N-Isocyanates, N-Isothiocyanates and Their Masked/Blocked Derivatives: Synthesis and Reactivity

Jean-François Vincent-Rocan; André M. Beauchemin

doi:10.1055/s-0036-1588066

Synthesis, Table of Contents

Synthesis 2016; 48(21): 3625-3645
DOI: 10.1055/s-0036-1588066

review

N-Isocyanates, N-Isothiocyanates and Their Masked/Blocked Derivatives: Synthesis and Reactivity

Jean-François Vincent-Rocan

Centre for Catalysis Research and Innovation, Department of Chemistry and Biomolecular Sciences, University of Ottawa, 10 Marie-Curie, Ottawa, ON, K1N 6N5, Canada Email: andre.beauchemin@uottawa.ca

,

André M. Beauchemin*

Centre for Catalysis Research and Innovation, Department of Chemistry and Biomolecular Sciences, University of Ottawa, 10 Marie-Curie, Ottawa, ON, K1N 6N5, Canada Email: andre.beauchemin@uottawa.ca

› Author Affiliations

Abstract

All articles of this category

Abstract

In contrast to C-substituted isocyanates which are frequently used reagents in synthesis, nitrogen-substituted isocyanates (N-isocyanates) remained a scientific curiosity in the literature for over a century. The amphoteric character of these reactive intermediates, which results in their propensity to dimerize, prevented the development of their full synthetic potential. In this review, the pioneering work that led to the development of reliable methods for their synthesis, established the existence of such species by spectroscopy, and allowed a delineation of their basic reactivity is presented. The high reactivity of these intermediates has been controlled through the use of masked precursors to regulate their concentration via a reversible equilibrium, a strategy which is also used in industrial processes utilizing C-isocyanates. This control led to the development of more complex reactions, including reaction cascades that allow the rapid synthesis of heterocycles possessing the N–N–C=O motif, which is widely present in agrochemicals and pharmaceuticals. This review covers the literature of N-isocyanates and their sulfur analogues, N-isothiocyanates, until April 2016.

1 Introduction

2 Formation of N-Isocyanates

2.1 Rearrangement of Carbamoyl Azides

2.2 Ring Opening of Heterocycles

2.3 Thermolysis of Hydrazine Derivatives

3 Formation of N-Isothiocyanates

4 Isolation and Observation

4.1 Isolation and Observation of N-Isothiocyanates

4.2 Isolation and Observation of N-Isocyanates

5 Reactivity

5.1 Reactivity of N-Isothiocyanates

5.2 Reactivity of N-Isocyanates

6 Conclusion

Key words

isocyanatoamines - isocyanatoimines - nitrogen-substituted isocyanates - heterocyclic chemistry - cascade reactions - amphoteric reagents

Full Text

References

References

For reviews on isocyanates and their use in industry, see:

1a Six C, Richter F. Ullmann’s Encyclopedia of Industrial Chemistry. Vol. 20. Wiley-VCH; Weinheim: 2012: 63-82
1b Isocyanates, Organic. In Kirk-Othmer Encyclopedia of Chemical Technology. 3rd ed., Vol. 19 Wiley; New York: 1982: 28-62
1c Wang Z. Comprehensive Organic Name Reactions and Reagents. Wiley; New York: 2009

For an entry in the polyurethane literature, see:

1d Engels H.-W, Pirkl H.-G, Albers R, Albach RW, Krause J, Hoffman A, Casselmann H, Dormish J. Angew. Chem. Int. Ed. 2013; 52: 9422

2a Wicks DA, Wicks ZW. Jr. Prog. Org. Coat. 1999; 36: 148
2b Wicks DA, Wicks ZW. Jr. Prog. Org. Coat. 2001; 41: 1
2c Wicks ZW. Jr, Jones FN, Pappas SP, Wicks DA. Organic Coatings: Science and Technology. Wiley-VCH; Weinheim: 2007
2d Delebecq E, Pascault J.-P, Boutevin B, Ganachaud F. Chem. Rev. 2013; 113: 80

3 Such intermediates have also been referred to as isocyanatoamines and isocyanatoimines in the literature; however, the simpler nomenclature (e.g., amino isocyanate) was somewhat more prevalent. The latter nomenclature (e.g., N-isocyanates) is used herein.
4 Reichen W. Chem. Rev. 1978; 78: 569
5 Wentrup C, Finnerty JJ, Koch R. Curr. Org. Chem. 2011; 15: 1745
6 Curtius ZT. Angew. Chem. 1914; 27: 213

7a Stollé R. J. Prakt. Chem. 1927; 116: 192
7b Stollé R. J. Prakt. Chem. 1928; 117: 185

8 Kurz M, Reichen W. Tetrahedron Lett. 1978; 1433
9 Lwowski W, DeMauriac R, Mattingly TW. Jr, Scheiffele E. Tetrahedron Lett. 1964; 3285
10 Lwowski W, DeMauriac RA, Murray RA, Lunow L. Tetrahedron Lett. 1971; 425
11 Reichen W. Helv. Chim. Acta 1976; 59: 2601
12 Reichen W. Helv. Chim. Acta 1977; 60: 498
13 Del Signore G, Fioravanti S, Pellacani L, Tardella PA. Tetrahedron 2001; 57: 4623
14 Wadsworth WS, Emmons WD. J. Org. Chem. 1967; 32: 1279
15 Kerber RC, Ryan TJ. J. Org. Chem. 1971; 36: 1566
16 Seckinger K. Helv. Chim. Acta 1973; 56: 2061
17 Tserng K.-Y, Bauer L. J. Org. Chem. 1973; 38: 3498
18 Lockley WJ. S, Ramakrishnan VT, Lwowski W. Tetrahedron Lett. 1974; 2621
19 Heep U. Tetrahedron 1975; 31: 77
20 Ramakrishnan K, Fulton JB, Warkentin J. Tetrahedron Lett. 1976; 2685
21 Gilchrist TL, Rees CW, Tuddenham D. J. Chem. Soc., Perkin Trans. 1 1981; 3214
22 Jones DW. J. Chem. Soc., Chem. Commun. 1982; 766
23 Theis W, Bethäuser W, Regitz M. Chem. Ber. 1985; 118: 28
24 Senet J.-P, Vergne G, Wooden GP. Tetrahedron Lett. 1986; 27: 6319
25 Squillacote M, De Felippis J. J. Org. Chem. 1994; 59: 3564

For amidoisocyanates in azapeptide analogues, see:

26a Magrath J, Abeles RH. J. Med. Chem. 1992; 35: 4279
26b Han H, Janda KD. J. Am. Chem. Soc. 1996; 118: 2539
26c Xing R, Hanzlik RP. J. Med. Chem. 1998; 41: 1344

27 Busch M. J. Chem. Soc. 1901; 80: 488
28 Acree SF. Ber. Dtsch. Chem. Ges. 1903; 36: 3154
29 Larsen C, Anthoni U, Christophersen C, Nielsen PH. Acta Chem. Scand. 1969; 23: 322
30 Wibers N, Hübler G. Z. Naturforsch. B 1978; 33: 575
31 Kirilin AD, Dokuchayev AA, Sokova NB, Chernyshev EA. Russ. Chem. Bull. 1999; 48: 169
32 Shah SN, Chudgar KN. Molecules 2000; 5: 657
33 Garland K, Gan W, Depatie-Sicard C, Beauchemin AM. Org. Lett. 2013; 15: 4074

34a Cranwell PB, Russell AT, Smith CD. Synlett 2016; 27: 131
34b Cranwell PB, Russell AT. J. Chem. Educ. 2016; 93: 949

35 Kozai S, Takaoka S, Maruyama T. Tetrahedron Lett. 2002; 43: 2633

36a Proulx C, Sabatino D, Hopewell R, Spiegel J, García RamosY, Lubell WD. Future Med. Chem. 2011; 3: 1139
36b Gante J. Synthesis 1989; 405

37 McElhinney RS. J. Chem. Soc. 1966; 950

38a El-Hewhi Z, Taeger E, Funge F. J. Prakt. Chem. 1962; 18: 275
38b Delépine M. Bull. Soc. Chim. Fr. 1902; 587
38c Delépine M, Schving P. Bull. Soc. Chim. Fr. 1910; 896
38d Aubert P, Knott EB, Williams LA. J. Chem. Soc. 1951; 2188
38e Knott EB. J. Chem. Soc. 1956; 1644

39 Anthoni U, Larsen C, Nielsen PH. Acta Chem. Scand. 1966; 20: 1714
40 Anthoni U, Larsen C, Nielsen PH. Acta Chem. Scand. 1968; 22: 309
41 Hünig S, Kiessel M. Chem. Ber. 1958; 91: 380

42a Moller J, Anthoni U, Larsen C, Nielsen PH. Acta Chem. Scand. 1968; 22: 2493
42b Anthoni U, Larsen C, Nielsen PH. Acta Chem. Scand. 1969; 23: 537

43 Larsen C, Anthoni U, Nielsen PH. Acta Chem. Scand. 1969; 23: 320
44 Anthoni U, Berg C. Acta Chem. Scand. 1969; 23: 3602
45 Berg C. J. Chem. Soc., Chem. Commun. 1974; 122
46 Anthoni U, Larsen C, Nielsen PH. Acta Chem. Scand. 1967; 21: 2061
47 Lwowski W, DeMauriac RA, Thompson M, Wilde RE, Chen S.-Y. J. Org. Chem. 1975; 40: 2608
48 Maier G, Teles JH. Chem. Ber. 1989; 122: 745
49 Teles JH, Maier G, Hess BA. Jr, Schaad LJ. Chem. Ber. 1989; 122: 749
50 Maier G, Naumann M, Reisenauer HP, Eckwert J. Angew. Chem., Int. Ed. Engl. 1996; 35: 1696
51 Schulz A, Kalpötke TM. Inorg. Chem. 1996; 35: 4791
52 Zeng X, Beckers H, Willner H. Angew. Chem. Int. Ed. 2011; 50: 482
53 Zeng X, Gerken M, Beckers H, Willner H. Inorg. Chem. 2010; 49: 9694
54 Pasinszki T, Krebsz M, Tarczay G, Wentrup C. J. Org. Chem. 2013; 78: 11985
55 Li H, Wan H, Wu Z, Li D, Bégué D, Wentrup C, Zeng X. Chem. Eur. J. 2016; 22: 7856
56 Anthoni U, Larsen C, Nielsen PH. Acta Chem. Scand. 1967; 21: 1201
57 Beckett T, Dyson GM. J. Chem. Soc. 1937; 1358
58 Anthoni U, Larsen C, Nielsen PH. Acta Chem. Scand. 1967; 21: 2571
59 Anthoni U, Larsen C, Nielsen PH. Acta Chem. Scand. 1967; 21: 2580
60 Anthoni U, Larsen C, Nielsen PH. Acta Chem. Scand. 1968; 22: 1898
61 Anthoni U, Dahl O, Larsen C, Nielsen PH. Acta Chem. Scand. 1969; 23: 943
62 Anthoni U, Larsen C, Nielsen PH. Acta Chem. Scand. 1969; 23: 1439
63 Anthoni U, Larsen C, Nielsen PH. Acta Chem. Scand. 1969; 23: 3385
64 Larsen C, Jakobsen P. Acta Chem. Scand. 1970; 24: 1445
65 Vincent-Rocan J.-F, Clavette C, Leckett K, Beauchemin AM. Chem. Eur. J. 2015; 21: 3886
66 Vincent-Rocan J.-F, Derasp JS, Beauchemin AM. Chem. Commun. 2015; 51: 16405

67a Alt GH, Chupp JP. Tetrahedron Lett. 1970; 3155
67b Chupp JP. J. Heterocycl. Chem. 1971; 8: 571

68 Lockley WJ. S, Lwowski W. Tetrahedron Lett. 1974; 4263
69 Lwowski W, Kanemasa S, Murray RA, Ramakrishnan VT, Thiruvengadam TK, Yoshida K, Subbaraj A. J. Org. Chem. 1986; 51: 1719
70 Gibson HH. Jr, Weissinger K, Abashawl A, Hall G, Lawshae T, LeBlanc K, Moody J, Lwowski W. J. Org. Chem. 1986; 51: 3858
71 Roveda J.-G, Clavette C, Hunt AD, Whipp CJ, Gorelsky SI, Beauchemin AM. J. Am. Chem. Soc. 2009; 131: 8740
72 Ivanovich RA, Clavette C, Vincent-Rocan J.-F, Roveda J.-G, Gorelski SI, Beauchemin AM. Chem. Eur. J. 2016; 22: 7906
73 Clavette C, Gan W, Bongers A, Markiewicz T, Toderian A, Gorelsky SI, Beauchemin AM. J. Am. Chem. Soc. 2012; 134: 16111
74 Bongers A, Moon PJ, Beauchemin AM. Angew. Chem. Int. Ed. 2015; 54: 15516
75 Gan W, Moon PJ, Clavette C, Das Neves N, Markiewicz T, Toderian AB, Beauchemin AM. Org. Lett. 2013; 15: 1890
76 Lavergne K, Bongers A, Betit L, Beauchemin AM. Org. Lett. 2015; 17: 3612
77 Clavette C, Vincent-Rocan J.-F, Beauchemin AM. Angew. Chem. Int. Ed. 2013; 52: 12705
78 Vincent-Rocan J.-F, Ivanovich RA, Clavette C, Leckett K, Bejjani J, Beauchemin AM. Chem. Sci. 2016; 7: 315

For selected reviews on hydroaminations, see:

79a Müller TE, Hultzsch KC, Yus M, Foubelo F, Tada M. Chem. Rev. 2008; 108: 3795
79b Müller TE, Beller M. Chem. Rev. 1998; 98: 675
79c Bernoud E, Lepori C, Mellah M, Schulz E, Hannedouche J. Catal. Sci. Technol. 2015; 5: 2017

For similar Cope-type hydroamination reactivity of hydrazine derivatives, see:

79d Cebrowski PH, Roveda J.-G, Moran J, Gorelsky SI, Beauchemin AM. Chem. Commun. 2008; 492
79e Loiseau F, Clavette C, Raymond M, Roveda J.-G, Burrell A, Beauchemin AM. Chem. Commun. 2011; 47: 562
79f Beauchemin AM. Org. Biomol. Chem. 2013; 11: 7039

80 Ivanovich RA, Vincent-Rocan J.-F, Elkaeed EB, Beauchemin AM. Org. Lett. 2015; 17: 4898
81 Derasp JS, Vincent-Rocan J.-F, Beauchemin AM. Org. Lett. 2016; 18: 658
82 Shao J, Liu X, Tang P, Luo J, Chen W, Yu Y. Org. Lett. 2015; 17: 4502