Abstract
The oxidative coupling of methylarenes and N,N-dialkylformamides was developed, and the appropriate reaction conditions were established. By using I2 as the catalyst, and tert-butyl hydroperoxide (TBHP) as the oxidant, the reaction provided N,N-dialkylamides or N-alkylamides with moderate yields via multiple sp3 C-H bonds activation of methylarenes in aqueous and metal-free conditions.
References
Crespo L, Sanclimens G, Pons M, Giralt E, Royo M, Albericio F. Peptide and amide bond-containing dendrimers. Chem Rev, 2005, 105: 1663–1681
Carey JS, Laffan D, Thomson C, Williams MT. Analysis of the reactions used for the preparation of drug candidate molecules. Org Biomol Chem, 2006, 4: 2337–2347
Greenberg A, Breneman CM, Liebman JF. The Amide Linkage: Structural Significance in Chemistry, Biochemistry and Materials Science. New York: John Wiley & Sons, 2000
Boas U, Brask J, Jensen KJ. Backbone amide linker in solid-phase synthesis. Chem Rev, 2009, 109: 2092–2118
Valeur E, Bradley M. Amide bond formation: beyond the myth of coupling reagents. Chem Soc Rev, 2009, 38: 606–631
Allen CL, Williams JMJ. Metal-catalysed approaches to amide bond formation. Chem Soc Rev, 2011, 40: 3405–3415
García-Álvarez R, Crochet P, Cadierno V. Metal-catalyzed amide bond forming reactions in an environmentally friendly aqueous medium: nitrile hydrations and beyond. Green Chem, 2013, 15: 46–66
Zhou B, Du JJ, Yaxi Yang YX, Li YC. Rhodium(III)-catalyzed intermolecular direct amidation of aldehyde C-H bonds with N-chloroamines at room temperature. Org Lett, 2013, 15: 2934–2937
Zhou B, Yang YX, Shi JJ, Feng HJ, Li YC. Rhodium-catalyzed synthesis of amides from aldehydes and azides by chelation-assisted C-H bond activation. Chem Eur J, 2013, 19: 10511–10515
Fu ZQ, Lee JB, Kang BJ, Hong SH. Dehydrogenative amide synthesis: azide as a nitrogen source. Org Lett, 2012, 14: 6028–6031
Li CJ, Yoo WJ. Highly efficient oxidative amidation of aldehydes with amine hydrochloride salts. J Am Chem Soc, 2006, 128: 13064–13065
Zhu MW, Fujita KI, Yamaguchi R. Aerobic oxidative amidation of aromatic and cinnamic aldehydes with secondary amines by CuI/2-pyridonate catalytic system. J Org Chem, 2012, 77: 9102–9109
Zhang C, Zong XL, Zhang LR, Jiao N. Copper-catalyzed aerobic oxidative cross-dehydrogenative coupling of amine and α-carbonyl aldehyde: a practical and efficient approach to α-ketoamides with wide substrate scope. Org Lett, 2012, 14: 3280–3283
Xie YX, Song RJ, Yang XH, Xiang JN, Li JH. Coppercatalyzed amidation of acids using formamides as the amine source. Eur J Org Chem, 2013: 5737–5742
Ghosh SC, Ngiam JSY, Chai CLL, Seayad AM, Dang TT, Chen AQ. Iron-catalyzed efficient synthesis of amides from aldehydes and amine hydrochloride salts. Adv Synth Catal, 2012, 354: 1407–1412
Li YM, Jia F, Li ZP. Iron-catalyzed oxidative amidation of tertiary amines with aldehydes. Chem Eur J, 2013, 19: 82–86
Zhang C, Xu ZJ, Shen T, Wu GL, Zhang LR, Jiao N. Mnpromoted aerobic oxidative C-C bond cleavage of aldehydes with dioxygen activation: a simple synthetic approach to formamides. Org Lett, 2012, 14: 2362–2365
Vanjari R, Guntreddi T, Singh KN. MnO2 promoted sequential C-O and C-N bond formation via C-H activation of methylarenes: a new approach to amides. Org Lett, 2013, 15: 4908–4911
Kang BJ, Fu ZQ, Hong SH. Ruthenium-catalyzed redox-neutral and single-step amide synthesis from alcohol and nitrile with complete atom economy. J Am Chem Soc, 2013, 135: 11704–11707
Owston NA, Parker AJ, Williams JMJ. Iridium-catalyzed conversion of alcohols into amides via oximes. Org Lett, 2007, 9: 73–75
Owston NA, Parker AJ, Williams JMJ. Highly efficient ruthenium-catalyzed oxime to amide rearrangement. Org Lett, 2007, 9: 3599–3601
Liu ZJ, Zhang J, Chen SL, Shi E, Xu Y, Wan XB. Cross coupling of acyl and aminyl radicals: direct synthesis of amides catalyzed by Bu4NI with TBHP as an oxidant. Angew Chem Int Ed, 2012, 51: 3231–3235
Li HM, Xie J, Xue QC, Cheng YX, Zhu CJ. Metal-free n-Bu4NI-catalyzed direct synthesis of amides from alcohols and N,N-disubstituted formamides. Tetrahedron Lett, 2012, 53: 6479–6482
Xu K, Hu YB, Zhang S, Zha ZG, Wang ZY. Direct amidation of alcohols with N-substituted formamides under transition-metal-free conditions. Chem Eur J, 2012, 18: 9793–9797
Mai WP, Wang HH, Li ZC, Yuan JW, Xiao YM, Yang LR, Mao P, Qu LB. nBu4NI-catalyzed direct synthesis of a-ketoamides from aryl methyl ketones with dialkylformamides in water using TBHP as oxidant. Chem Commun, 2012, 48: 10117–10119
Wei W, Shao Y, Hu HY, Zhang F, Zhang C, Xu Y, Wan XB. Coupling of methyl ketones and primary or secondary amines leading to α-ketoamides. J Org Chem, 2012, 77: 7157–7165
Yin ZW, Sun PP. Palladium catalyzed direct ortho-acylation through an oxidative coupling of acetanilides with toluene derivatives. J Org Chem, 2012, 77: 11339–11344
Xu ZP, Xiang B, Sun PP. Palladium catalyzed direct ortho C-H acylation of 2-arylpyridines using toluene derivatives as acylation reagents. RSC Adv, 2013, 3: 1679–1682
Heys JR, Elmore CS. Meta-substituent effects on organoiridium-catalyzed ortho-hydrogen isotope exchange. J Labelled Compd Rad, 2009, 52: 189–200
Marcus AP, Lee AS, Davis RL, Tantillo DJ, Sarpong R. Pronounced steric effects of substituents in the nazarov cyclization of aryl dienyl ketones. Angew Chem Int Ed, 2008, 47: 6379–6383
Xia ZH, Zhu Q. A transition-metal-free synthesis of arylcarboxyamides from aryl diazonium salts and isocyanides. Org Lett, 2013, 15: 4110–4113
Vice S, Bara T, Bauer A, Evans C, Ford J, Josien H, McCombie S, Miller M, Nazareno D, Palani A, Tagat J. Concise formation of 4-benzyl piperidines and related derivatives using a Suzuki protocol. J Org Chem, 2001, 66: 2487–2492
Muzart J. N,N-dimethylformamide: much more than a solvent. Tetrahedron, 2009, 65: 8313–8323
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Dedicated to Professor Qian Changtao on the occasion of his 80th birthday.
SUN PeiPei obtained his BSc from Anhui University in 1985 and a MSc from East China Normal University in 1994. After obtaining a PhD from Hangzhou University in 1997, he joined the faculty of Nanjing Normal University as an associate professor of chemistry. He has ever been as a visiting scholar and as a postdoctoral fellow at Shanghai Institute of Organic Chemistry, the Chinese Academy of Sciences, Tsing Hua University (Hsinchu, Taiwan, China) and Nanjing University, respectively. He became a full professor at Nanjing Normal University in 2005. His research interests include organometallic chemistry, organic synthetic methodology and organic materials.
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Du, B., Sun, P. Syntheses of amides via iodine-catalyzed multiple sp3 C-H bonds oxidation of methylarenes and sequential coupling with N,N-dialkylformamides. Sci. China Chem. 57, 1176–1182 (2014). https://doi.org/10.1007/s11426-014-5098-7
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DOI: https://doi.org/10.1007/s11426-014-5098-7