Synthesis, Table of Contents Synthesis 2022; 54(16): 3595-3604DOI: 10.1055/a-1817-1965 paper Potassium tert-Butoxide Facilitated Amination of Carboxylic Acids with N,N-Dimethylformamide Yuanjing Huang , Jing Zhang ∗Recommend Article Abstract Buy Article All articles of this category Abstract Herein a practical and efficient potassium tert-butoxide (KO t Bu)-facilitated amination of carboxylic acids with N,N-dimethylamine is described. In the presence of catalytic amount of KO t Bu, a variety of aliphatic and aromatic carboxylic acids are transformed to N,N-dimethylamides using DMF as the dimethylamine reagent with the assistance of trimethylacetic anhydride. The applicability of this protocol is demonstrated by late-stage dimethylamidation of complex drug molecules. A plausible reaction mechanism involving KO t Bu-facilitated in situ amine generation from formamide decomposition and anhydride-mediated condensation is proposed on the basis of mechanistic investigations. Key words Key wordsamidation - N,N-dimethylformamide - carboxylic acid - potassium tert-butoxide Full Text References References 1a Prasher P, Sharma M. Drug Dev. Res. 2021; 82: 945 1b Kumari S, Carmona AV, Tiwari AK, Trippier PC. J. Med. Chem. 2020; 63: 12290 1c Sun S, Jia Q, Zhang Z. Bioorg. Med. Chem. Lett. 2019; 29: 2535 1d Borges A, Gillespie D, Nag A. Supramol. Chem. 2019; 31: 575 1e Mahesh S, Tang K.-C, Raj M. Molecules 2018; 23: 2615 1f Brown DG, Boström J. J. Med. Chem. 2016; 59: 4443 1g Roughley SD, Jordan AM. J. Med. Chem. 2011; 54: 3451 1h Robello M, Barresi E, Baglini E, Salerno S, Taliani S, Settimo FD. J. Med. Chem. 2021; 64: 3508 1i Scheiner S, Wang L. J. Am. Chem. Soc. 1993; 115: 1958 1j Johansson A, Kollman P, Rothenberg S, McKelvey J. J. Am. Chem. Soc. 1974; 96: 3794 1k Wood F, Ramsden DK, King G. Nature 1966; 212: 606 2 Liu W, Hou C, Li J, Ma X, Zhang Y, Hu M, Huang Y. J. Enzyme Inhib. Med. Chem. 2020; 35: 187 3 Zandi TA, Townsend CA. Proc. Natl. Acad. Sci. U.S.A. 2021; 118: 1 4 Kim DK, Lee K.-H, Kim S.-j, Kim S.-J, Lee SJ, Park CH, Kim B-T, Song G-S, Moon B-S, Ryu S-Y. J. Pharmacol. Exp. Ther. 2019; 369: 318 5 Svensson LA. Agents Actions Suppl. 1988; 23: 271 6a Procopio D, Siciliano C, Trombino S, Dumitrescu DE, Suciu F, Di Gioia ML. Org. Biomol. Chem. 2022; 20: 1137 6b Upadhyay R, Rana R, Maurya SK. ChemCatChem 2021; 13: 1867 6c Santos AS, Silva AM. S, Marques MM. B. Eur. J. Org. Chem. 2020; 2501 6d Massolo E, Pirola M, Benaglia M. Eur. J. Org. Chem. 2020; 4641 6e Reddy TN, de Lima DP. Asian J. Org. Chem. 2019; 8: 1227 6f de Figueiredo RM, Suppo J.-S, Campagne J.-M. Chem. Rev. 2016; 116: 12029 6g Lundberg H, Tinnis F, Selander N, Adolfsson H. Chem. Soc. Rev. 2014; 43: 2714 6h Pattabiraman VR, Bode JW. Nature 2011; 480: 471 7a Pedrood K, Bahadorikhalili S, Lotfi V, Larijani B, Mahdavi M. Mol. Divers. 2022; 26: 1311 7b Sabatini MT, Boulton LT, Sneddon HF, Sheppard TD. Nat. Catal. 2019; 2: 10 7c Al-Warhi TI, Al-Hazimi HM. A, El-Faham A. J. Saudi Chem. Soc. 2012; 16: 97 7d El-Faham A, Albericio F. Chem. Rev. 2011; 111: 6557 7e Valeur E, Bradley M. Chem. Soc. Rev. 2009; 38: 606 7f Han S.-Y, Kim Y.-A. Tetrahedron 2004; 60: 2447 8a Sutar YB, Bhagat SB, Telvekar VN. Tetrahedron Lett. 2015; 56: 6768 8b Yamaguchi K, Miyaguchi H, Hirakawa K, Ohno Y, Kanawaku Y. Forensic Toxicol. 2021; 39: 134 8c Wang S.-M, Zhao C, Zhang X, Qin H.-L. Org. Biomol. Chem. 2019; 17: 4087 8d Enel M, Leygue N, Saffon N, Galaup C, Picard C. Eur. J. Org. Chem. 2018; 1765 8e Sharma R, Soman SS. Synth. Commun. 2016; 46: 1307 9a Heravi M.M, Ghavidel M, Mohammadkhani L. RSC Adv. 2018; 8: 27832 9b Ding S, Jiao N. Angew. Chem. Int. Ed. 2012; 51: 9226 9c Muzart J. Tetrahedron 2009; 65: 8313 9d Zhang C, Wang Q, Tian S, Zhang J, Li J, Zhou L, Lu J. Org. Biomol. Chem. 2020; 18: 4723 9e Lei LS, Xue CG, Xu XT, Jin DP, Wang SH, Bao W, Liang H, Zhang K, Asiri AM. Org. Biomol. Chem. 2019; 17: 3723 9f Mohebali H, Mahjoub AR, Karimi M, Heydari A. Appl. Organomet. Chem. 2019; 33: 4822 9g Subhedar DD, Gupta SS. R, Bhanage BM. Catal. Lett. 2018; 148: 3102 9h Gupta SS. R, Nakhate AV, Deshmukh GP, Periasamy S, Samudrala PS, Bhargava SK, Kantam ML. ChemistrySelect 2018; 3: 8436 9i Bao Y.-S, Wang L, Jia M, Xu A, Agula B, Baiyin M, Zhaorigetu B. Green Chem. 2016; 18: 3808 10a Samudrala PS, Nakhate AV, Gupta SS. R, Rasal KB, Deshmukh GP, Gadipelly CR, Theegala S, Dumbre DK, Periasamy S, Chary Komandur VR, Bhargava SK, Kantam ML. Appl. Catal., B 2019; 240: 348 10b Kadam RG, Petr M, Zbořil R, Gawande MB, Jayaram RV. ACS Sustainable Chem. Eng. 2018; 6: 12935 10c Mohammad A, Chandra P, Ghosh T, Carraro M, Mobin SM. Inorg. Chem. 2017; 56: 10596 10d Bi X, Li J, Shi E, Wang H, Gao R, Xiao J. Tetrahedron 2016; 72: 8210 10e Liu H.-Q, Liu J, Zhang Y.-H, Shao C.-D, Yu J.-X. Chin. Chem. Lett. 2015; 26: 11 10f Saberi D, Mahdudi S, Cheraghi S, Heydari A. J. Organomet. Chem. 2014; 772: 222 10g Kumar PS, Kumar GS, Kumar RA, Reddy NV, Rajender Reddy K. Eur. J. Org. Chem. 2013; 1218 10h Li H, Pan C, Cheng Y, Zhu C. Tetrahedron Lett. 2013; 54: 6679 10i Priyadarshini S, Joseph PJ. A, Kantam ML. RSC Adv. 2013; 3: 18283 10j Wang H, Guo LN, Duan XH. Org. Biomol. Chem. 2013; 11: 4573 10k Xie Y.-X, Song R.-J, Yang X.-H, Xiang J.-N, Li J.-H. Eur. J. Org. Chem. 2013; 5737 10l Yan H, Yang H, Lu L, Liu D, Rong G, Mao J. Tetrahedron 2013; 69: 7258 11 Kumagai T, Anki T, Ebi T, Konishi A, Matsumoto K, Kurata H, Kubo T, Katsumoto K, Kitamura C, Kawase T. Tetrahedron 2010; 66: 8968 12 Kawano S, Saito K, Yamada T. Chem. Lett. 2018; 47: 584 13 Ciszek JW, Keane ZK, Cheng L, Stewart MP, Yu LH, Natelson D, Tour J. J. Am. Chem. Soc. 2006; 128: 3179 14 Bi X, Li J, Shi E, Li Y, Liu Y, Wang H, Xiao J. Phosphorus, Sulfur, Silicon Relat. Elem. 2019; 194: 236 15 Tortoioli S, Bannwart L, Abele S. Synthesis 2016; 48: 2069 16a Dunetz JR, Magano J, Weisenburger GA. Org. Process Res. Dev. 2016; 20: 140 16b Montalbetti Christian AG. N, Falque V. Tetrahedron 2005; 61: 10827 17a Zhang F, Li L, Zhang J, Gong H. Sci. Rep. 2019; 9: 2787 17b Zhang M.-Z, Guo Q.-H, Sheng W.-B, Guo C.-C. Adv. Synth. Catal. 2015; 357: 2855 17c Zhang Y, Sun H, Zhang W, Gao Z, Yang P, Gu J. Appl. Catal., A 2015; 496: 9 17d Seidensticker T, Furst MR. L, Frauenlob R, Vondran J, Paetzold E, Kragl U, Vorholt AJ. ChemCatChem 2015; 7: 4085 17e Iranpoor N, Firouzabadi H, Rizi ZT, Erfan S. RSC Adv. 2014; 4: 43178 17f Cho SH, Kim JY, Lee SY, Chang S. Angew. Chem. Int. Ed. 2009; 48: 9127 17g Wan Y, Alterman M, Larhed M, Hallberg A. J. Org. Chem. 2002; 67: 6232 17h Rasal KB, Yadav GD. Catal. Today 2018; 309: 51 18 Huang H, Yuan G, Li X, Jiang H. Tetrahedron Lett. 2013; 54: 7156 19 Ekoue-Kovi K, Wolf C. Org. Lett. 2007; 9: 3429 20 Ong DY, Yen Z, Yoshii A, Revillo Imbernon J, Takita R, Chiba S. Angew. Chem. Int. Ed. 2019; 58: 4992 21 Zhang M.-Z, Guo Q.-H, Sheng W.-B, Guo C.-C. Adv. Synth. Catal. 2015; 357: 2855 22 Djukanovic D, Heinz B, Mandrelli F, Mostarda S, Filipponi P, Martin B, Knochel P. Chem. Eur. J. 2021; 27: 13977 23 Titze M, Heitkämper J, Junge T, Kästner J, Peters R. Angew. Chem. Int. Ed. 2021; 60: 5544 24 Wei S, Mao Y, Shi S.-L. Synlett 2021; 32: 1670 25 Zeng M.-T, Xu W, Liu M, Liu X, Chang C.-Z, Zhu H, Dong Z.-B. Synth. Commun. 2017; 47: 1434 26 Sutherland M, Li A, Kaghad A, Panagopoulos D, Li F, Szewczyk M, Smil D, Scholten C, Bouché L, Stellfeld T, Arrowsmith CH, Barsyte D, Vedadi M, Hartung V, Steuber H, Britton R, Santhakumar V. ChemMedChem 2021; 16: 1116 27 Sakamoto T, Kondo Y, Takazawa N, Yamanaka H. J. Chem. Soc., Perkin Trans. 1 1996; 1927 28 Kuhn B, Mohr P, Stahl M. J. Med. Chem. 2010; 53: 2601 29 Zhao Y, Snieckus V. J. Am. Chem. Soc. 2014; 136: 11224 30 Holǐk M, Turečková M, Mannschreck A, Stühler G. Magn. Reson. Chem. 1982; 19: 121 31 Abe H, Matsunaga S, Takekawa S, Watanabe M. Patent WO2004046107A1, 2004 32 Uehara A, Olivero S, Michelet B, Martin-Mingot A, Thibaudeau S, Duñach E. Eur. J. Org. Chem. 2019; 46 33 Iranpoor N, Panahi F, Roozbin F, Erfan S, Rahimi S. Eur. J. Org. Chem. 2016; 1781 34 Kim I, Kang G, Lee K, Park B, Kang D, Jung H, He Y-T, Baik M-H, Hong S. J. Am. Chem. Soc. 2019; 141: 9239 35 Bannwart L, Abele S, Tortoioli S. Synthesis 2016; 48: 2069 36 Sandoval BA, Clayman PD, Oblinsky DG, Oh S, Nakano Y, Bird M, Scholes GD, Hyster TK. J. Am. Chem. Soc. 2021; 143: 1735 37 Rodríguez-Fernández M, Yan X, Collados JF, White PB, Harutyunyan SR. J. Am. Chem. Soc. 2017; 139: 14224 38 Lai M, Wu Z, Su F, Yu Y, Jing Y, Kong J, Wang Z, Wang S, Zhao M. Eur. J. Org. Chem. 2020; 198 39 Deibl N, Kempe R. J. Am. Chem. Soc. 2016; 138: 10786 40 Porte V, Di Mauro G, Schupp M, Kaiser D, Maulide N. Chem. Eur. J. 2020; 26: 15509 41 Li Z, Liu L, Xu K, Huang T, Li X, Song B, Chen T. Org. Lett. 2020; 22: 5517 42 Loscher C, McCarthy C, Guiry P, Murphy C, Maingot C. Patent WO2016185025A1, 2016 43 Zhang Y.-L, Guo R.-T, He J.-H, Wang X.-C. Org. Lett. 2019; 21: 4239 44 Cuvigny T, Hullot P, Mulot P, Larcheveque M, Normant H. Can. J. Chem. 1979; 57: 1201 45 Hobbs CF, Weingarten H. J. Org. Chem. 1974; 39: 918 46 Pallesen JS, Narayanan D, Tran KT, Solbak SM. Ø, Marseglia G, Sørensen LM. E, Høj LJ, Munafó F, Carmona RM. C, Garcia AD, Desu HL, Brambila R, Johansen TN, Popowicz GM, Sattler M, Gajhede M, Bach A. J. Med. Chem. 2021; 64: 4623 47 Tasso SM, Moon SC, Bruno-Blanch LE, Estiú GL. Bioorg. Med. Chem. 2004; 12: 3857 48 Clemenceau A, Thesmar P, Gicquel M, Le Flohic A, Baudoin O. J. Am. Chem. Soc. 2020; 142: 15355 49 Bauer A, Maulide N. Chem. Sci. 2019; 10: 9836 50 Rajadhyaksha MN, Jadhav VK, Shrigadi NB, Panandikar AM. Patent IN2010MU03291A, 2013 Supplementary Material Supplementary Material Supporting Information
