The Xanthate Route to Amines, Anilines, and Other Nitrogen Compounds. A Brief Account

This article is dedicated with respect and admiration to Professor Martin G. Banwell (Australian National University).

Abstract

An overview of a convergent, modular route to protected amines, anilines, and related compounds hinging on the degenerate radical addition-transfer of xanthates is presented. Emphasis is placed on the importance of the stabilization of the starting radical by imides and other structures.

1 Introduction

2 The Degenerate Xanthate Transfer Process and Examples of Amine Synthesis

3 Stabilization of Radicals by Imides. Initial Observations and the Radical Aminomethylation of Alkenes

4 More Elaborate Phthalimide-Substituted Xanthates

5 Polyamines and β-Lactams

6 Anilines and Related Derivatives

7 Further Synthetic Variations

8 Outlook and Perspectives

Key words

radicals - xanthates - amines - polyamines - anilines - β-lactams

• References

• 1 Amino Group Chemistry . Ricci A. Wiley-VCH; Weinheim: 2008
• 2 For a review on azides, see: Bräse S, Gil C, Knepper K, Zimmermann V. Angew. Chem. Int. Ed. 2005; 44: 5188
• 3 Synthetic Applications of 1,3-Dipolar Cycloaddition Chemistry Toward Heterocycles and Natural Products. Padwa A, Pearson WH. John Wiley & Sons; New York: 2002
• 4 Chatterjee AK In Handbook of Metathesis . Vol. 2. Grubbs RH, O’Leary DJ. Wiley-VCH; Weinheim: 2015: 246
• 5 Overman LE, Carpenter NE. Org. React. 2005; 66: 1

For recent reviews of hydroamination and aminoalkylations of alkenes, see:
• 6a Nishina N, Yamamoto Y. Top. Organomet. Chem. 2013; 43: 115
• 6b Hesp K, Stradiotto M. ChemCatChem 2010; 2: 112
• 6c Müller TE, Hultzsch KC, Yus M, Foubelo F, Tada M. Chem. Rev. 2008; 108: 3795
• 6d Eilbracht P, Bärfacker L, Buss C, Hollmann C, Kitsos-Rzychon BE, Kranemann CL, Rishe T, Roggenbuck R, Schmidt A. Chem. Rev. 1999; 99: 3329

For examples of recent advances in this field, see:
• 6e Yang Y, Shi S.-L, Niu D, Liu P, Buchwald SL. Science 2015; 349: 62
• 6f Piou T, Rovis T. Nature 2015; 527: 86
• 7a Radicals in Organic Synthesis . Renaud P, Sibi MP. Wiley-VCH; Weinheim: 2001
• 7b Zard SZ. Radical Reactions in Organic Synthesis . Oxford University Press; New York: 2003
• 8 For a review on nitrogen-centered radicals, see: Zard SZ. Chem. Soc. Rev. 2008; 37: 1603
• 9 Encyclopedia of Radicals in Chemistry, Biology and Materials . Chatgilialoglu C, Studer A. Wiley-VCH; Weinheim: 2012

For reviews, see:
• 10a Zard SZ. Angew. Chem., Int. Ed. Engl. 1997; 36: 672
• 10b Quiclet-Sire B, Zard SZ. Chem. Eur. J. 2006; 12: 6002
• 10c Quiclet-Sire B, Zard SZ. Top. Curr. Chem. 2006; 264: 201
• 10d Zard SZ. Org. Biomol. Chem. 2007; 5: 205
• 10e Zard SZ. Aust. J. Chem. 2006; 59: 663
• 10f Quiclet-Sire B, Zard SZ. Pure Appl. Chem. 2011; 83: 519
• 11 Han S, Zard SZ. Tetrahedron 2015; 71: 3680
• 12 Li S, Zard SZ. Org. Lett. 2013; 15: 5898
• 13a Barton DH. R, Jang DO, Jaszberenyi JCs. Tetrahedron Lett. 1992; 33: 5709
• 13b Boivin J, Jrad R, Juge S, Nguyen VT. Org. Lett. 2003; 5: 1645
• 14a Gagosz F, Zard SZ. Org. Lett. 2003; 5: 2655
• 14b Gagosz F, Zard SZ. Org. Synth. 2007; 84: 32
• 15 Heinrich M, Zard SZ. Org. Lett. 2004; 6: 4969
• 16 Qin L, Zard SZ. Org. Lett. 2015; 17: 1577
• 17 Boivin J, Pothier J, Zard SZ. Tetrahedron Lett. 1999; 40: 3701
• 18 Boutillier P, Quiclet-Sire B, Zafar SN, Zard SZ. Tetrahedron: Asymmetry 2010; 21: 1649
• 19a Georghe A, Quiclet-Sire B, Vila X, Zard SZ. Org. Lett. 2005; 7: 1653
• 19b Georghe A, Quiclet-Sire B, Vila X, Zard SZ. Tetrahedron 2007; 63: 7187
• 20 Quiclet-Sire B, Zard SZ. Org. Lett. 2008; 10: 3279
• 21 Aminoalkyl radicals are considered to be stabilized by a favorable two-orbital–three-electron interaction. Diminishing the availability of the lone pair on nitrogen (e.g., by protonation) causes a destabilization of the aminoalkyl radical, see: Mayer PM, Glukhovtsev MN, Gauld JW, Radom L. J. Am. Chem. Soc. 1997; 119: 12889
• 22a Bouhadir G, Legrand N, Quiclet-Sire B, Zard SZ. Tetrahedron Lett. 1999; 40: 277
• 22b Thang SH, Chong YK, Mayadunne RT. A, Moad G, Rizzardo E. Tetrahedron Lett. 1999; 40: 2435
• 23 Hargreaves MK, Pritchard JG, Dave HR. Chem. Rev. 1970; 70: 439 ; and references cited therein
• 24 Quiclet-Sire B, Yanagisawa Y, Zard SZ. Chem. Commun. 2014; 50: 2324
• 25 Quiclet-Sire B, Zard SZ. J. Am. Chem. Soc. 2015; 137: 6762
• 26 Quiclet-Sire B, Zard SZ. Org. Lett. 2013; 15: 5886
• 27 Braun M.-G, Zard SZ. Org. Lett. 2011; 13: 776
• 28a Huang Z, Xu J. Tetrahedron 2013; 69: 10272
• 28b Huang Z, Xu J. Tetrahedron 2013; 69: 1050
• 28c Kakaei S, Chen N, Xu J. Tetrahedron 2013; 69: 302
• 29 Quiclet-Sire B., Zard S. Z. unpublished observations.
• 30 Easton CJ, Hutton CA, Rositano G, Tan EW. J. Org. Chem. 1991; 56: 5614

For reviews on the Wohl–Ziegler reaction, see:
• 31a Djerrassi C. Chem. Rev. 1948; 43: 271
• 31b Horner L, Winkelman EM. Angew. Chem. 1959; 71: 349
• 32 Han S, Jones RA, Quiclet-Sire B, Zard SZ. Tetrahedron 2014; 70: 7192
• 33 Frey PA. Acc. Chem. Res. 2014; 47: 540
• 34 Spiteller P, von Nussbaum F. β-Amino Acids in Natural Products . In Enantioselective Synthesis of β-Amino Acids . Juaristi E, Soloshonok V. Wiley; Hoboken: 2005: 2nd ed., 19-91
• 35 Quiclet-Sire B, Revol G, Zard SZ. Org. Lett. 2009; 11: 3554
• 36 Quiclet-Sire B, Revol G, Zard SZ. Tetrahedron 2010; 66: 6656
• 37 For examples of additions of S-(N,N-diacetylmethyl)-O-ethyl xanthate, see: Salomon P. Ph.D. Dissertation. École Polytechnique; France: 2014
• 38 Klapper M, Hamciuc C, Dyllick-Brenzinger R, Müllen K. Angew. Chem. Int. Ed. 2003; 42: 4687
• 39 Han S, Zard SZ. Org. Lett. 2014; 16: 5386
• 40 Auzmendi-Murua I, Bozelli JW. J. Phys. Chem. A. 2012; 116: 7550
• 41 Quiclet-Sire B, Zard SZ. Heterocycles 2010; 82: 263
• 42 Cooper RD. G, José FL. J. Am. Chem. Soc. 1972; 94: 1021
• 43 For a rare example, see: Fliri H, Mak CP. J. Org. Chem. 1985; 50: 3438
• 44 Beyersbergen van Henegouwen WG, Fieseler RM, Rutjes FP. J. T, Hiemstra H. J. Org. Chem. 2000; 65: 8317
• 45 Lebreux F, Quiclet-Sire B, Zard SZ. Org. Lett. 2009; 11: 2844
• 46 Quiclet-Sire B, Sortais B, Zard SZ. Synlett 2002; 903
• 47 Liu Z, Qin L, Zard SZ. Org. Lett. 2012; 14: 5976
• 48a Liu Z, Qin L, Zard SZ. Org. Lett. 2014; 16: 2704
• 48b Laot Y, Petit L, Tran ND. M, Zard SZ. Aust. J. Chem. 2011; 64: 416
• 48c Laot Y, Petit L, Zard SZ. Org. Lett. 2010; 12: 3426
• 49a Qin L, Liu Z, Zard SZ. Org. Lett. 2014; 16: 2966
• 49b Laot Y, Petit L, Zard SZ. Chem. Commun. 2010; 46: 5784
• 49c El Qacemi M, Ricard L, Zard SZ. Chem. Commun. 2006; 4422
• 50a Paleo E, Osornio YM, Miranda LD. Org. Biomol. Chem. 2011; 9: 361
• 50b Flórez-López E, Gomez-Pérez LB, Miranda LD. Tetrahedron Lett. 2010; 51: 6000
• 50c Reyes-Gutiérrez PE, Torres-Ochoa RO, Martínez R, Miranda LD. Org. Biomol. Chem. 2009; 7: 1388
• 50d Osornio YM, Cruz-Almanza R, Jiménez-Montaño V, Miranda LD. Chem. Commun. 2003; 2316
• 51 Debien L, Quiclet-Sire B, Zard SZ. Acc. Chem. Res. 2015; 48: 1237
• 52a Brioche J, Michalak M, Quiclet-Sire B, Zard SZ. Org. Lett. 2011; 13: 6296
• 52b Debien L, Quiclet-Sire B, Zard SZ. Org. Lett. 2011; 13: 5676
• 52c Debien L, Braun M.-G, Quiclet-Sire B, Zard SZ. Org. Lett. 2013; 15: 6250
• 52d Debien L, Quiclet-Sire B, Zard SZ. Org. Lett. 2012; 14: 5118

For reviews, see:
• 53a Ollivier C, Renaud P. Chem. Rev. 2001; 101: 3415
• 53b Darmency V, Renaud P. Top. Curr. Chem. 2006; 263: 71
• 54 Charrier N, Gravestock D, Zard SZ. Angew. Chem. Int. Ed. 2006; 45: 6520
• 55 Barbier F, Pautrat F, Quiclet-Sire B, Zard SZ. Synlett 2002; 811
• 56a Panchaud P, Renaud P. J. Org. Chem. 2004; 69: 3205
• 56b Panchaud P, Ollivier C, Renaud P, Zigmantas S. J. Org. Chem. 2004; 69: 2755
• 56c Ollivier C, Renaud P. J. Am. Chem. Soc. 2001; 123: 4717
• 56d Ollivier C, Renaud P. J. Am. Chem. Soc. 2000; 122: 6496
• 57a Kim S. Adv. Synth. Catal. 2004; 346: 19
• 57b Kim S, Lim CJ. Angew. Chem. Int. Ed. 2002; 41: 3265
• 57c Kim S, Song H.-J, Choi T.-L, Yoon J.-Y. Angew. Chem. Int. Ed. 2001; 40: 2524
• 58 Katritzky AR, Button MA. C, Denisenko S. Heterocycles 2001; 54: 301