Application of Fundamental Organometallic Chemistry to the Development of a Gold-Catalyzed Synthesis of Sulfinate Derivatives†
Miles W. Johnson
Department of Chemistry, University of California, Berkeley, Berkeley, CA 94720 (USA)
Search for more papers by this authorScott W. Bagley
Pfizer Worldwide Medicinal Chemistry, Groton, CT 06340 (USA)
Search for more papers by this authorProf. Neal P. Mankad
Department of Chemistry, University of Illinois at Chicago (USA)
Search for more papers by this authorProf. Robert G. Bergman
Department of Chemistry, University of California, Berkeley, Berkeley, CA 94720 (USA)
Search for more papers by this authorCorresponding Author
Dr. Vincent Mascitti
Pfizer Worldwide Medicinal Chemistry, Groton, CT 06340 (USA)
Vincent Mascitti, Pfizer Worldwide Medicinal Chemistry, Groton, CT 06340 (USA)
F. Dean Toste, Department of Chemistry, University of California, Berkeley, Berkeley, CA 94720 (USA)
Search for more papers by this authorCorresponding Author
Prof. F. Dean Toste
Department of Chemistry, University of California, Berkeley, Berkeley, CA 94720 (USA)
Vincent Mascitti, Pfizer Worldwide Medicinal Chemistry, Groton, CT 06340 (USA)
F. Dean Toste, Department of Chemistry, University of California, Berkeley, Berkeley, CA 94720 (USA)
Search for more papers by this authorMiles W. Johnson
Department of Chemistry, University of California, Berkeley, Berkeley, CA 94720 (USA)
Search for more papers by this authorScott W. Bagley
Pfizer Worldwide Medicinal Chemistry, Groton, CT 06340 (USA)
Search for more papers by this authorProf. Neal P. Mankad
Department of Chemistry, University of Illinois at Chicago (USA)
Search for more papers by this authorProf. Robert G. Bergman
Department of Chemistry, University of California, Berkeley, Berkeley, CA 94720 (USA)
Search for more papers by this authorCorresponding Author
Dr. Vincent Mascitti
Pfizer Worldwide Medicinal Chemistry, Groton, CT 06340 (USA)
Vincent Mascitti, Pfizer Worldwide Medicinal Chemistry, Groton, CT 06340 (USA)
F. Dean Toste, Department of Chemistry, University of California, Berkeley, Berkeley, CA 94720 (USA)
Search for more papers by this authorCorresponding Author
Prof. F. Dean Toste
Department of Chemistry, University of California, Berkeley, Berkeley, CA 94720 (USA)
Vincent Mascitti, Pfizer Worldwide Medicinal Chemistry, Groton, CT 06340 (USA)
F. Dean Toste, Department of Chemistry, University of California, Berkeley, Berkeley, CA 94720 (USA)
Search for more papers by this authorThis research was supported in part by a grant from the NIHGMS (RO1 GM073932). M.W.J. is grateful to the National Science Foundation (no. DGE1106400) and UC Berkeley for pre-doctoral research fellowships. N.P.M. acknowledges the National Institute of Health for a Kirchstein-NRSA postdoctoral fellowship. S.W.B. thanks Andrei Shavyna, Aaron Smith, and Kevin Hesp for helpful discussions. William J. Wolf (UC Berkeley) and Brian Samas (Pfizer) are thanked for assistance with X-ray crystallographic studies.
Abstract
The development of a gold(I)-catalyzed sulfination of aryl boronic acids is described. This transformation proceeds through an unprecedented mechanism which exploits the reactivity of gold(I)–heteroatom bonds to form sulfinate anions. Further in situ elaboration of the sulfinate intermediates leads to the corresponding sulfones and sulfonamides, two pharmacophores routinely encountered in drug discovery.
Supporting Information
As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re-organized for online delivery, but are not copy-edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors.
| Filename | Description |
|---|---|
| ange_201400037_sm_miscellaneous_information.pdf1.1 MB | miscellaneous_information |
Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.
References
- 1For recent reviews, see:
- 1aA. Corma, A. Leyva-Pérez, M. J. Sabater, Chem. Rev. 2011, 111, 1657–1712;
- 1bN. D. Shapiro, F. D. Toste, Synlett 2010, 675–691.
- 2
- 2aG. Zhang, L. Cui, Y. Wang, L. Zhang, J. Am. Chem. Soc. 2010, 132, 1474–1475;
- 2bW. E. Brenzovich, D. Benitez, A. D. Lackner, H. P. Shunantona, E. Tkatchouk, W. A. Goddard, F. D. Toste, Angew. Chem. 2010, 122, 5651–5654;
10.1002/ange.201002739 Google ScholarAngew. Chem. Int. Ed. 2010, 49, 5519–5522;
- 2cA. D. Melhado, W. E. Brenzovich, A. D. Lackner, F. D. Toste, J. Am. Chem. Soc. 2010, 132, 8885–8887.
- 3
- 3aD. S. Laitar, P. Müller, T. J. Gray, J. P. Sadighi, Organometallics 2005, 24, 4503–4505;
- 3bS. Dupuy, L. Crawford, M. Bühl, A. M. Z. Slawin, S. P. Nolan, Adv. Synth. Catal. 2012, 354, 2380–2386;
- 3cE. Y. Tsui, P. Müller, J. P. Sadighi, Angew. Chem. 2008, 120, 9069–9072;
10.1002/ange.200803842 Google ScholarAngew. Chem. Int. Ed. 2008, 47, 8937–8940;
- 3dM. W. Johnson, S. L. Shevick, F. D. Toste, R. G. Bergman, Chem. Sci. 2013, 4, 1023–1027.
- 4
- 4aA. Johnson, R. J. Puddephatt, J. L. Quirk, J. Chem. Soc. Chem. Commun. 1972, 938–939;
- 4bA. Johnson, R. J. Puddephatt, J. Chem. Soc. Dalton Trans. 1977, 1384–1388.
- 5M. Aresta, G. Vasapollo, J. Organomet. Chem. 1971, 26-33, C 51–53.
- 6For the synthesis of gold(I) organosulfinates and organosulfonates via salt metathesis, see: P. Römbke, A. Schier, H. Schmidbaur, J. Chem. Soc. Dalton Trans. 2001, 2482–2486.
- 7
- 7aB. Nguyen, E. J. Emmett, M. C. Willis, J. Am. Chem. Soc. 2010, 132, 16372–16373;
- 7bH. Yang, Y. Li, M. Jiang, J. Wang, H. Fu, Chem. Eur. J. 2011, 17, 5652–5660;
- 7cS. Ye, J. Wu, Chem. Commun. 2012, 48, 7753–7755;
- 7dJ. R. DeBergh, N. Niljianskul, S. L. Buchwald, J. Am. Chem. Soc. 2013, 135, 10638–10641;
- 7eX. Tang, L. Huang, C. Qi, X. Wu, W. Wu, H. Jiang, Chem. Commun. 2013, 49, 6102–6104;
- 7fE. J. Emmett, B. R. Hayter, M. C. Willis, Angew. Chem. 2013, 125, 12911–12915;
10.1002/ange.201305369 Google ScholarAngew. Chem. Int. Ed. 2013, 52, 12679–12683;
- 7gC. S. Richards-Taylor, D. C. Blakemore, M. C. Willis, Chem. Sci. 2014, 5, 222–228;
- 7hA. Shavnya, S. B. Coffey, A. C. Smith, V. Mascitti, Org. Lett. 2013, 15, 6226–6229.
- 8For other methods to synthesize sulfones and sulfonamides from aryl boronic acids, see:
- 8aC. Beaulieu, D. Guay, Z. Wang, D. A. Evans, Tetrahedron Lett. 2004, 45, 3233;
- 8bB. P. Bandgar, S. V. Bettigeri, J. Phopase, Org. Lett. 2004, 6, 2105;
- 8cF. Huang, R. A. Batey, Tetrahedron Lett. 2007, 48, 7667; ref. [7c,d].
- 9For a review on NHCs in gold catalysis, see: N. Marion, S. P. Nolan, Chem. Soc. Rev. 2008, 37, 1776–1782.
- 10A gold sulfinate previously reported in the literature (Ref. [5]) was also structurally characterized. See the Supporting Information for further details.
- 11K. E. Roth, S. A. Blum, Organometallics 2010, 29, 1712–1716.
- 12For a review of SO2 insertion into metal–carbon bonds, see: A. Wojcicki, Adv. Organomet. Chem. 1974, 12, 31–81.
- 13See the Supporting Information for a complete survey of gold catalysts and solvents.
- 14Phosphine-supported gold alkoxides are rare and have only been isolated using electron-deficient alkoxide ligands: S. Komiya, M. Iwata, T. Sone, A. Fukuoka, J. Chem. Soc. Chem. Commun. 1992, 1109–1110.
- 15W. E. Byrd, Inorg. Chem. 1962, 1, 762–768.
- 16Reaction of IPrAu(4-CNCH6H4) with SO2 also results in no reaction. See the Supporting Information for further details.
- 17For examples of pharmaceuticals possessing both indazolyl and sulfonyl moieties, see:
- 17aH. Rueeger, R. Lueoend, O. Rogel, J.-M. Rondeau, H. Möbitz, R. Machauer, L. Jacobsen, M. Staufenbiel, S. Desrayaud, U. Neumann, J. Med. Chem. 2012, 55, 3364–3386;
- 17bD. Spinks, L. S. Torrie, S. Thompson, J. R. Harrison, J. A. Frearson, K. D. Read, A. H. Fairlamb, P. G. Wyatt, I. H. Gilbert, ChemMedChem 2012, 7, 95–106.
- 18The two libraries provided a 93 % (sulfone synthesis) and 100 % (sulfonamide synthesis) success rate as measured by product successfully isolated and characterized (1H and 13C NMR spectroscopy, and LCMS).
Citing Literature
This is the
German version
of Angewandte Chemie.
Note for articles published since 1962:
Do not cite this version alone.
Take me to the International Edition version with citable page numbers, DOI, and citation export.
We apologize for the inconvenience.
