Copper(II)-Catalyzed Conversion of Aryl/Heteroaryl Boronic Acids, Boronates, and Trifluoroborates into the Corresponding Azides: Substrate Scope and Limitations

 

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Abstract

We report the copper(II)-catalyzed conversion of organoboron compounds into the corresponding azide derivatives. A systematic series of phenylboronic acid derivatives is evaluated to examine the importance of steric and electronic effects of the substituents on reaction yield as well as functional group compatibility. Heterocyclic substrates are also shown to participate in this mild reaction while compounds incorporating B-C(sp^³) bonds are unreactive under the reaction conditions. The copper(II)-catalyzed boronic acid-azide coupling reaction is further extended to both boronate esters and potassium organotrifluoroborate salts. The method described herein complements existing procedures for the preparation of aryl azides from the respective amino, triazene, and halide derivatives and we expect that it will greatly facilitate copper- and ruthenium-catalyzed azide-alkyne cycloaddition reactions for the preparation of diversely functionalized 1-aryl- or 1-heteroaryl-1,2,3-triazoles derivatives.

References

• 1 Tron GC. Pirali T. Billington RA. Canonico PL. Sorba G. Genazzani AA. Med. Res. Rev.  2008,  28:  278 
  CrossrefPubMedGoogle Scholar
• For some representative recent examples, see:
• 2a Gupte A. Boshoff HI. Wilson DJ. Neres J. Labello NP. Somu RV. Xing C. Barry CE. Aldrich CC. J. Med. Chem.  2008,  51:  7495 
  Google Scholar
• 2b Giffin MJ. Heaslet H. Brik A. Lin Y.-C. Cauvi G. Wong C.-H. McRee DE. Elder JH. Stout CD. Torbett BE. J. Med. Chem.  2008,  51:  6263 
  Google Scholar
• 2c Gill C. Jadhav G. Shaikh M. Kale R. Ghawalkar A. Nagargoje D. Shiradkar M. Bioorg. Med. Chem. Lett.  2008,  18:  6244 
  Google Scholar
• 2d Klein M. Dinér P. Dorin-Semblat D. Doering C. Grotli M. Org. Biomol. Chem.  2009,  7:  3421 
  Google Scholar
• 2e Maurya SK. Gollapalli DR. Kirubakaran S. Zhang M. Johnson CR. Benjamin NN. Hedstrom L. Cuny GD. J. Med. Chem.  2009,  52:  4623 
  Google Scholar
• 2f Upadhayaya RS. Kulkarni GM. Vasireddy NR. Vandavasi JK. Dixit SS. Sharma V. Chattopadhyaya J. Bioorg. Med. Chem.  2009,  17:  4681 
  Google Scholar
• 3 Avermaria F. Zimmermann V. Bräse S. Synlett  2004,  1163 
  Article in Thieme ConnectGoogle Scholar
• 4 Barral K. Moorhouse AD. Moses JE. Org. Lett.  2007,  9:  1809 
  CrossrefPubMedGoogle Scholar
• 5 Zhu W. Ma D. Chem. Commun.  2004,  888 
  CrossrefGoogle Scholar
• 6 Morgan J. Pinhey JT. J. Chem. Soc., Perkin Trans. 1  1990,  715 
  CrossrefGoogle Scholar
• 7 Huber M.-L. Pinhey JT. J. Chem. Soc., Perkin Trans. 1  1990,  721 
  CrossrefGoogle Scholar
• 8 Tao C.-Z. Cui X. Li J. Liu A.-X. Liu L. Guo Q.-X. Tetrahedron Lett.  2007,  48:  3525 
  CrossrefGoogle Scholar
• 9 Chan DMT. Monaco KL. Wang R.-P. Winters MP. Tetrahedron Lett.  1998,  39:  2933 
  CrossrefGoogle Scholar
• 10 Lam PYS. Clark CG. Saubern S. Adams J. Winters MP. Chan DMT. Combs A. Tetrahedron Lett.  1998,  39:  2941 
  CrossrefGoogle Scholar
• 11 Hansch C. Leo A. Taft RW. Chem. Rev.  1991,  91:  165 
  Google Scholar
• 12 Molander GA. Ellis N. Acc. Chem. Res.  2007,  40:  275 
  CrossrefPubMedGoogle Scholar
• 13 Tornøe CW. Christensen C. Meldal M. J. Org. Chem.  2002,  67:  3057 
  CrossrefPubMedGoogle Scholar
• 14 Rostovtsev VV. Green LG. Fokin VV. Sharpless KB. Angew. Chem. Int. Ed.  2002,  41:  2596 
  Google Scholar
• 15 Chan DMT. Lam PYS. Recent Advances in Copper-Promoted C-Heteroatom Bond Cross-Coupling Reactions with Boronic Acids and Derivatives, In Boronic Acids   Hall DG. Wiley-VCH; Weinheim: 2005. 
  Google Scholar
• 16 Bertz SH. Cope S. Murphy M. Ogle CA. Taylor BJ. J. Am. Chem. Soc.  2007,  129:  7208 
  CrossrefGoogle Scholar
• 17 Pudlo M. Csányi D. Moreau F. Hajós G. Riedl Z. Sapi J. Tetrahedron  2007,  63:  10320 
  CrossrefGoogle Scholar
• 18 Cho YA. Kim DS. Ahn HR. Canturk B. Molander GA. Ham J. Org. Lett.  2009,  11:  4330 
  CrossrefGoogle Scholar