Novel Synthetic Approach to Arylboronates via Rhodium-Catalyzed Carbon–Cyano Bond Cleavage of Nitriles

Abstract

A new rhodium-catalyzed method for preparing arylboronates from aryl cyanides through the cleavage of carbon–cyano bonds is described. This unprecedented transformation of nitriles allows the use of a cyano group as a boryl equivalent and the regioselective introduction of a boryl group at a late stage of the synthesis.

Key words

rhodium - catalysis - borylation - nitrile - C–CN bond cleavage

• References

• 1a Miyaura N, Suzuki A. Chem. Rev. 1995; 95: 2457
• 1b Suzuki A, Brown HC. Organic Synthesis via Boranes . Aldrich; Milwaukee: 2003
• 1c Hall DG. Boronic Acids . Wiley-VCH; Weinheim: 2005
• 1d Miyaura N. Bull. Chem. Soc. Jpn. 2008; 81: 1535

Selected examples:
• 2a Ishiyama T, Miyaura N. Chem. Rec. 2004; 3: 271
• 2b Zhu W, Ma D. Org. Lett. 2006; 8: 261
• 2c Wilson DA, Wilson CJ, Moldoveanu C, Resmerita A.-M, Corcoran P, Hoang LM, Rosen BM, Percec V. J. Am. Chem. Soc. 2010; 132: 1800
• 2d Ma Y, Song C, Jiang W, Xue G, Cannon JF, Wang X, Andrus MB. Org. Lett. 2003; 5: 4635
• 2e Huang K, Yu D.-G, Heng S.-F, Wu Z.-H, Shi Z.-J. Chem.–Eur. J. 2011; 17: 786

Reviews:
• 3a Cho J.-Y, Tse MK, Holmes D, Maleczka RE, Smith III MR, Ishiyama T, Takagi J, Ishida K, Miyaura N, Anastasi NR, Hartwig JF, Kellogg RM. Chemtracts 2002; 15: 195
• 3b Mkhalid IA. I, Barnard JH, Marder TB, Murphy JM, Hartwig JF. Chem. Rev. 2010; 110: 890

Selected examples of ortho C–H borylation by using directing groups:
• 3c Ishiyama T, Isou H, Kikuchi T, Miyaura N. Chem. Lett. 2011; 40: 1007
• 3d Ros A, López-Rodríguez R, Estepa B, Álvarez E, Fernández R, Lassaletta JM. J. Am. Chem. Soc. 2012; 134: 4573
• 3e Robbins DW, Boebel TA, Hartwig JF. J. Am. Chem. Soc. 2010; 132: 4068
• 3f Yamazaki K, Kawamorita S, Ohmiya H, Sawamura M. Org. Lett. 2010; 12: 3978
• 3g Kawamorita S, Miyazaki T, Ohshima H, Iwai T, Sawamura M. J. Am. Chem. Soc. 2011; 133: 19310
• 3h Dai H.-X, Yu J.-Q. J. Am. Chem. Soc. 2011; 134: 134

Reviews on C–CN bond activation:
• 4a Tobisu M, Chatani N. Chem. Soc. Rev. 2008; 37: 300
• 4b Nakao Y, Hiyama T. Pure Appl. Chem. 2008; 80: 1097
• 5a Tobisu M, Kita Y, Chatani N. J. Am. Chem. Soc. 2006; 128: 8152
• 5b Tobisu M, Kita Y, Ano Y, Chatani N. J. Am. Chem. Soc. 2008; 130: 15982
• 6a Tobisu M, Nakamura R, Kita Y, Chatani N. J. Am. Chem. Soc. 2009; 131: 3174
• 6b Tobisu M, Nakamura R, Kita Y, Chatani N. Bull. Korean Chem. Soc. 2010; 31: 582
• 7 Kita Y, Tobisu M, Chatani N. Org. Lett. 2010; 12: 1864
• 8 Tobisu M, Kinuta H, Kita Y, Rémond E, Chatani N. J. Am. Chem. Soc. 2012; 134: 115
• 9 Aryl bromide was borylated under the presented conditions. Competition studies revealed that relative reactivity of ArBr/ArCN towards Rh-catalyzed borylation to be ca. 1:2.4
• 10a Noguchi H, Hojo K, Suginome M. J. Am. Chem. Soc. 2007; 129: 758
• 10b Noguchi H, Shioda T, Chou C.-M, Suginome M. Org. Lett. 2008; 10: 377
• 11 Kabalka GW, Das BC, Das S. Tetrahedron Lett. 2002; 43: 2323
• 12 Commercially available from Kanto Chemical Co., Inc. as Cyhalofop butyl
• 13a Krizan TD, Martin JC. J. Am. Chem. Soc. 1983; 105: 6155
• 13b Uchiyama M, Koike M, Kameda M, Kondo Y, Sakamoto T. J. Am. Chem. Soc. 1996; 118: 8733
• 13c Naka H, Uchiyama M, Matsumoto Y, Wheatley AE. H, McPartlin M, Morey JV, Kondo Y. J. Am. Chem. Soc. 2007; 129: 1921
• 13d Usui S, Hashimoto Y, Morey JV, Wheatley AE. H, Uchiyama M. J. Am. Chem. Soc. 2007; 129: 15102
• 13e Kakiuchi F, Sonoda M, Tsujimoto T, Chatani N, Murai S. Chem. Lett. 1999; 1083
• 13f Chotana GA, Rak MA, Smith III MR. J. Am. Chem. Soc. 2005; 127: 10539
• 13g Li W, Xu Z, Sun P, Jiang X, Fang M. Org. Lett. 2011; 13: 1286
• 14 Ishiyama T, Nobuta Y, Hartwig JF, Miyaura N. Chem. Commun. 2003; 2924
• 15 Giordano G, Crabtree RH. Inorg. Synth. 1979; 19: 218