Copper-Catalyzed Selective S-Arylation of 1,2-Bis(o-amino-1H-pyrazolyl) Disulfides with
Arylboronic Acids

Pei-Song Luo; Feng Wang; Jin-Heng Li; Ri-Yuan Tang; Ping Zhong

doi:10.1055/s-0028-1083357

PAPER

Copper-Catalyzed Selective S-Arylation of 1,2-Bis(o-amino-1H-pyrazolyl) Disulfides with Arylboronic Acids

Pei-Song Luo^a, Feng Wang^b, Jin-Heng Li*^a,b, Ri-Yuan Tang^a, Ping Zhong*^a
^a College of Chemistry and Materials Science, Wenzhou University, Wenzhou 325035, P. R. of China
^b Key Laboratory of Chemical Biology & Traditional Chinese Medicine Research (Ministry of Education), Hunan Normal University, Changsha 410081, P. R. of China
Fax: +86(731)8872101; e-Mail: jhli@hunnu.edu.cn;

Abstract

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Abstract

Copper-catalyzed oxidative S-arylation of 1,2-bis(o-amino-1H-pyrazolyl) disulfides with arylboronic acids for the synthesis of (o-amino-1H-pyrazolyl)aryl sulfides has been developed in the presence of CuI, 1,10-phenanthroline, and O₂. A variety of dipyrazolyl disulfides bearing free NH₂ groups underwent the reaction with arylboronic acids efficiently to selectively afford the corresponding S-arylation products in moderate to excellent yield. It is noteworthy that amino groups are tolerated well, and a series of fipronil analogues are prepared.

Key words

copper - 1,10-phenanthroline - S-arylation - 1,2-bis(o-amino-1H-pyrazolyl) disulfides - arylboronic acid - (o-amino-1H-pyrazolyl)aryl sulfide

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References

<A NAME="RF21808SS-1A">1a</A> Buntain IG, Hatton LR, Hawkins DW, Pearson CJ, and Roberts DA. inventors; Eur. Pat. Appl. 295117 A1. ; Chem. Abstr. 1990, 112, 35845

<A NAME="RF21808SS-1B">1b</A> Wu T.-T. inventors; US Patent 5814652. ; Chem. Abstr. 1998, 129, 256473

<A NAME="RF21808SS-1C">1c</A> Caboni P. Sammelson RE. Casida JE. J. Agric. Food Chem. 2003, 24: 7055

<A NAME="RF21808SS-1D">1d</A> Wang Y. Chackalamannil S. Hu Z. Clader JW. Greenlee W. Billard W. Binch H. Crosby G. Ruperto V. Duffy RA. McQuade R. Lachowicz J. Bioorg. Med. Chem. Lett. 2000, 10: 2247

<A NAME="RF21808SS-1E">1e</A> Nielson SF. Nielson EO. Olsen GM. Liljefors T. Peters D. J. Med. Chem. 2000, 43: 2217

<A NAME="RF21808SS-1F">1f</A> De Martino G. Edler MC. La Regina G. Cosuccia A. Barbera MC. Barrow D. Nicholson RI. Chiosis G. Brancale A. Hamel E. Artico M. Silvestri R. J. Med. Chem. 2006, 49: 947

<A NAME="RF21808SS-2A">2a</A> Metzner P. Thuillier A. In Sulfur Reagents in Organic Synthesis Katritzky AR. Meth-Cohn O. Rees CW. Academic Press; San Diego: 1994.

<A NAME="RF21808SS-2B">2b</A> Kondo T. Mitsudo T. Chem. Rev. 2000, 100: 3205

<A NAME="RF21808SS-2C">2c</A> Ley SV. Thomas AW. Angew. Chem., Int. Ed. 2003, 42: 5400

<A NAME="RF21808SS-3A">3a</A> Kosugi M. Shimizu T. Migita T. Chem. Lett. 1978, 13

<A NAME="RF21808SS-3B">3b</A> Suzuki H. Abe H. Osuka A. Chem. Lett. 1980, 1363

<A NAME="RF21808SS-3C">3c</A> Bowman WR. Heaney H. Smith PHG. Tetrahedron Lett. 1984, 25: 5821

<A NAME="RF21808SS-3D">3d</A> Ciattini PG. Morera E. Ortar G. Tetrahedron Lett. 1995, 36: 4133

<A NAME="RF21808SS-3E">3e</A> Zheng N. Mcwilliams C. Fleitz FJ. Armstrong JD. Volante RPJ. J. Org. Chem. 1998, 63: 9606

<A NAME="RF21808SS-3F">3f</A> Bates CG. Gujadhur RK. Venkataraman D. Org. Lett. 2002, 4: 2803

<A NAME="RF21808SS-3G">3g</A> Kwong FY. Buchwald SL. Org. Lett. 2002, 4: 3517

<A NAME="RF21808SS-3H">3h</A> Bates CG. Saejueng P. Doherty MQ. Venkataraman D. Org. Lett. 2004, 6: 5005

<A NAME="RF21808SS-3I">3i</A> Deng W. Zou Y. Wang Y.-F. Liu L. Guo Q.-X. Synlett 2004, 1254

<A NAME="RF21808SS-3J">3j</A> Gendre F. Yang M. Diaz P. Org. Lett. 2005, 7: 2719

<A NAME="RF21808SS-3K">3k</A> Zheng Y. Du X. Bao W. Tetrahedron Lett. 2006, 47: 1217

<A NAME="RF21808SS-3L">3l</A> Zhu D. Xu L. Wu F. Wan B. Tetrahedron Lett. 2006, 47: 5781

<A NAME="RF21808SS-3M">3m</A> Chen Y.-J. Chen H.-H. Org. Lett. 2006, 8: 5609

<A NAME="RF21808SS-3N">3n</A> Wang Z. Mo H. Bao W. Synlett 2007, 91

<A NAME="RF21808SS-3O">3o</A> Lv X. Bao W. J. Org. Chem. 2007, 72: 3863

<A NAME="RF21808SS-3P">3p</A> Kabir MS. Van Linn ML. Monte A. Cook JM. Org. Lett. 2008, 10: 3363

<A NAME="RF21808SS-3Q">3q</A> Itoh T. Mase T. Org. Lett. 2004, 6: 4587

<A NAME="RF21808SS-3R">3r</A> Sperotto E. van Klink GPM. de Vries JG. van Koten G. J. Org. Chem. 2008, 73: 5625

<A NAME="RF21808SS-3S">3s</A> Zhang Y. Ngeow KC. Ying JY. Org. Lett. 2007, 9: 3495

<A NAME="RF21808SS-3T">3t</A> Wong Y.-C. Jayanth TT. Cheng C.-H. Org. Lett. 2006, 8: 5613

<A NAME="RF21808SS-3U">3u</A> Lee J.-Y. Lee PH. J. Org. Chem. 2008, 73: 7413

<A NAME="RF21808SS-4A">4a</A> Chowdhury S. Roy S. Tetrahedron Lett. 1997, 38: 2149

<A NAME="RF21808SS-4B">4b</A> Kundu A. Roy S. Organometallics 2000, 19: 105

<A NAME="RF21808SS-4C">4c</A> Nishino T. Okada M. Kuroki T. Watanabe T. Nishiyama Y. Sonoda N. J. Org. Chem. 2002, 67: 8696

<A NAME="RF21808SS-4D">4d</A> Nishino T. Nishiyama Y. Sonoda N. Chem. Lett. 2003, 928

<A NAME="RF21808SS-4E">4e</A> Ranu BC. Mandal T. J. Org. Chem. 2004, 69: 5793

<A NAME="RF21808SS-4F">4f</A> Ajiki K. Tanaka K. Org. Lett. 2005, 7: 4193

<A NAME="RF21808SS-4G">4g</A> Kumar S. Engman L. J. Org. Chem. 2006, 71: 5400

<A NAME="RF21808SS-4H">4h</A> Millois C. Diaz P. Org. Lett. 2000, 2: 1705

<A NAME="RF21808SS-4I">4i</A> Taniguchi N. Onami T. Synlett 2003, 829

<A NAME="RF21808SS-4J">4j</A> Taniguchi N. Onami T. J. Org. Chem. 2004, 69: 915

<A NAME="RF21808SS-4K">4k</A> Taniguchi N. J. Org. Chem. 2004, 69: 6904

<A NAME="RF21808SS-4L">4l</A> Taniguchi N. Synlett 2005, 1687

<A NAME="RF21808SS-5A">5a</A> Herradura PS. Pendola KA. Guy RK. Org. Lett. 2000, 2: 2019

<A NAME="RF21808SS-5B">5b</A> Savarin C. Srogl J. Liebeskind LS. Org. Lett. 2002, 4: 4309

<A NAME="RF21808SS-5C">5c</A> Prokopcova H. Kappe CO. J. Org. Chem. 2007, 72: 4440

<A NAME="RF21808SS-6A">6a</A> Miyaura N. In Metal-Catalyzed Cross-Coupling Reactions Vol. 1: de Meijere A. Diederich F. Wiley-VCH; Weinheim: 2004. p.41-123

<A NAME="RF21808SS-6B">6b</A> Taniguchi N. Synlett 2006, 1351

<A NAME="RF21808SS-6C">6c</A> Taniguchi N. J. Org. Chem. 2007, 72: 1241

<A NAME="RF21808SS-7">7</A> Wang Z.-L. Tang R.-Y. Luo P.-S. Deng C.-L. Zhong P. Li J.-H. Tetrahedron 2008, 64: 10670

For selected papers on the copper-catalyzed N-arylation of an organoboronic acid with an amino group, see:

<A NAME="RF21808SS-8A">8a</A> Chan DMT. Monaco KL. Wang R.-P. Winters MP. Tetrahedron Lett. 1998, 39: 2933

<A NAME="RF21808SS-8B">8b</A> Lam PYS. Clark CG. Saubern S. Adams J. Winters MP. Chan DMT. Combs A. Tetrahedron Lett. 1998, 39: 2941

<A NAME="RF21808SS-8C">8c</A> Chan DMT. Lam PYS. In Boronic Acids: Preparation and Application in Organic Synthesis and Medicine Hall DG. Wiley-VCH; Weinheim: 2005. p.205-240

<A NAME="RF21808SS-8D">8d</A> Lan J.-B. Chen L. Yu X.-Q. You J.-S. Xie R.-G. Chem. Commun. 2004, 188

<A NAME="RF21808SS-8E">8e</A> Hamada T. Ye X. Stahl SS. J. Am. Chem. Soc. 2008, 130: 833

<A NAME="RF21808SS-8F">8f</A> Bénard S. Neuville L. Zhu J. J. Org. Chem. 2008, 73: 6441

<A NAME="RF21808SS-8G">8g</A> Sasaki M. Dalili S. Yudin AK. J. Org. Chem. 2003, 68: 2045

<A NAME="RF21808SS-8H">8h</A> Kantam ML. Venkanna GT. Sridhar C. Sreedhar B. Choudary BM. J. Org. Chem. 2006, 71: 9522

<A NAME="RF21808SS-8I">8i</A> Chen S. Huang H. Liu X. Shen J. Jiang H. Liu H. J. Comb. Chem. 2008, 10: 358

<A NAME="RF21808SS-8J">8j</A> Combs AP. Tadesse S. Rafalski M. Haque TS. Lam PYS. J. Comb. Chem. 2002, 4: 179

Oxygen may play at least three roles in the present reaction including: (1) promoting the generation of Cu(SR)Ar from Cu(I)SR and ArB(OH)₂ to accelerate the catalytic cycle, (2) regenerating the active Cu(I) species from the Cu(SR)Ar intermediate, and (3) restraining N-arylations of organoboronic acids with amines. See refs. 6 and 8.