding oximes. Syntheses of bis-, tris-, and tetrakis(1,3-selenazoles) are discussed as well. 1,3,4-6H-Selenadiazines are available from selenosemicarbazides and can undergo ring-contraction or deselenation reactions. Most syntheses rely on the application of selenocarboxylic amides, selenourea and related building blocks which are conveniently available by reaction of the corresponding oxygen analogues with P₄Se₁₀.

1 Introduction

2 Selenocarboxylic Amides

3 2,4,5-Tri- and 2,4-Disubstituted 1,3-Selenazoles

4 Bis(1,3-selenazoles)

5 2-Amino-1,3-selenazoles

6 2-Unsubstituted 1,3-Selenazoles

7 1,3,4-Selenadiazines

8 Conclusions

Keywords

cyclizations - heterocycles - nitrogen - regioselectivity - selenium

Publication History

Received: 05 November 2021

Accepted after revision: 16 November 2021

Article published online:
17 December 2021

• References

• 1a Rafique J, Canto RF. S, Saba S, Barbosa FA. R, Braga AL. Curr. Org. Chem. 2016; 20: 166
• 1b Goldstein BM, Kennedy SD, Hennen WJ. J. Am. Chem. Soc. 1990; 112: 8265 ; and references cited therein

Reviews:
• 2a Bulka E. Advances in Heterocyclic Chemistry, Vol. 2 1963; 343
• 2b Larsen R, Shinkai I. 1,3-Selenazoles . Comprehensive Heterocyclic Chemistry II, Vol. 3 . Katritzky A, Rees CW, Scriven EF. V. Elsevier Science; Oxford: 1996. Chapt. 8
• 2c Pfeiffer W.-D. 1,3-Selenazoles, In Science of Synthesis, Vol. 11. Schaumann E. Thieme; Stuttgart: 2002
• 2d Wirth T. Organoselenium Chemistry. Modern Developments in Organic Synthesis 2000
• 2e Koketsu M, Nada F, Ishihara H. Synthesis 2002; 195 and references cited therein
• 2f Koketsu M, Ishihara H. Curr. Org. Chem. 2003; 7: 175
• 3a Lai L.-L, Reid DH. Synthesis 1993; 870
• 3b Klayman DL, Griffins TS. J. Am. Chem. Soc. 1973; 95: 197 For the use of LiAlH4/Se, see
• 3c Ishihara H, Koketsu M, Fukuta Y, Nada F. J. Am. Chem. Soc. 2001; 123: 8408
• 3d Koketsu M, Fukuta Y, Ishihara H. Tetrahedron Lett. 2001; 42: 6333
• 4 Ogawa A, Miyaka J, Karasaki Y, Murai S, Sonoda N. J. Org. Chem. 1985; 50: 384
• 5 Kaminski R, Glass RS, Skowronska A. Synthesis 2001; 1308
• 6 Cohen VJ. Synthesis 1978; 668
• 7 Brauer B. Handbuch der präparativen anorganischen Chemie 1960; 732
• 8 Geisler K, Jacobs A, Künstler A, Mattes M, Girrleit I, Zimmermann B, Bulka E, Pfeiffer W.-D, Langer P. Synlett 2002; 1983
• 9 For P₄Se₁₀, see: Kudchadker MV, Zingaro RA, Irgolic KJ. Can. J. Chem. 1968; 46: 1415

For the synthesis of N,N-disubstituted selenocarboxylic amides, see:
• 10a Collhard-Charon C, Renson M. Bull. Soc. Chim. Belg. 1963; 72: 304
• 10b Jensen KA, Nielsen PH. Acta Chim. Scand. 1966; 20: 597 See also
• 10c Sukhai RS, de Jong R, Brandsma L. Synthesis 1977; 888
• 11 Geisler K, Pfeiffer W.-D, Künzler A, Below H, Bulka E, Langer P. Synthesis 2004; 875
• 12a Dunbar RE, Painter EP. J. Am. Chem. Soc. 1947; 69: 1833
• 12b Metzger J, Bailly P. Bull. Soc. Chim. Fr. 1955; 1249
• 13 Zhou Y, Linder A, Heimgartner H. Helv. Chim. Acta 2000; 83: 1576
• 14 Douglass IB. J. Am. Chem. Soc. 1937; 59: 740
• 15 Flaig R, Hartmann H. Helv. Chim. Acta 1997; 45: 875
• 16 Zingaro RA, Benett FC, Hammar GW. J. Org. Chem. 1953; 18: 292
• 17a Bulka EAhlers K.-D, Tucek E. Chem. Ber. 1967; 100: 1459
• 17b Bulka E, Ahlers K.-D. Z. Chem. 1963; 3: 349
• 17c Bulka EAhlers K.-D, Tucek E. Chem. Ber. 1967; 100: 1367
• 18 Pfeiffer W.-D, Ahlers K.-D, Falodun A, Villinger A, Langer P. Phosphorus, Sulfur Silicon Relat. Elem. 2014; 189: 324
• 19 Bodtke A, Kandt M, Pfeiffer W.-D, Langer P. Phosphorus, Sulfur Silicon Relat. Elem. 2007; 182: 209
• 20 Geisler K, Pfeiffer W.-D, Müller C, Nobst E, Bulka E, Langer P. Synthesis 2003; 1215
• 21 Geisler K, Künstler A, Bulka E, Pfeiffer W.-D, Langer P. Synlett 2003; 1195
• 22 Geisler K, Künzler A, Bulka E, Pfeiffer W.-D, Langer P. Synthesis 2004; 97
• 23 Geisler K, Below H, Möller A, Bulka E. Z. Chem. 1984; 24: 99
• 24 Below H, Pfeiffer W.-D, Geisler K, Lalk M, Langer P. Eur. J. Org. Chem. 2005; 3637
• 25 Below H, Pfeiffer W.-D, Geisler K, Saghyan AS, Fischer C, Langer P. J. Heterocycl. Chem. 2015; 52: 592
• 26 Pfeiffer W.-D, Roßberg H, Kelzhanova N, Saginayev AT, Villinger A, Langer P. Heterocyles 2014; 88: 1397
• 27a Jira T, Stelzer A, Pfeiffer WD, Schopplich C, Siegert S, Kindermann M. Pharmazie 1997; 52: 831
• 27b Pfeiffer WD, Roßberg H. Pharmazie 1993; 48: 732
• 28 Pfeiffer WD, Dilk E, Roßberg H, Langer P. Synlett 2003; 2392