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A study of enantioselective syntheses by Sharpless asymmetric oxidation for aryl sulfoxides containing oxygen groups at the ortho position

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Abstract

While ortho-alkoxy aryl sulfoxides including various substituents were synthesized by Sharpless asymmetric oxidation reaction, we optimized the reaction conditions and screened better combination of starting materials to obtain high enantioselectivity. The result suggested new information that electron-withdrawing substituents on the aromatic ring have a strong influence upon enantioselectivity of the products. Also, several chiral ligands for Sharpless asymmetric oxidation reaction were evaluated to improve the enantioselectivity.

Graphic abstract

High enantioselectivity of ortho-alkoxy aryl chiral sulfoxides have been achieved by Sharpless oxidation reaction using Ti(O-i-Pr)4 and diethyl tartrate under anhydrous condition. In particular, the enantioselctivity of products was influenced by electron-withdrawing substituents on the aromatic ring, such as nitro, ester and aldehyde groups.

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References

  1. Trost B M and Rao M 2015 Development of chiral sulfoxide ligands for asymmetric catalysis Angew. Chem. Int. Ed. 54 5026

    Article  CAS  Google Scholar 

  2. Pulis A P and Procter D J 2016 C-H Coupling reactions directed by sulfoxides: teaching an old functional group new tricks Angew. Chem. Int. Ed. 55 9842

    Article  CAS  Google Scholar 

  3. Pellissier H 2006 Use of chiral sulfoxides in asymmetric synthesis Tetrahedron 62 5559

    Article  CAS  Google Scholar 

  4. Fernández I, Valdiva V, Leal M P and Khiar N 2007 C2-Symmtric bissulfoxides as organocatalysts in the allylation of benzoyl hydrazones: spacer and concentration effects Org. Lett. 9 2215

    Article  PubMed  CAS  Google Scholar 

  5. Otocka S, Kwiatkowska M, Madalińska L and Kiełbasiński P 2017 Chiral organosulfur ligands/catalysts with a stereogenic sulfur atom: applications in asymmetric synthesis Chem. Rev. 117 4147

    Article  CAS  PubMed  Google Scholar 

  6. Äbelö A, Andersson T B, Antonsson M, Naudot A K, Skånberg I and Weidolf L 2000 Stereoselective metabolism of omeprazole by human cytochrome P450 enzymes Drug Metab. Dispos. 28 966

    PubMed  Google Scholar 

  7. Flynn G A and Ash R J 1983 Necessity of the sulfoxide moiety for the biochemical and biological properties of an analog of sparsomycin Biochem. Biophys. Res. 114 1

    Article  CAS  Google Scholar 

  8. Hansen J L, Schmeing T M, Moore P B and Steitz T A 2002 Structural insights into peptide bond formation PNAS 99 11670

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  9. Bentley R 2005 Role of sulfur chirality in the chemical processes of biology Chem. Soc. Rev. 34 609

    Article  CAS  PubMed  Google Scholar 

  10. Xiong F, Yang B-B, Zhang J and Li L 2018 Enantioseparation, stereochemical assignment and chiral recognition mechanism of sulfoxide-containing drugs Molecules 23 2680

    Article  PubMed Central  CAS  Google Scholar 

  11. Matsui T, Dekishima Y and Ueda M 2014 Biotechnological production of chiral organic sulfoxides: current state and perspectives Appl. Microbiol. Biotechol. 98 7699

    Article  CAS  Google Scholar 

  12. Goundry W R F, Adams B, Benson H, Demeritt J, McKown S, Mulholland K, et al. 2017 Development and scale-up of a biocatalytic process to form a chiral sulfoxide Org. Process. Res. Dev. 21 107

    Article  CAS  Google Scholar 

  13. Butler B T, Silvey G, Houston D M, Borcherding D R, Vaughn V L, Mcphail A T, et al. 1992 The resolution, isolation, and pharmacological characterization of the enantiomers of a benzamide containing a chiral sulfoxide Chirality 4 155

    Article  CAS  PubMed  Google Scholar 

  14. Kashiyama E, Todaka T, Odomi M, Tanokura Y, Johnson D B, Yokoi T, et al. 1994 Stereoselective pharmacokinetics and interconversions of flosequinan enantiomers containing chiral sulphoxide in rat Xenobiotica 24 369

    Article  CAS  PubMed  Google Scholar 

  15. Katsuki H, Yagi H, Arimori K, Nakamura C, Nakano M, Katafuchi S, et al. 1996 Determination of R (+)- and S (-)-lansoprazole using chiral stationary-phase liquid chromatography and their enantioselective pharmacokinetics in humans Pharm. Res. 13 611

    Article  CAS  PubMed  Google Scholar 

  16. Donovan J L, Malcolm R J, Markowitz J S and De Vane C L 2003 Chiral analysis of d- and l-modafinil in human serum: application to human pharmacokinetic studies Ther. Drug Monit. 25 197

    Article  CAS  PubMed  Google Scholar 

  17. Delatour P, Benoit E, Besse S and Boukraa A 1991 Comparative enantioselectivity in the sulphoxidation of albendazole in man, dogs and rats Xenobiotica 21 217

    Article  CAS  PubMed  Google Scholar 

  18. Cristofol C, Virkel G, Alvarez L, Sánchez S, Arboix M and Lanusse C 2001 Albendazole sulphoxide enantiomeric ratios in plasma and target tissues after intravenous administration of ricobendazole to cattle J. Vet. Pharmacol. Therap. 24 117

    Article  CAS  Google Scholar 

  19. Fernández I and Khiar N 2003 Recent developments in the synthesis and utilization of chiral sulfoxides Chem. Rev. 103 3651

    Article  PubMed  CAS  Google Scholar 

  20. Pitchen P, Duñach E, Deshmukh M N and Kagan H B 1984 An efficient asymmetric oxidation of sulfides to sulfoxides J. Am. Chem. Soc. 106 8188

    Article  CAS  Google Scholar 

  21. Zhao S H, Samuel O and Kagan H B 1987 Asymmetric oxidation of sulfides mediated by chiral titanium complexes: mechanistic and synthetic aspects Tetrahedron 43 5135

    Article  CAS  Google Scholar 

  22. Kagan H B and Rebiere F 1992 Some routes to chiral sulfoxides with very high enantiomeric excesses Synlett 1992 643

    Google Scholar 

  23. Saitoh M, Kunitomo J, Kimura E, Yamano T, Itoh F and Kori M 2010 Enantioselective synthesis of the novel chiral sulfoxide derivatives as a glycogen synthase kinase 3β inhibitor Chem. Pharm. Bull. 58 1252

    Article  CAS  Google Scholar 

  24. Capozzi M A M, Cardellicchio C, Naso F and Tortorella P 2000 Substituted benzene anions as leaving groups in the reaction of sulfinyl derivatives with Grignard reagents: a new and convenient route to dialkyl sulfoxides in high enantiomeric purity J. Org. Chem. 65 2843

    Article  CAS  PubMed  Google Scholar 

  25. Bolm C, Müller P and Harms K 1996 Sulfoximine-titanium reagents in enantioselective trimethylsilylcyanations of aldehydes Acta Chem. Scand. 50 305

    Article  CAS  Google Scholar 

  26. Wang P, Chen J, Cun L, Deng J, Zhu J and Liao J 2009 Aryl tert-butyl sulfoxide-promoted highly enantioselective addition of allyltrichlorosilane to aldehydes Org. Biomol. Chem. 7 3741

    Article  CAS  PubMed  Google Scholar 

  27. Lin Z, Gong L, Celik M A, Harms K, Frenking G and Meggers E 2011 Asymmetric coordination chemistry by chiral-auxiliary-mediated dynamic resolution under thermodynamic control Chem. Asian J. 6 474

    Article  CAS  PubMed  Google Scholar 

  28. Mohd A, Anitha T, Reddy K R, Wencel-Delord J and Colobert F 2019 P-Stereogenic phosphonates via dynamic kinetic resolution: a route towards enantiopure tertiary phosphine oxides Eur. J. Org. Chem. 2019 7836

    Article  CAS  Google Scholar 

  29. Tang Y, Sun Y, Liu J and Duttwyler S 2016 Facile synthesis of enantioenriched phenol-sulfoxides and their aluminum complexes Org. Bioorg. Chem. 14 5580

    Article  CAS  Google Scholar 

  30. Gong L, Lin Z, Harms K and Meggers E 2010 Isomerization-induced asymmetric coordination chemistry: from auxiliary control to asymmetric catalysis Angew. Chem. Int. Ed. 49 7955

    Article  CAS  Google Scholar 

  31. Seidel F W, Frieß S, Heinemann F W, Chelouan A, Scheurer A, Grasruck A, et al. 2018 C2-Symmetric (SO)N(SO) sulfoxide pincer complexes of Mg and Pd: Helicity switch by ambidentate S/O-coordination and isolation Organometallics 37 1160

    Article  CAS  Google Scholar 

  32. Li Z-Z, Wen A-H, Yao S-Y and Ye B-H 2015 Enantioselective syntheses of sulfoxides in octahedral ruthenium(II) complexes via a chiral-at-metal strategy Inorg. Chem. 54 2726

    Article  CAS  PubMed  Google Scholar 

  33. Li Z-Z, Yao S-Y, Wu J-J and Ye B-H 2014 In situ generation of sulfoxides with predetermined chirality via a structural template with a chiral-at-metal ruthenium complex Chem. Commun. 50 5644

    Article  CAS  Google Scholar 

  34. Yao S-Y, Chen X-Y, Ou Y-L and Ye B-H 2017 Chiral recognition and dynamic thermodynamic resolution of sulfoxides by chiral iridium(III) complexes Inorg. Chem. 56 878

    Article  CAS  PubMed  Google Scholar 

  35. Rocaboy R, Anastasiou I and Baudoin O 2019 Redox-Neutral Coupling between Two C(sp3)-H bonds enabled by 1,4-palladium shift for the synthesis of fused heterocycles Chem. Int. Ed. 58 14625

    Article  CAS  Google Scholar 

  36. Stephenson G R, Roe C and Sandoe E J 2011 Electrophilic C12 building blocks for alkaloids: 1,1 Iterative organoiron-mediated routes to (±)-lycoramine and (±)-maritidine Eur. J. Org. Chem. 9 1664

    Article  CAS  Google Scholar 

  37. Liu J-G, Naruta Y and Tani F 2007 Synthetic models of the active site of cytochrome c oxidase: influence of tridentate or tetradentate copper chelates bearing a His-Tyr linkage mimic on dioxygen adduct formation by heme/Cu complexes Chem. Eur. J. 13 6365

    Article  CAS  PubMed  Google Scholar 

  38. Carson M , Giese M W and Coghlan M J 2008 An intra/intermolecular Suzuki sequence to Benzopyridyloxepines containing geometrically pure exocyclic tetrasubstituted alkenes Org. Lett. 10 2701

    Article  CAS  PubMed  Google Scholar 

  39. Obaro-Best O, Reed J, Norfadilah A A F B, Monahan R and Sunasee R 2016 Bismuth trichloride-mediated cleavage of phenolic methoxymethyl ethers Synth. Commun. 46 586

    Article  CAS  Google Scholar 

  40. Hughes C C and Trauner D 2004 Palladium-catalyzed couplings to nucleophilic heteroarenes: the total synthesis of (-)-frondosin B Tetrahedron 60 9675

    Article  CAS  Google Scholar 

  41. Knewtson K E, Rane D and Peterson B R 2018 Targeting fluorescent sensors to endoplasmic reticulum membranes enables detection of peroxynitrite during cellular phagocytosis ACS Chem. Biol. 13 2595

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  42. Basabe P, Diego A, Delgado S, Díez D, Marcos I S and Urones J G 2003 Short and efficient synthesis of (+)-subersic acids Tetrahedron 59 9173

    Article  CAS  Google Scholar 

  43. Chausset-Boissarie L, Àrvai R, Cumming G R, Besnard C and Kündig E P 2010 Total synthesis of (±)-Vertine with Z-selective RCM as a key step Chem. Commun. 46 6264

    Article  CAS  Google Scholar 

  44. Inoue T, Takada M, Suzuki T and Saito K 1994 Process for producing trisubstituted benzene, and intermediate PCT Int. Appl. 10 9424099

    Google Scholar 

  45. Kalgutkar A S, Kozak K R, Crews B C, Hochgesang G P Jr and Marnett K J 1998 Covalent modification of cyclooxygenase-2 (COX-2) by 2-acetoxyphenyl alkyl sulfides, a new class of selective COX-2 inactivators J. Med. Chem. 41 4800

    Article  CAS  PubMed  Google Scholar 

  46. Donner P L, Randolph J T, Krueger A C, Betebenner D A, Hutchinson D K, Liu D, et al. 2009 Uracil derivatives as HCV inhibitors and their preparation, pharmaceutical compositions and use in the treatment of hepatitis C PCT Int. Appl. 25 2009039135

    Google Scholar 

  47. Peng L, Wen Y, Chen Y, Yuan Z, Zhou Y, Cheng X, et al. 2018 Biocatalytic preparation of chiral sulfoxides through asymmetric reductive resolution by methionine sulfoxide reductase A ChemCatChem 10 3284

    Article  CAS  Google Scholar 

  48. Jalba A, Régnier N and Ollevier T 2017 Enantioselective aromatic sulfide oxidation and tandem kinetic resolution using aqueous H2O2 and chiral iron-bis(oxazolinyl)bipyridine catalysts Eur. J. Org. Chem. 2017 1628

    Article  CAS  Google Scholar 

  49. Oyaizu K, Mikami T, Mitsuhashi F and Tsuchida E 2002 Synthetic routes to polyheteroacenes: characterization of a heterocyclic ladder polymer containing phenoxathiinium-type building blocks Macromolecules 35 67

    Article  CAS  Google Scholar 

  50. Lau S Y W and Keay B A 2001 A highly efficient strategy for the synthesis of 3-substituted salicylic acids by either directed ortho-lithiation or halogen-metal exchange of substituted MOM protected phenols followed by carboxylation Can. J. Chem. 79 1541

    CAS  Google Scholar 

  51. Mispelaere-Canivet C, Spindler J-F, Perrio S and Beslin P 2005 Pd2(dba)3/Xantphos-catalyzed cross-coupling of thiols and aryl bromides/triflates Tetrahedron 61 5253

    Article  CAS  Google Scholar 

  52. Itoh T and Mase T 2004 A general palladium-catalyzed coupling of aryl bromides/triflates and thiols Org. Lett. 6 4587

    Article  CAS  PubMed  Google Scholar 

  53. Nawrot D, Kolenič M, Kuneš J, Kostelansky F, Miletin M, Novakova V and Zimcik P 2018 Transalkylation of alkyl aryl sulfides with alkylating agents Tetrahedron 74 594

    Article  CAS  Google Scholar 

  54. Thompson A, Garabatos-Perera J R and Gillis H M 2008 Asymmetric oxidation of 2-(arylsulfenyl)pyrroles Can. J. Chem. 86 676

    Article  CAS  Google Scholar 

  55. Brunel J-M, Diter P, Duetsch M and Kagan H B 1995 Highly enantioselective oxidation of sulfides mediated by a chiral titanium complex J. Org. Chem. 60 8086

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. Faculty of Pharmaceutical Sciences, Josai University, 1-1 Keyakidai, Sakado, Saitama, 350-0295, Japan

    Takanori Takei, Jun Takayama, Meiyan Xuan & Takeshi Sakamoto

  2. Faculty of Sciences, Josai University, 1-1 Keyakidai, Sakado, Saitama, 350-0295, Japan

    Misa Tomoda & Hiroshi Miyamae

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  1. Takanori Takei
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  2. Jun Takayama
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  3. Meiyan Xuan
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  4. Misa Tomoda
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Correspondence to Jun Takayama.

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Takei, T., Takayama, J., Xuan, M. et al. A study of enantioselective syntheses by Sharpless asymmetric oxidation for aryl sulfoxides containing oxygen groups at the ortho position. J Chem Sci 133, 28 (2021). https://doi.org/10.1007/s12039-021-01887-5

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