Abstract
The chiral metal complex produced in situ from (R)-6,6\(^{\prime }\)-Diphenyl-BINOL and \(\mathrm{Ti}(\mathrm{O}-{} { i}-\mathrm{Pr})_{4}\) as a catalytic system for asymmetric sulfoxidation of aryl methyl and aryl benzyl sulfides in the presence of 70% aqueous TBHP as the oxidant has been investigated. The influence of variation of reagents mole ratios, temperature, solvent and oxidant was examined, and the optimized conditions were then used to oxidize a number of aryl methyl and aryl benzyl sulfides, producing sulfoxides in high enantiopurities (up to 90% ee) and good yields (up to 81%).
Graphic Abstract
(R)-6,6’-Diphenyl Binol in combination with \(\hbox {Ti(O-i-Pr)}_{4}\) has been developed as an efficient chiral ligand for the asymmetric oxidation of aryl methyl and aryl benzyl sulfides by using 70% aqueous TBHP as an oxidant. High enantioselectivity and good chemical yield have been achieved for various aryl methyl and aryl benzyl sulfides.
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References
Solladie G 1983 In Asymmetric Synthesis Vol. 2 James D Morrison (Ed.) (Florida: Academic Press) p. 157
Sklute G, Amsallem D, Shabli A, Varghese J P and Marek I 2003 Four-component reactions for a new diastereoselective synthesis of chiral quaternary centers J. Am. Chem. Soc. 125 11776
Carreno M C, Garcia R J L, Martin A M, Pedregal C, Rodriguez J H, Rubio A, Sanchez J and Solladie G 1990 Stereoselective reductions of 2-keto sulfoxides with hydrides J. Org. Chem. 55 2120
Ruano J L G and De la P B C 1999 Asymmetric [4+2] cycloadditions mediated by sulfoxides Top. Curr. Chem. 204 1
Lee A W M and Chan W H 1997 Chiral acetylenic sulfoxides and related compounds in organic synthesis Top. Curr. Chem. 190 103
Arai Y and Koizumi T 1993 Chiral sulfinylethenes as efficient dienophiles for asymmetric diels-alder reactions Sulfur Rep. 15 41
Renaud P and Gerster M 1998 Use of lewis acids in free radical reactions Angew. Chem. Int. Ed. 37 2562
Toru T, Watanabe Y, Mase N, Tsusaka M, Hayakawa T and Ueno Y 1996 Diastereofacial control in the radical addition to chiral \(\upalpha \)-sulfinyl enones Pure Appl. Chem. 68 711
Fernandez I, Valdivia V, Leal M P and Khiar N 2007 \(C_{2}\)-symmetric bissulfoxides as organocatalysts in the allylation of benzoyl hydrazones: spacer and concentration effects Org. Lett. 9 2215
Cotton H, Elebring T, Larsson M, Li L, Sorensen H and von Unge S 2000 Asymmetric synthesis of esomeprazole Tetrahedron: Asymm. 11 3819
Wojaczynska E and Wojaczynski J 2010 Enantioselective synthesis of sulfoxides: 2000–2009 Chem. Rev. 110 4303
Bryliakov K P and Talsi E P 2008 Transition metal catalyzed asymmetric oxidation of sulfides Curr. Org. Chem. 12 386
Plitt P, Pritzkow H, Oeser T and Kraemer R 2005 Biphenyl derived oxovanadium (IV) and copper (II) salen-type complexes—structure and redox tuning J. Inorg. Biochem. 99 1230
Pitchen P, Dunach E, Deshmukh M N and Kagan H B 1984 An efficient asymmetric oxidation of sulfides to sulfoxides J. Am. Chem. Soc. 106 8188
Pitchen P and Kagan H B 1984 An efficient asymmetric oxidation of sulfides to sulfoxides Tetrahedron Lett. 25 1049
Furia F, Modena G and Seraglia R 1984 Synthesis of chiral sulfoxides by metal-catalyzed oxidation with \(t\)-Butyl hydroperoxide Synthesis 325
Sharpless K B and Katsuki T 1980 The first practical method for asymmetric epoxidation J. Am. Chem. Soc. 102 5974
Rossiter B E, Katsuki T and Sharpless K B 1981 Asymmetric epoxidation provides shortest routes to four chiral epoxy alcohols which are key intermediates in syntheses of methymycin, erythromycin, leukotriene C-1, and disparlure J. Am. Chem. Soc. 103 464
Brunel J M 2005 BINOL: a versatile chiral reagent Chem. Rev. 105 857
Chen Y, Yekta S and Yudin A K 2003 Modified BINOL ligands in asymmetric catalysis Chem. Rev. 103 3155
Sasai H, Tokunaga T, Watanabe S, Suzuki T, Itoh N and Shibasaki M 1995 Efficient diastereoselective and enantioselective nitroaldol reactions from prochiral starting materials: utilization of La-Li-6,6’-disubstituted BINOL complexes as asymmetric catalysts J. Org. Chem. 60 7388
Terada M, Motoyama Y and Mikami K 1994 Diastereoselective and enantioselective glyoxylate-ene reaction catalyzed by new class of binaphthol-derived titanium complex Tetrahedron Lett. 36 6693
Qian C T, Huang T S, Zhu C J and Sun J 1998 Synthesis of 3,\(3^\prime \)-, 6,\(6^\prime \)- and 3,\(3^\prime \),6,\(6^\prime \)-substituted binaphthols and their application in the asymmetric hydrophosphonylation of aldehydes—an obvious effect of substituents of BINOL on the enantioselectivity J. Chem. Soc., Perkin Trans. 1 2097
Qian C T, Zhu C J and Huang T S 1998 Enantioselective trimethylsilylcyanation of aldehydes catalyzed by chiral lanthanoid alkoxides J. Chem. Soc., Perkin Trans. 1 2131
Chen R, Qian C and Vries J G 2001 Asymmetric epoxidation of \(\upalpha ,\upbeta \)-unsaturated ketones catalyzed by chiral ytterbium complexes Tetrahedron Lett. 42 6919
G E O’Mahony, A Ford and A R Maguire 2012 Copper-catalyzed asymmetric oxidation of sulfides J. Org. Chem. 77 3288
Acknowledgements
The authors are thankful to the M/S Lupin Limited and the authorities of Manipal Academy of Higher Education for the research program. We also acknowledge the valuable guidance, support and suggestions from Dr. P. R. Upadhyay, Dr. Milind Sindkhedkar and Dr. Vijaya Desai.
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Maddireddy, N.V., Godbole, H.M., Singh, G.P. et al. Catalytic asymmetric oxidation of sulfides to sulfoxides using (R)-6,6\(^{\prime }\)-Diphenyl-BINOL as a chiral ligand. J Chem Sci 131, 64 (2019). https://doi.org/10.1007/s12039-019-1635-4
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DOI: https://doi.org/10.1007/s12039-019-1635-4