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

Hirotaka Kinuta; Yusuke Kita; Emmanuelle Rémond; Mamoru Tobisu; Naoto Chatani

doi:10.1055/s-0031-1290370

Synthesis, Table of Contents

Synthesis 2012; 44(19): 2999-3002
DOI: 10.1055/s-0031-1290370

practical synthetic procedures

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

Hirotaka Kinuta

^aDepartment of Applied Chemistry, Faculty of Engineering, Osaka University, Suita, Osaka 565-0871, Japan, Email: chatani@chem.eng.osaka-u.ac.jp

,

Yusuke Kita

^aDepartment of Applied Chemistry, Faculty of Engineering, Osaka University, Suita, Osaka 565-0871, Japan, Email: chatani@chem.eng.osaka-u.ac.jp

,

Emmanuelle Rémond

^aDepartment of Applied Chemistry, Faculty of Engineering, Osaka University, Suita, Osaka 565-0871, Japan, Email: chatani@chem.eng.osaka-u.ac.jp

,

Mamoru Tobisu*

^bCenter for Atomic and Molecular Technologies, Graduate School of Engineering, Osaka University, Suita, Osaka 565-0871, Japan, Email: tobisu@chem.eng.osaka-u.ac.jp

,

Naoto Chatani*

^aDepartment of Applied Chemistry, Faculty of Engineering, Osaka University, Suita, Osaka 565-0871, Japan, Email: chatani@chem.eng.osaka-u.ac.jp

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Abstract

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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

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References

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

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