Amination of Arylboronic Compounds via the Copper-Catalyzed Addition of Arylboronic Esters to Azodicarboxylates

Abstract

Arylboronic esters add to di-tert-butyl azodicarboxylate under mild reaction conditions (at room temperature) to afford aryl-substituted­ hydrazine derivatives in good yields. The reaction tolerates a wide variety of functional groups.

Key words

amination - arylboronic esters - azodicarboxylates - copper - homogeneous catalysis

• References


For reviews on organoboron compounds, see:
• 1a Hall DG. Boronic Acids: Preparation, Applications in Organic Synthesis and Medicine. Wiley-VCH; Weinheim: 2005
• 1b Hall DG. Boronic Acids: Preparation and Applications in Organic Synthesis, Medicine and Materials. Vol. 2. Wiley-VCH; Weinheim: 2011

For recent reviews on amination of organoboron compounds, see:
• 2a Qiao JX, Lam PY. S. Synthesis 2011; 829
• 2b Rao KS, Wu T.-S. Tetrahedron 2012; 68: 7735
• 3a Chan DM. T, Monaco KL, Wang R.-P, Winters MP. Tetrahedron Lett. 1998; 39: 2933
• 3b Lam PY. S, Clark CG, Saubern S, Adams J, Winters MP, Chan DM. T, Combs A. Tetrahedron Lett. 1998; 39: 2941
• 3c Yoo W.-J, Tsukamoto T, Kobayashi S. Angew. Chem. Int. Ed. 2015; 54: 6587
• 4a Liu S, Yu Y, Liebeskind LS. Org. Lett. 2007; 9: 1947
• 4b Zhang Z, Yu Y, Liebeskind LS. Org. Lett. 2008; 10: 3005
• 4c Liu S, Liebeskind LS. J. Am. Chem. Soc. 2008; 130: 6918
• 4d Matsuda N, Hirano K, Satoh T, Miura M. Angew. Chem. Int. Ed. 2012; 51: 3642
• 4e Rucker RP, Whittaker AM, Dang H, Lalic G. Angew. Chem. Int. Ed. 2012; 51: 3953
• 4f Moon S.-Y, Nam J, Rathwell K, Kim W.-S. Org. Lett. 2014; 16: 338
• 4g Moon S.-Y, Kim UB, Sung D.-B, Kim W.-S. J. Org. Chem. 2015; 80: 1856
• 5 Uemura T, Chatani N. J. Org. Chem. 2005; 70: 8631

For papers on the addition of arylboronic acids to azodicarboxylate, see, Cu catalyst:
• 6a Kisseljova K, Tšubrik O, Sillard R, Mäeorg S, Mäeorg U. Org. Lett. 2006; 8: 43
• 6b Shibue T, Fukuda Y. Tetrahedron Lett. 2014; 55: 4102

Pd catalyst:
• 6c Muñiz K, Iglesias A. Angew. Chem. Int. Ed. 2007; 46: 6350

For recent reviews on C–H borylation, see:
• 7a Ishiyama T, Miyaura N. J. Organomet. Chem. 2003; 680: 3
• 7b Ishiyama T, Miyaura N. Chem. Rec. 2004; 3: 271
• 7c Mkhalid IA. I, Barnard JH, Marder TB, Murphy JM, Hartwig JF. Chem. Rev. 2010; 110: 890
• 7d Hartwig JF. Chem. Soc. Rev. 2011; 40: 1992
• 7e Hartwig JF. Acc. Chem. Res. 2012; 45: 864
• 7f Ros A, Fernández R, Lassaletta JM. Chem. Soc. Rev. 2014; 43: 3229
• 8a Huang K, Yu D.-G, Zheng S.-F, Wu Z.-H, Shi Z.-J. Chem. Eur. J. 2011; 17: 786
• 8b Kinuta H, Tobisu M, Chatani N. J. Am. Chem. Soc. 2015; 137: 1593
• 8c Kinuta H, Hasegawa J, Tobisu M, Chatani N. Chem. Lett. 2015; 44: 366
• 8d Zarate C, Manzano R, Martin R. J. Am. Chem. Soc. 2015; 137: 6754
• 9a Tobisu M, Kinuta H, Kita Y, Rémond E, Chatani N. J. Am. Chem. Soc. 2012; 134: 115
• 9b Kinuta H, Kita Y, Rémond E, Tobisu M, Chatani N. Synthesis 2012; 44: 2999
• 10 Reaction conditions used in ref. 5: arylboronic acid (1 mmol), di-tert-butyl azodicarboxylate (2, 0.5 mmol), Cu(OAc)₂ (0.05 mmol), THF (1 mL), r.t., 20 h, under N_2.

The reaction conditions in the papers reported by Sawamura and Roithova were used as reference for optimizing our reaction conditions:
• 11a Ohmiya H, Yokokawa N, Sawamura M. Org. Lett. 2010; 12: 2438
• 11b A small amount of water can be efficiently suppressed the formation of the copper clusters, and improved the solubility of copper acetate: Tsybizova A, Ryland BL, Tsierkezos N, Stahl SS, Roithová J, Schröder D. Eur. J. Inorg. Chem. 2014; 1407
• 12a Zaltsgendler I, Leblanc Y, Bernstein MA. Tetrahedron Lett. 1993; 34: 2441
• 12b Velarde-Ortiz R, Guijarro A, Rieke RD. Tetrahedron Lett. 1998; 39: 9157
• 12c Bombek S, Lenaršič R, Kočevar M, Saint-Jalmes L, Desmurs J.-R, Polanc S. Chem. Commun. 2002; 1494
• 12d Amaoka Y, Kamijo S, Hoshikawa T, Inoue M. J. Org. Chem. 2012; 77: 9959
• 12e Zhu M.-K, Chen Y.-C, Loh T.-P. Chem. Eur. J. 2013; 19: 5250
• 13a Tsuda T, Hashimoto T, Saegusa T. J. Am. Chem. Soc. 1972; 94: 658
• 13b Lemmen TH, Goeden GV, Huffman JC, Geerts RL, Caulton KG. Inorg. Chem. 1990; 29: 3680
• 14 Ma F.-F, Peng Z.-Y, Li W.-F, Xie X.-M, Zhang Z. Synlett 2011; 2555
• 15 Kabalka GW, Guchhait SK. Org. Lett. 2003; 5: 4129