Cu(OAc)₂-Catalyzed Thiolation of Acyl C–H Bonds with Thiols Using TBHP as an Oxidant

Abstract

Cu(OAc)₂-promoted TBHP oxidative coupling reaction of formamides with thiols successfully proceeded through direct C–H bond activation of formamides. The corresponding S-phenyl dialkyl thiocarbamate compounds were formed with high yield under solvent-free conditions.

Key words

TBHP - Cu(OAc)₂ - thiolation - thiols - formamide

• References and Notes

• 1a Bichler P, Jennifer AL. Top. Organomet. Chem. 2010; 31: 39
• 1b Dvorak CA, Schmitz WD, Poon DJ. Angew. Chem. Int. Ed. 2000; 39: 1664
• 1c Murru S, Patal BK, Bras JL, Muzart J. J. Org. Chem. 2009; 74: 2217
• 1d Berger MD, Dutia M, Powell D, Floyd BM, Torres N, Mallon R, Wojciechowicz D, Kim S, Feldberg L, Collins K, Chaudhary I. Bioorg. Med. Chem. 2008; 16: 9202
• 1e Chen-Hsien W. Synthesis 1981; 622
• 2a Denise A, Colby RG, Jonathan A. Chem. Rev. 2010; 110: 624
• 2b Gerald D. Handbook of C–H Transformation, Applications in Organic Synthesis. WILEY-VCH Verlag GmbH & Co. KGaA; Weinheim: 2005
• 2c Gunay A, Klaus H. Chem. Rev. 2010; 110: 1060
• 2d Thomas WL, Melanie SS. Chem. Rev. 2010; 110: 1147
• 3 Chen X, Hao X.-S, Goodhue CE, Yu J.-Q. J. Am. Chem. Soc. 2006; 128: 6790
• 4 Fukuzawa S.-I, Shimizu S.-I, Atsuumi Y, Haga M, Ogata K. Tetrahedron Lett. 2009; 50: 2374
• 5 Zhang S, Qian P, Zhang M, Hu M, Cheng J. J. Org. Chem. 2010; 75: 6732
• 6 Tang R, Xie Y, Xie Y, Xiang J, Li J. Chem. Commun. 2011; 47: 12867
• 7 Ding ST, Jiao N. Angew. Chem. Int. Ed. 2012; 51: 1
• 8a Barve BD, Wu Y, Chuang D, Chung Y, Tsai Y, Wu S, Michal K, Du Y, Hsieh C, Wang J, Chang F. Eur. J. Org. Chem. 2012; 6760
• 8b Sawant DN, Wagh YS, Bhatte KD, Bhanage BM. J. Org. Chem. 2011; 76: 5489
• 8c Li Y, Xie Y, Zhang R, Jin K, Wang X, Duan C. J. Org. Chem. 2011; 76: 5444
• 9a Kumar GS, Maheswari CU, Kumar RA, Kantam ML, Reddy KR. Angew. Chem. Int. Ed. 2011; 50: 11748
• 9b He T, Li H, Li P, Wang L. Chem. Commun. 2011; 47: 8946
• 10 Typical Procedure: Under a N₂ atmosphere, a reaction vessel was charged with 1a (or 1b, 1c) (1.0 mmol), ArSH 2 (1.2 mmol), Cu(OAc)₂·H₂O (10 mol%), and 70% aq TBHP (4 mmol). The mixture was stirred at 120 °C and monitored by TLC. Upon completion of the reaction (approximately 12 h), the mixture was cooled to r.t. and mixed with H₂O (15.0 mL). The product was then extracted with CH₂Cl₂ (3 × 10 mL). The organic layers were combined, dried over anhyd Na₂SO₄, concentrated under reduced pressure, and purified over a column of silica gel (EtOAc–hexane as eluent) to give product 3a in 87% yield. ¹H NMR (300 MHz, CDCl₃): δ = 7.34−7.43 (m, 4 H), 3.72 (t, J = 5.1 Hz, 4 H), 3.59 (t, J = 4.8 Hz, 4 H). ¹³C NMR (75 MHz, CDCl₃): δ = 164.6, 135.9, 134.8, 128.2, 125.5, 65.4, 44.3. The identity and purity of other products were confirmed by ¹H NMR and ¹³C NMR spectroscopic analysis.
• 11 Liu Z, Zhang J, Chen S, Shi E, Xu Y, Wan X. Angew. Chem. Int. Ed. 2012; 51: 3231
• 12a Xie J, Huang Z. Angew. Chem. Int. Ed. 2010; 49: 10181
• 12b Sadananda R, Lee R, Heryadi D, Shen C, Wu J, Zhang P, Huang K, Liu X. J. Org. Chem. 2011; 76: 8999
• 12c Dai C, Xu Z, Huang F, Yu Z, Gao Y. J. Org. Chem. 2012; 77: 4414