Synthesis, Table of Contents Synthesis 2018; 50(24): 4855-4866DOI: 10.1055/s-0037-1610254 paper © Georg Thieme Verlag Stuttgart · New York Efficient Synthesis of Sulfinate Esters and Sulfinamides via Activated Esters of p-Toluenesulfinic Acid Sayed Habibul Gafur , Stephanie L. Waggoner , Eric Jacobsen , Christopher G. Hamaker , Shawn R. Hitchcock* Department of Chemistry, Illinois State University, Normal, IL 61790-4160, USA Email: hitchcock@ilstu.edu › Author Affiliations Recommend Article Abstract Buy Article All articles of this category Abstract Sulfinate esters were prepared by the process of activating p-toluenesulfinic acid with either cyanuric chloride, methanesulfonyl chloride, or 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC-HCl). Activation of p-toluenesulfinic acid with cyanuric chloride led to the formation of sulfinate esters that were accompanied by the formation of the corresponding sulfones. The use of methanesulfonyl chloride for activation via methanesulfonic p-toluenesulfinic anhydride afforded mixtures of sulfinate esters and methanesulfonates. The use of the carbodiimide EDC proved to yield the best results with the highly selective formation of the target sulfinate esters. The use of trimethylacetic p-toluenesulfinic anhydride or cyanuric chloride to achieve the synthesis of sulfinamides proved to be ineffective due to poor chemoselectivity of the nucleophilic attack on the activated p-toluenesulfinic acid anhydride. Ultimately, the use of EDC-HCl to form the sulfinamides proved to be the best pathway for synthesis. Key words Key wordssulfinate ester - sulfinic acid - sulfinamide - cyanuric chloride - EDC - activated ester Full Text References References 1a Robak MT. Herbage MA. Ellman JA. Chem. Rev. 2010; 110: 3600 1b Khiar N. Fernandez I. Chem. Rev. 2003; 103: 3651 2 Malwal SR. Labade A. Andhalkar AS. Sengupta K. Chakrapani H. Chem. Commun. 2014; 50: 11533 3 Hemmi M. Shindo Y. Nakajima T. Nishiyama S. Oka K. Sato M. Hiruta Y. Citterio D. Suzuki K. Chem. Asian J. 2018; 13: 648 4a Douglass IB. J. Org. Chem. 1965; 30: 633 4b Douglass IB. Farah BS. Thomas EG. J. Org. Chem. 1960; 26: 1996 5a Peltier HM. Evans JW. Ellman JA. Org. Lett. 2005; 7: 1733 5b Evans JW. Fierman MB. Miller SJ. Ellman JA. J. Am. Chem. Soc. 2004; 126: 8134 5c Khiar N. Alcudia F. Espartero J.-L. Rodríguez L. Fernández I. J. Am. Chem. Soc. 2000; 122: 7598 5d Whitesell JK. Wong M.-S. J. Org. Chem. 1991; 56: 4552 5e Harpp DN. Friedlander BT. Larsen C. Steliou K. Stockton A. J. Org. Chem. 1978; 43: 3481 6a Tranquilino A. Andrade SR. C. P. da Silva AP. M. Menezes PH. Oliveira RA. Tetrahedron Lett. 2017; 58: 1265 6b Huang M. Hu L. Shen H. Liu Q. Hussain MI. Pan J. Xiong Y. Green Chem. 2016; 18: 1874 7a Hajipour AR. Falahati AR. Ruoho AE. Tetrahedron Lett. 2006; 47: 2717 7b Furukawa M. Ohkawara T. Noguci Y. Nishikawa M. Tomimatsu M. Chem. Pharm. Bull. 1980; 28: 134 7c Furukawa M. Okawara T. Noguchi Y. Nishikawa M. Synthesis 1978; 441 7d Miyaji Y. Minato H. Kobayashi M. Bull. Chem. Soc. Jpn. 1971; 44: 862 8 Klunder JM. Sharpless KB. J. Org. Chem. 1987; 52: 2598 9a Pogaku N. Krishna PR. Prapurna YL. Synth. Commun. 2017; 47: 1239 9b Kadari L. Krishna PR. Prapurna YL. Adv. Synth. Cat. 2016; 358: 3863 10 Bu B. Li Z. Qian P. Han J. Pan Y. Chem. Asian J. 2015; 11: 478 11 Choudhary D. Khatri V. Basak K. Org. Lett. 2018; 20: 1703 12 Jacobsen E. Chavda MK. Zikpi KM. Waggoner SL. Passini DJ. Wolfe JA. Larson R. Beckley C. Hamaker CG. Hitchcock SR. Tetrahedron Lett. 2017; 58: 3073 13 Blotny G. Tetrahedron Lett. 2003; 44: 1499 14a Blotny G. Tetrahedron 2006; 62: 9507 14b De Luca L. Giacomelli G. Porcheddu A. Org. Lett. 2002; 4: 553 14c De Luca L. Giacomelli G. Porcheddu A. J. Org. Chem. 2001; 66: 7907 15a Alcohols derived from the Baylis–Hillman reaction also form sulfones. See reference 12. 15b Benzylic and allylic sulfinate esters can be rearranged to sulfones by palladium-catalyzed 1,3-rearrangements, see: Jagusch T. Gais H.-J. Bondarev O. J. Org. Chem. 2004; 69: 2731 Alternate sulfinamide syntheses: 16a Dai Q. Zhang J. Adv. Synth. Catal. 2018; 360: 1123 16b Harmata M. Zheng P. Huang C. Gomes MG. Ying W. Ranyanil K.-O. Balan G. Calkins NL. J. Org. Chem. 2007; 72: 683 16c Drabowicz J. Pacholczyk M. Phosphorus, Sulfur Relat. Elem. 1987; 29: 257 16d Furukawa M. Okawara T. Synthesis 1976; 339 17 Afonso CA. M. Lourenço NM. T. Rosatella A. deA. Molecules 2006; 11: 81 Supplementary Material Supplementary Material Supporting Information
