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Methanesulfonic anhydride-promoted sustainable synthesis of thioesters from feedstock acids and thiols

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Abstract

An unprecedented metal-, halogen- and solvent-free, MSAA-promoted S-carbonylation of thiols with feedstock acids has been developed. This new transformation provides an efficient and atom-economic strategy for the synthesis of thioesters in a single operation from readily available and inexpensive starting materials. The reaction avoids the use of expensive and hazardous coupling reagents, bases and generates water as the only by-product, thus making this chemical synthetic process more viable, environment-friendly and contributing towards sustainable chemistry.

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An efficient and novel strategy was established for dehydrative nucleophilic substitution reaction of feedstock acids with thiols, which systematically unravels the feasibility and practicality of thioester formation in a step- and atom-economical fashion.

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References

  1. Khour C B, Darth, C B, Lalnger A and Daves M E 1994 Studies on the catalytic oxidation of alkanes and alkenes by titanium silicates J. Catal. 149 195

    Article  Google Scholar 

  2. Andrade C K Z and Alves L M 2005 Environmentally benign solvents in organic synthesis: Current topics Curr. Org. Chem. 9 195

    CAS  Google Scholar 

  3. Aparicio S and Alcalde R 2009 The green solvent ethyl lactate: an experimental and theoretical characterization Green Chem. 11 65

    CAS  Google Scholar 

  4. Elkington J 1994 Towards the sustainable corporation: win-win-win sustainable development Calif. Manag. Rev. 36 90

    Google Scholar 

  5. Staunton J and Weissman K J 2001 Polyketide biosynthesis: A millennium review Nat. Prod. Rep. 18 380

    Article  CAS  Google Scholar 

  6. Yang H, Li H, Wittenberg R, Egi M, Huang W and Liebeskind L S 2007 Ambient temperature synthesis of high enantiopurity N-protected peptidyl ketones by peptidyl thiol ester-boronic acid cross-coupling J. Am. Chem. Soc. 129 1132

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  7. Crich D and Sharma I 2009 Epimerization-free block synthesis of peptides from thioacids and amines with the Sanger and Mukaiyama reagents Angew. Chem. Int. Ed. 48:2355

    Article  CAS  Google Scholar 

  8. Kunchithapatham K, Eichman C C and Stambuli J P 2011 Synthesis of diaryl ketones via a phosphine-free Fukuyama reaction Chem. Commun. 47 12679

    CAS  Google Scholar 

  9. Keating T A and Walsh C T 1999 Initiation, elongation, and termination strategies in polyketide and polypeptide antibiotic biosynthesis Curr. Opin. Chem. Biol. 3 598

    Article  CAS  Google Scholar 

  10. Khosla C, Tang Y, Chen A Y, Schnarr N A and Cane D E 2007 Structure and mechanism of the 6-deoxyerythronolide B synthase Annu. Rev. Biochem. 76 195

    Article  CAS  Google Scholar 

  11. Tokuyama H, Yokoshima S, Yamashita T and Fukuyama T 1998 A novel ketone synthesis by a palladium-catalyzed reaction of thiol esters and organozinc reagents Tetrahedron Lett. 39 3189

    CAS  Google Scholar 

  12. Ueda M, Seki K and Imai Y 1981 S- and N-acyl derivatives of 2-mercaptobenzoxazole: New, highly reactive acylating agents for synthesis of amides and esters Synthesis 12 991

    Article  Google Scholar 

  13. Mehta V P, Sharma A and Eycken E V 2008 The first palladium-catalyzed desulfitative sonogashira-type cross-coupling of (hetero)aryl thioethers with terminal alkynes Org. Lett. 10 1147

    CAS  Google Scholar 

  14. Azuma H, Okano K and Tokuyama H 2011 Synthesis of acylsilanes by palladium-catalyzed cross-coupling reaction of thiol esters and silylzinc chlorides Chem. Lett. 40 959

    CAS  Google Scholar 

  15. Kotsuki H, Yoshimura N, Ushio Y, Ohtsuka T and Ochi M 1986 Facile reduction of benzenethiol esters under mild conditions with zinc borohydride Chem. Lett. 15 1003

    Google Scholar 

  16. Fukuyama T, Lin S C and Li L 1990 Facile reduction of ethyl thiol esters to aldehydes: application to a total synthesis of (+)-neothramycin A methyl ether J. Am. Chem. Soc. 112 7050

    Article  CAS  Google Scholar 

  17. Nagashima E, Suzuki K and Sekiya M 1983 Reactions of 2,2-dichlorovinyl and 2,2-dichlorovinylidene sulfides with butyllithium Chem. Pharm. Bull. 31 3306

    Article  CAS  Google Scholar 

  18. Yousif N M, Pedersen U, Yde B and Lawesson S O 1984 Studies on organophosphorus compounds. XLVIII. Synthesis of dithioesters from phosphorus- and sulfur-containing reagents and carboxylic acids and their derivatives Tetrahedron 40 2663

    Article  CAS  Google Scholar 

  19. Alvarez-Ibarra C, Mendoza M, Orellana G and Quiroga M L 1989 A novel method of synthesis of 2-(methylthio)-1,3-oxazoles Synthesis 7 560

    Article  Google Scholar 

  20. Steglich W and Höfle G 1969 N,N-Dimethyl-4-pyridinamine, a very effective acylation catalyst Angew. Chem. Int. Ed. Engl. 8 981

    Article  CAS  Google Scholar 

  21. Vedejs E, Bennett N S Conn L M, Diver S T, Gingras M, Lin S, Oliver P A and Peterson M J 1993 Tributylphosphine-catalyzed acylations of alcohols: scope and related reactions J. Org. Chem. 58 7286

    Article  CAS  Google Scholar 

  22. Ishihara K, Kubota M, Kurihara H and Yamamoto H 1996 scandium trifluoromethanesulfonate as an extremely active Lewis acid catalyst in acylation of alcohols with acid anhydrides and mixed anhydrides J. Org. Chem. 61 4560

    Article  CAS  PubMed  Google Scholar 

  23. Ishihara K, Kubota M and Yamamoto H 1996 A new scandium complex as an extremely active acylation catalyst Synlett 39 265

    Article  Google Scholar 

  24. Procopiou P A, Baugh S P D, Flack S S and Inglis G G A 1998 An extremely powerful acylation reaction of alcohols with acid anhydrides catalyzed by trimethylsilyl trifluoromethanesulfonate J. Org. Chem. 63 2342

    Article  CAS  Google Scholar 

  25. Saravanan P and Singh V K 1999 An efficient method for acylation reactions Tetrahedron Lett. 40 2611

    CAS  Google Scholar 

  26. Pansare S V, Malusare M G, Pansare S V, Malusare M G and Rai A N 2000 Magnesium bromide catalyzed acylation of alcohols Synth. Commun. 30 2587

    CAS  Google Scholar 

  27. Derdau V and Snieckus V 2001 Condensation of laterally lithiated o-methyl and o-ethyl benzamides with imines mediated by (-)-sparteine. Enantioselective synthesis of tetrahydroisoquinolin-1-ones J. Org. Chem. 66 1992

    Article  CAS  PubMed  Google Scholar 

  28. Nakae Y, Kusaki I and Sato T 2001 Lithium perchlorate catalyzed acetylation of alcohols under mild reaction conditions Synlett 10 1584

    Article  Google Scholar 

  29. Orita A, Tanahashi C, Kakuda A and Otera J 2001 Highly powerful and practical acylation of alcohols with acid anhydride catalyzed by Bi(OTf)3 J. Org. Chem. 66 8926

    Article  CAS  PubMed  Google Scholar 

  30. Kumar P, Pandey R K, Bodas M S, Dagade S P, Dongare M K and Ramaswamy A V 2002 Acylation of alcohols, thiols, and amines with carboxylic acids catalyzed by yttria-zirconia-based lewis acid J. Mol. Catal A Chem. 181 207

    Article  CAS  Google Scholar 

  31. Shah S T A, Khan K M, Heinricha A M and Voelter W 2002 An alternative approach towards the syntheses of thioethers and thioesters using CsF-Celite in acetonitrile Tetrahedron Lett. 43 828

    Google Scholar 

  32. Chakraborti A K and Gulhane R 2003 Indium(III) chloride as a new, highly efficient, and versatile catalyst for acylation of phenols, thiols, alcohols, and amines. Tetrahedron Lett. 44 6749

    Article  CAS  Google Scholar 

  33. Hao Z, Xi W, Wang P and Cai M 2009 Ruthenium(III) chloride catalyzed acylation of alcohols, phenols, and thiols in room temperature ionic liquids Molecules 14 3528

    Article  PubMed  PubMed Central  CAS  Google Scholar 

  34. Basu B, Paul S and Nanda A K 2010 Silica-promoted facile synthesis of thioesters and thioethers: A highly efficient, reusable and environmentally safe solid support Green Chem. 12 767

    Article  CAS  Google Scholar 

  35. Werner K, Robert K H, Christina S, Fritz H, Christine S, Hannelore D and Jurgen S 2012 A single-cell NMR membrane transport assay Eur. J. Chem. 9 2501

    Google Scholar 

  36. Prajapti S K, Nagarsenkar A and Babu B N 2014 Tris(pentafluorophenyl)borane catalyzed acylation of alcohols, phenols, amines, and thiophenols under solvent-free condition Tetrahedron Lett. 55 1784

    Article  CAS  Google Scholar 

  37. Sucheta K, Reddy G S R, Ravi D and Rao N R 1994 A novel, general route to the synthesis of carboxylic acid esters and thiol esters Tetrahedron Lett. 35 4415

    Article  CAS  Google Scholar 

  38. Bandgar B P and Pandit S S 2004 A novel and direct synthesis of thiolesters using cyanuric chloride under mild conditions J. Sulfur Chem. 25 343

    Article  CAS  Google Scholar 

  39. Roy H N, Sarker A K and Al Mamun A H 2010 Rapid and regiospecific phenylthiolation of some organic acids catalyzed by AlCl3 in the presence of excess anhydrous ZnCl2 Synth. Commun. 40 2158

    CAS  Google Scholar 

  40. Lara R G, Rodrigues D C, Samue R, Mendes Panatieri R B, Jacob R G, Alves D, Lenardáo E J and Perin G 2011 Synthesis of thiol esters by the reaction of ricinoleic acid with thiols under solvent-free conditions Synth. Commun. 41 2974

    CAS  Google Scholar 

  41. El-Azab A S, Abdel-Aziz and A A.-M 2012 An efficient synthesis of thioesters via TFA-catalyzed reaction of carboxylic acid and thiols: remarkably facile C-S bond formation Phosphorus, Sulfur Silicon Relat. Elem. 187 1046

  42. Katritzky A R, He H Y and Suzuki K 2000 N-acylbenzotriazoles: neutral acylating reagents for the preparation of primary, secondary, and tertiary amides J. Org. Chem. 65 8210

    Article  CAS  PubMed  Google Scholar 

  43. Prasad H S, Srinivasa G R, Gowda D C 2005 Convenient, cost-effective, and mild method for the N-acetylation of anilines and secondary amines Synth. Commun. 35 1189

    CAS  Google Scholar 

  44. Taylor J E, Jones M D, Williams J M J and Bull S D 2012 N-acyl DBN tetraphenylborate salts as N-acylating agents J. Org. Chem. 77 2808

    Article  CAS  PubMed  Google Scholar 

  45. Taylor J E, Williams J M J, Bull S D 2012 N-Acyl 1,5-diazabicyclo[4.3.0] non-5-ene (DBN) tetraphenylborate salts as O-acylating agents Tetrahedron Lett. 53 4074

    Article  CAS  Google Scholar 

  46. Chikkulapalli A, Aavula S K, Mona R N P, Karthikeyan C, Kumar V C, Sulur M G and Sumathi S 2015 Convenient N-acetylation of amines in N,N-dimethylacetamide with N,N-carbonyldiimidazole Tetrahedron Lett. 56 3799

    Article  CAS  Google Scholar 

  47. Gernon M D, Wu M, Buszta T and Janney P 1999 Environmental benefits of methanesulfonic acid. Comparative properties and advantages Green Chem. 1 127

    Article  CAS  Google Scholar 

  48. Jamshad M, Murrell J C and Fülöp V 2007 Purification and crystallization of the hydroxylase component of the methanesulfonate monooxygenase from Methylosulfonomonas methylovora strain M2 Protein Expr. Purif. 52 472

    Article  CAS  Google Scholar 

  49. Susperregui N, Delcroix D, Martin-Vaca B, Bourissou D and Maron, L 2010 Ring-opening polymerization of ε-caprolactone catalyzed by sulfonic acids: Computational evidence for bifunctional activation J. Org. Chem. 75 6581

    Article  CAS  PubMed  Google Scholar 

  50. Boyle R and Venkataramani E S 1995 Biodegradation of methanesulfonic acid PCT Int. Appl. WO 9521135 (CAN 123:207938)

  51. Stott P E, Bradshaw J S, Parish W W and Copper J W 1980 Modified crown ether catalysts. 2. Synthesis of alkanoyl-, aroyl-, α-hydroxyalkyl- and alkylbenzo and alkylcyclohexano crown ethers J. Org. Chem. 45 4716

    Article  CAS  Google Scholar 

  52. Kelly T R and Ghoshal M 1985 Expeditious synthesis of resistomycin J. Am. Chem. Soc. 107 3879

    Article  CAS  Google Scholar 

  53. Eck G, Julia M, Pfeiffer B and Rolando C 1985 Access to the spiro hydrindandione ring system of fredericamycin A through a Friedel-Crafts reaction Tetrahedron Lett. 26 4723

    CAS  Google Scholar 

  54. Li J J, Mitchell L H and Dow R L 2010 Thyroid receptor agonists for the treatment of androgenetic alopecia Biorg. Med. Chem. Lett. 20 306

    Article  CAS  Google Scholar 

  55. Wu Z, Guo W, Lian G and Yu B 2010 Synthesis of mangiferin, isomangiferin, and homomangiferin J. Org. Chem. 75 5725

    Article  CAS  PubMed  Google Scholar 

  56. Sharghi H and Kaboudon B J 1998 Alumina in methanesulfonic acid (AMA) as a new efficient reagent for direct acylation of phenol derivatives and Fries rearrangement. a convenient synthesis of o-hydroxyarylketones J. Chem. Res., Synop. 10 628

    Article  Google Scholar 

  57. Sharghi H and Hosseini-Sarvari M 2004 Simple and improved procedure for the regioselective acylation of aromatic ethers with carboxylic acids on the surface of graphite in the presence of methanesulfonic acid Synthesis 13 2165

    Article  CAS  Google Scholar 

  58. Sharghi H, Hosseini-Sarvari M and Eskandari R 2006 Direct acylation of phenol and naphthol derivatives in a mixture of graphite and methanesulfonic acid Synthesis 12 2047

    Article  CAS  Google Scholar 

  59. Wilkinson M C 2011 “Greener” Friedel-Crafts acylations: a metal- and halogen-free methodology Org. Lett 13 2232

    CAS  Google Scholar 

  60. Choudhary G, Peddinti R K 2011 An expeditious, highly efficient, catalyst-free and solvent-free synthesis of nitroamines and nitrosulfides by Michael addition Green Chem. 13 276

    Article  CAS  Google Scholar 

  61. Parumala S K R and Peddinti R K 2015 Iodine catalyzed cross-dehydrogenative C–S coupling by C(sp2–H bond activation: direct access to aryl sulfides from aryl thiols Green Chem. 17 4068

    Article  CAS  Google Scholar 

  62. Singh P and Peddinti R K 2017 Waste-free swift synthesis of symmetrical and unsymmetrical diarylmethyl thioethers from diaryl carbinols Synthesis 49 3633

    Article  CAS  Google Scholar 

  63. Singh P, Singh U P and Peddinti R K 2017 PTSA-catalyzed functionalization of hydroquinones with benzhydryl alcohols in water Tetrahedron Lett. 58 2813

    CAS  Google Scholar 

  64. Singh P and Peddinti R K 2017 Metal-free alkyl(aryl) transfer–aromatization–alkylation domino approach: facile synthesis of branched hydroquinones from p-quinols and diaryl carbinols ChemistrySelect 2 3622

    Article  CAS  Google Scholar 

  65. Singh P and Peddinti R K 2017 Harnessing the catalytic behaviour of 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP): An expeditious synthesis of thioesters Tetrahedron Lett. 58 1875

    Article  CAS  Google Scholar 

  66. Singh S and Yadav L D S 2012 The direct thioesterification of aldehydes with disulfides via NHC-catalyzed carbonyl umpolung strategy Tetrahedron Lett. 53 5136

    CAS  Google Scholar 

  67. Dan W, Deng H, Chen J, Ding J and Wu H 2010 A new odorless one-pot synthesis of thioesters and selenoesters promoted by Rongalite® Tetrahedron 66 7384

    Article  CAS  Google Scholar 

  68. Feng J, Lv M-F, Lu G-P and Cai C 2015 Direct oxidative coupling of thiols and benzylic ethers via C(sp3)–H activation and C–O cleavage to lead thioesters Org. Biomol. Chem. 13 677

    Article  CAS  Google Scholar 

  69. Rong G, Mao J, Liu D, Yan H, Zheng Y and Chen J 2015 Formation of C(sp2)–S bonds through decarboxylation of α-oxocarboxylic acids with disulfides or thiophenols RSC Adv. 5 26461

    Article  CAS  Google Scholar 

  70. Zhu X, Shi Y, Mao H, Cheng Y and Zhu C 2013 Tetraethylammonium bromide-catalyzed oxidative thioesterification of aldehydes and alcohols Adv. Synth. Catal. 355 3558

    Article  CAS  Google Scholar 

  71. Ali W, Guin S, Rout S K, Gogoi A and Patel B K 2014 Thioesterification of alkylbenzenes with thiols via copper-catalyzed cross-dehydrogenative coupling without a directing group Adv. Synth. Catal. 356 3099

    Article  CAS  Google Scholar 

  72. He C, Qian X and Sun P 2014 Syntheses of thiol and selenol esters by oxidative coupling reaction of aldehydes with RYYR (Y = S, Se) under metal-free conditions Org. Biomol. Chem. 12 6072

    Article  CAS  Google Scholar 

  73. Shakoor S M A, Choudhary S, Bajaj K, Muthyala M K, Kumar A and Sakhuja R 2015 Imidazolium-supported benzotriazole: an efficient and recoverable activating reagent for amide, ester and thioester bond formation in water RSC Adv. 5 82199

    Article  CAS  Google Scholar 

  74. Yan K, Yang D, Wei W, Zhao J, Shuai Y, Tian L and Wang H 2015 Catalyst-free direct decarboxylative coupling of α-keto acids with thiols: A facile access to thioesters Org. Biomol. Chem. 13 7323

    Article  CAS  Google Scholar 

  75. Pijper T C, Robertus J, Browne W R and Feringa B L 2015 Mild Ti-mediated transformation of t-butyl thio-ethers into thio-acetates Org. Biomol. Chem. 13 265

    Article  CAS  Google Scholar 

  76. Kashyap B and Phukan P 2013 A new ferrocene-based bulky pyridine as an efficient reusable homogeneous catalyst RSC Adv. 3 15327

    CAS  Google Scholar 

  77. Katritzky A R, Shestopalov A A and Suzuki K 2004 A new convenient preparation of thiol esters utilizing N-acylbenzotriazoles Synthesis 11 1806

    Article  CAS  Google Scholar 

  78. Uno T, Inokuma T and Takemoto Y 2012 NHC-catalyzed thioesterification of aldehydes by external redox activation Chem. Commun. 48 1901

    CAS  Google Scholar 

  79. Iranpoor N, Firouzabadi H, Khalili D and Motevalli S 2008 Easily prepared azopyridines as potent and recyclable reagents for facile esterification reactions. An efficient modified mitsunobu reaction J. Org. Chem. 73 4882

    Article  CAS  PubMed  Google Scholar 

  80. Swain S P, Chou Y-L and Hou D-R 2015 Thioesterifications free of activating agent and thiol: A three-component reaction of carboxylic acids, thioureas, and michael acceptors Adv. Synth. Catal. 357 2644

    Article  CAS  Google Scholar 

  81. Lai C and Backes B J 2007 Efficient preparation of S-aryl thioacetates from aryl halides and potassium thioacetate Tetrahedron Lett. 48 3033

    Article  CAS  Google Scholar 

  82. Petrillo G, Novi M, Garbarino G and Filiberti M 1989 The reaction between arenediazonium tetrafluoroborates and alkaline thiocarboxylates in DMSO: A convenient access to aryl thiolesters and other aromatic sulfur derivatives Tetrahedron 45 7411

    Article  CAS  Google Scholar 

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Acknowledgements

P.S. thanks UGC (New Delhi) for a research fellowship.

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  1. Department of Chemistry, Indian Institute of Technology Roorkee, Roorkee, Uttarakhand, 247 667, India

    Pallavi Singh & Rama Krishna Peddinti

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  1. Pallavi Singh
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Correspondence to Rama Krishna Peddinti.

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Singh, P., Peddinti, R.K. Methanesulfonic anhydride-promoted sustainable synthesis of thioesters from feedstock acids and thiols. J Chem Sci 133, 20 (2021). https://doi.org/10.1007/s12039-020-01871-5

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  • DOI: https://doi.org/10.1007/s12039-020-01871-5

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