Facile Preparation of Aryl Sulfides Using Palladium Catalysis under Mild Conditions

Abstract

A convenient method for C-S cross-coupling of aryl bromides with various thiols has been developed that involves the use of a 1,1′-bis(diphenylphosphino)ferrocene (DPPF)-ligated palladium complex with N,N-diisopropylethylamine (DIPEA) as the base. This coupling is tolerant of a wide range of functional groups, including hydroxy, amino, cyano, nitro, formyl, and carboxyl groups.

palladium - thiols - cross-coupling - C-S bond formation - sulfide

References and Notes

<A NAME="RU08410ST-1">1</A> Metzner P. Thuillier A. Sulfur Reagents in Organic Synthesis   Katritzky AR. Meth-Cohn O. Rees CW. Academic Press; London: 1994. 

<A NAME="RU08410ST-2A">2a</A> De Martino G. Edler MC. La Regina G. Coluccia 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="RU08410ST-2B">2b</A> Alcaraz ML. Atkinson S. Cornwall P. Foster AC. Gill DM. Humphries LA. Keegan PS. Kemp R. Merifield E. Nixon RA. Noble AJ. O’Beirne D. Patel ZM. Perkins J. Rowan P. Sadler P. Singleton JT. Tornos J. Watts AJ. Woodland IA. Org. Process Res. Dev.  2005,  9:  555 

<A NAME="RU08410ST-2C">2c</A> Liu LP. Stelmach JE. Natarajan SR. Chen MH. Singh SB. Schwartz CD. Fitzgerald CE. O’Keefe SJ. Zaller DM. Schmatz DM. Doherty JB. Bioorg. Med. Chem. Lett.  2003,  13:  3979 

<A NAME="RU08410ST-3">3</A> Kondo T. Mitsudo T. Chem. Rev.  2000,  100:  3205 

<A NAME="RU08410ST-4A">4a</A> Migita T. Shimizu T. Asami Y. Shiobara J. Kato Y. Kosugi M. Bull. Chem. Soc. Jpn.  1980,  53:  1385 

<A NAME="RU08410ST-4B">4b</A> Kosugi M. Shimizu T. Migita T. Chem. Lett.  1978,  13 

<A NAME="RU08410ST-5A">5a</A> Eichman CC. Stambuli JP. J. Org. Chem.  2009,  74:  4005 

<A NAME="RU08410ST-5B">5b</A> Dahl T. Tornoe CW. Bang-Andersen B. Nielsen P. Jorgensen M. Angew. Chem. Int. Ed.  2008,  47:  1726 

<A NAME="RU08410ST-5C">5c</A> Norris T. Leeman K. Org. Process Res. Dev.  2008,  12:  869 

<A NAME="RU08410ST-5D">5d</A> Lee JY. Lee PH. J. Org. Chem.  2008,  73:  7413 

<A NAME="RU08410ST-5E">5e</A> Mispelaere-Canivet C. Spindler JF. Perrio S. Beslin P. Tetrahedron  2005,  61:  5253 

<A NAME="RU08410ST-5F">5f</A> Itoh T. Mase T. Org. Lett.  2004,  6:  4587 

<A NAME="RU08410ST-6A">6a</A> Jammi S. Barua P. Rout L. Saha P. Punnlyamurthy T. Tetrahedron Lett.  2008,  49:  1484 

<A NAME="RU08410ST-6B">6b</A> Cao Y.-Q. Zhang Z. Guo Y.-X. Wu G.-Q. Synth. Commun.  2008,  38:  1325 

<A NAME="RU08410ST-6C">6c</A> Zhang YG. Ngeow KC. Ying JY. Org. Lett.  2007,  9:  3495 

<A NAME="RU08410ST-6D">6d</A> Millois C. Diaz P. Org. Lett.  2000,  2:  1705 

<A NAME="RU08410ST-7A">7a</A> Bagley MC. Dix MC. Fusillo V. Tetrahedron Lett.  2009,  50:  3661 

<A NAME="RU08410ST-7B">7b</A> Haldón E. Álvarez E. Nicasio MC. Pérez PJ. Organometallics  2009,  28:  3815 

<A NAME="RU08410ST-7C">7c</A> Herrero MT. SanMartin R. Domínguez E. Tetrahedron  2009,  65:  1500 

<A NAME="RU08410ST-7D">7d</A> Jammi S. Sakthivel S. Rout L. Mukherjee T. Mandal S. Mitra R. Saha P. Punniyamurthy T. J. Org. Chem.  2009,  74:  1971 

<A NAME="RU08410ST-7E">7e</A> Larsson PF. Correa A. Carril M. Norrby PO. Bolm C. Angew. Chem. Int. Ed.  2009,  48:  5691 

<A NAME="RU08410ST-7F">7f</A> Prasad DJC. Naidu AB. Sekar G. Tetrahedron Lett.  2009,  50:  1411 

<A NAME="RU08410ST-7G">7g</A> Rout L. Saha P. Jammi S. Punniyamurthy T. Eur. J. Org. Chem.  2008,  640 

<A NAME="RU08410ST-7H">7h</A> She J. Jiang Z. Wang YG. Tetrahedron Lett.  2009,  50:  593 

<A NAME="RU08410ST-7I">7i</A> Xu HJ. Zhao XY. Deng J. Fu Y. Feng YS. Tetrahedron Lett.  2009,  50:  434 

<A NAME="RU08410ST-7J">7j</A> Xu HJ. Zhao XY. Fu Y. Feng YS. Synlett  2008,  3063 

<A NAME="RU08410ST-7K">7k</A> Goyot O. Gingras M. Tetrahedron Lett.  2009,  50:  1977 

<A NAME="RU08410ST-7L">7l</A> Prasad DJC. Seker G. Synthesis  2010,  79 

<A NAME="RU08410ST-8">8</A> Wong Y.-C. Jayanth TT. Cheng C.-H. Org. Lett.  2006,  8:  5613 

<A NAME="RU08410ST-9A">9a</A> Correa A. Carril M. Bolm C. Angew. Chem. Int. Ed.  2008,  47:  2880 

<A NAME="RU08410ST-9B">9b</A> Wu J.-R. Lin C.-H. Lee C.-F. Chem. Commun.  2009,  4450 

<A NAME="RU08410ST-10">10</A> Reddy VP. Kumar AV. Swapna K. Rao KR. Org. Lett.  2009,  11:  1697 

<A NAME="RU08410ST-11A">11a</A> Alvaro E. Hartwig JF. J. Am. Chem. Soc.  2009,  131:  7858 

<A NAME="RU08410ST-11B">11b</A> Fernández-Rodríguez MA. Hartwig JF.
J. Org. Chem.  2009,  74:  1663 

<A NAME="RU08410ST-11C">11c</A> Fernandez-Rodriguez MA. Shen QL. Hartwig JF. Chem. Eur. J.  2006,  12:  7782 

<A NAME="RU08410ST-11D">11d</A> Fernandez-Rodriguez MA. Shen QL. Hartwig JF. J. Am. Chem. Soc.  2006,  128:  2180 

<A NAME="RU08410ST-12">12</A> Amatore C. Pflüger F. Organometallics  1990,  9:  2276 

<A NAME="RU08410ST-13">13</A>

Typical Experimental Procedure: To a solution of [Pd₂(dba)₃] (9.2 mg, 0.010 mmol) and DPPF (11.1 mg, 0.020 mmol) in toluene (1.0 mL) were added bromobenzene (0.11 mL, 1.0 mmol), DIPEA (0.19 mL, 1.1 mmol) and octanethiol (0.17 mL, 1.0 mmol) at r.t. The solution was stirred under reflux for 3 h then cooled to r.t. The reaction was quenched by addition of H₂O and extracted with EtOAc (3 × 10 mL), and the combined organic layers were washed with brine, dried (Na₂SO₄), and filtered. The filtrate was concentrated in vacuo and the residue was purified by flash column chroma-tography on silica gel to afford octyl phenyl sulfide (222.3 mg, quantitative).