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Manganese-salen catalyzed oxidative benzylic chlorination

  • Sheuli Sasmal
  • Sujoy Rana
  • Goutam Kumar Lahiri
  • Debabrata Maiti
Regular Article

Abstract

Metalloporphyrins are well-known to serve as the model for mimicking reactivities exhibited by cytochrome P450 hydroxylase. Recent developments on selective C–H halogenation using Mn-porphyrins provided the way for understanding the reactivity as well as mechanism of different halogenase enzymes. In this report, we demonstrated a method for benzylic C–H chlorination using easily prepared Mn(salen) complex as the catalyst, which shows a complementary reactivity of Mn-porphyrins. Here, NaOCl has been used as a chlorinating source as well as the oxidant. Efforts towards understanding the mechanism suggested the formation of the high-valent Mn(V)=O species which is believed to be the key intermediate to conduct this transformation.

Graphical abstract

SYNOPSIS Mn(salen)-catalyzed selective benzylic chlorination protocol has been developed using aqueous NaOCl solution. Reactions proceeded efficiently at room temperature and displayed good functional group tolerance. The mechanistic investigation demonstrated that \(\hbox {Mn}(\hbox {V}){=}\hbox {O}\) species is likely to be the key intermediate which is responsible to generate benzylic radical. EPR and ESI-MS studies confirmed the in situ formation of Mn(IV)-species.

Keywords

High-valent manganese salen hypochlorite benzylic chlorination 

Notes

Acknowledgements

This activity is supported by SERB, India (EMR/2015/000164). Financial support has been received from CSIR-India (Fellowship to S.R.).

Supplementary material

12039_2018_1511_MOESM1_ESM.pdf (1.2 mb)
Supplementary material 1 (pdf 1245 KB)

References

  1. 1.
    (a) Vaillancourt F H, Yeh E, Vosburg D A, Tsodikova S G and Walsh C T 2006 Nature’s inventory of halogenation catalysts: Oxidative strategies predominate Chem. Rev. 106 3364; (b) Fujimori D G and Walsh C T 2007 What’s new in enzymatic halogenations Curr. Opin. Chem. Biol. 11 553; (c) Rittle J and Green M T 2010 Cytochrome P450 compound I: Capture, characterization, and C–H bond activation kinetics Science 330 933; (d) Krebs C, Fujimori D G, Walsh C T and Bollinger J 2007 Non-Heme Fe(IV)–Oxo intermediates Acc. Chem. Res. 40 484; (e) Holm R H, Kennepohl P and Solomon E I 1996 Structural and functional aspects of metal sites in biology Chem. Rev. 96 2239; (f) Sono M, Roac M P, Coulte E D and Dawson J H 1996 Heme-containing oxygenases Chem. Rev. 96 2841; (g) Cook S A, Hill E A and Borovik A S 2015 Lessons from nature: A bio-inspired approach to molecular design Biochemistry 54 4167; (h) Que L Jr 2017 60 years of dioxygen activation J. Biol. Inorg. Chem. 22 171; (i) Huang X and Groves J T 2017 Beyond Ferryl–mediated hydroxylation: 40 Years of the rebound mechanism and C–H activation J. Biol. Inorg. Chem. 22 185Google Scholar
  2. 2.
    (a) Yosca T H, Rittle J, Krest C M, Onderko E L, Silakov A, Calixto J C, Behan R K and Green M T 2013 Iron(IV)hydroxide pKa and the role of thiolate ligation in C–H bond activation by cytochrome P450 Science 342 825; (b) Green M T, Dawson J H and Gray H B 2004 Oxoiron(IV) in chloroperoxidase compound II is basic: implications for P450 chemistry Science 304 1653; (c) Stone K L, Behan R K and Green M T 2005 X-ray absorption spectroscopy of chloroperoxidase compound I: Insight into the reactive intermediate of P450 chemistry Proc. Natl. Acad. Sci. U.S.A. 102 16563; (d) Wagenknecht H A and Woggon W D 1997 Identification of intermediates in the catalytic cycle of chloroperoxidase Chem. Biol. 4 367Google Scholar
  3. 3.
    (a) Groves J T 2005 In Cytochrome P450: Structure, mechanism and biochemistry Paul R Ortiz de Montellano (Ed.) (New York: Springer-US) p.1; (b) Kellner D G, Hung S C, Weiss K E and Sligar S G 2002 Kinetic characterization of compound I Formation in the thermostable cytochrome P450 CYP119 J. Biol. Chem. 277 9641; (c) Schlichting I, Berendzen J, Chu K, Stock A M, Maves S A, Benson D E, Sweet R M, Ringe D, Petsko G A and Sligar S G 2000 The catalytic pathway of cytochrome p450cam at atomic resolution Science 287 1615; (d) Egawa T, Shimada H and Ishimura Y 1994 Reaction of ferric cytochrome P450cam with peracids: Kinetic characterization of intermediates on the reaction pathway Biochem. Biophys. Res. Commun. 201 1464Google Scholar
  4. 4.
    (a) Chen Q and Li K 2014 Process for the preparation of benzoyl chloride from toluene, chlorine and benzoic acid China patent CN103787874 A; (b) Ding L, Tang J, Cui M, Bo C, Chen X and Qiao X 2011 Optimum design and analysis based on independent reaction amount for distillation column with side reactors: Production of benzyl chloride Ind. Eng. Chem. Res. 50 11143Google Scholar
  5. 5.
    Kimbrough R D and Bramlbtt R N 1969 Phosphorus pentachloride for the replacement of benzylic hydrogen with chlorine J. Org. Chem. 34 3655CrossRefGoogle Scholar
  6. 6.
    Dutta R L and Fernandas F V 1914 Chlorination by means of aqua regia. The chlorination of benzene, thiophene, toluene and mesitylene J. Am. Chem. Soc. 36 1007CrossRefGoogle Scholar
  7. 7.
    Kojima T, Matsuo H and Matsuda Y 1998 A novel and highly effective halogenation of alkanes with halides on oxidation with m-chloroperbenzoic acid: Looks old, but new reaction Chem. Lett. 27 1085CrossRefGoogle Scholar
  8. 8.
    Kajigaeshi S, Kakinami T, Moriwaki M, Tanaka T and Fujisaki S 1988 An effective chlorinating agent benzyltrimethylammonium tetrachloroiodate, benzylic chlorination of alkylaromatic compound Tetrahedron Lett. 29 5783CrossRefGoogle Scholar
  9. 9.
    Liu S, Zhang Q, Li H, Yang Y, Tian X and Whiting A 2015 A visible-light-induced \(\alpha \)-H chlorination of alkylarenes with inorganic chloride under NanoAg@AgCl Chem. Eur. J. 21 9671CrossRefGoogle Scholar
  10. 10.
    (a) Kenner J 1945 Oxidation and reduction in chemistry Nature 156 369; (b) Walling C and Jacknow B B 1960 Positive halogen compounds. I. The radical chain halogenation of hydrocarbons by t-butyl hypochlorite J. Am. Chem. Soc. 82 6108Google Scholar
  11. 11.
    (a) Che C M, Lo V K Y, Zhou C Y and Huang J S 2011 Selective functionalisation of saturated C–H bonds with metalloporphyrin catalysts Chem. Soc. Rev. 40 1950; (b) Meunier B, Visser S P D and Shaik S 2004 Mechanism of oxidation reactions catalyzed by cytochrome P450 enzymes Chem. Rev. 1043947Google Scholar
  12. 12.
    (a) Bernard M 1992 Metalloporphyrins as versatile catalysts for oxidation reactions and oxidative DNA cleavage Chem. Rev. 92 1411; (b) Bernadou J, Fabiano A S, Robert A and Meunier B 1994 “Redox Tautomerism” in high-valent metal-oxo-aquo complexes. Origin of the oxygen atom in epoxidation reactions catalyzed by water-soluble metalloporphyrins J. Am. Chem. Soc. 116 9375; (c) Balahura R J, Sorokin A, Bernadou J and Meunier B 1997 Origin of the oxygen atom in C–H bond oxidations catalyzed by a water-soluble metalloporphyrin Inorg. Chem. 36 3488Google Scholar
  13. 13.
    (a) Liu W and Groves J T 2010 Manganese porphyrins catalyze selective C–H bond halogenations J. Am. Chem. Soc. 132 12847; (b) Liu W, Huang X, Cheng M J, Nielsen R J, Goddard W A and Groves J T 2012 Oxidative aliphatic C–H fluorination with fluoride ion catalyzed by a manganese porphyrin Science 337 1322; (c) Huang X, Liu W, Ren H, Neelamegam R, Hooker J M and Groves J T 2014 Late stage benzylic C–H fluorination with [\(^{18}\)F] fluoride for PET imaging J. Am. Chem. Soc. 136 6842Google Scholar
  14. 14.
    (a) Jacobsen E N 1993 In Catalytic Asymmetric Synthesis Ojima I (Ed.) (New York: VCH) p. 159; (b) Jacobsen E N 2000 Asymmetric Catalysis of Epoxide Ring-Opening Reactions Acc. Chem. Res. 33 421; (c) Zhang W, Loebach J L, Wilson S R and Jacobsen E N 1990 Enantioselective Epoxidation of Unfunctionalized Olefins Catalyzed by Salen manganese complexes J. Am. Chem. Soc. 112 2801; (d) Irie R, Noda K, Ito Y and Katsuki T 1991 The Use of Chiral Sulfides in Catalytic Asymmetric Epoxidation Tetrahedron Lett. 32 1055; (e) McGarrigle E M and Gilheany D G 2005 Chromium– and Manganese–salen Promoted Epoxidation of Alkenes Chem. Rev. 105 1563Google Scholar
  15. 15.
    (a) Huang X, Bergsten T M and Groves J T 2015 Manganese-catalyzed late-stage aliphatic C–H azidation J. Am. Chem. Soc. 137 5300; (b) Liu W and Groves J T 2013 Manganese-catalyzed oxidative benzylic C–H fluorination by fluoride ions Angew. Chem. Int. Ed. 52 6024; (c) Liu W and Groves J T 2015 Manganese catalyzed C–H halogenation Acc. Chem. Res. 48 1727Google Scholar
  16. 16.
    (a) Chidambaram M, Sonavane S U, Zerda J D L and Sasson Y 2007 Didecyldimethylammonium bromide (DDAB): A universal, robust, and highly potent phase-transfer catalyst for diverse organic transformations Tetrahedron 63 7696; (b) Godajdar B M and Ansari B 2015 Preparation of novel magnetic dicationic ionic liquid polymeric phase transfer catalyst and their application in nucleophilic substitution reactions of benzyl halides in water J. Mol. Liq. 202 34Google Scholar
  17. 17.
    Collman J P, Zeng L and Braumanb J I 2004 Donor ligand effect on the nature of the oxygenating species in Mn\(^{{\rm III}}\)(salen)-catalyzed epoxidation of olefins: Experimental evidence for multiple active oxidants Inorg. Chem. 43 2672CrossRefGoogle Scholar
  18. 18.
    Zhao M and Lu W 2017 Visible light-induced oxidative chlorination of alkyl sp\(^{3}\) C–H bonds with NaCl/Oxone at room temperature Org. Lett. 19 4560CrossRefGoogle Scholar
  19. 19.
    Malapit C A, Ichiishi N and Sanford M S 2017 Pd-catalyzed decarbonylative cross-couplings of aroyl chlorides Org. Lett. 19 4142CrossRefGoogle Scholar
  20. 20.
    (a) Feth M P, Bolm C, Hildebrand J P, Köhler M, Beckmann O, Bauer M, Ramamonjisoa R and Bertagnolli H 2003 Structural investigation of high-valent manganese–salen complexes by UV/Vis, Raman, XANES, and EXAFS spectroscopy Chem. Eur. J. 9 1348Google Scholar
  21. 21.
    Kurahashi T, Kikuchi A, Tosha T, Shiro Y, Kitagawa T and Fujii H 2008 Transient intermediates from Mn(salen) with sterically hindered mesityl groups: Interconversion between \(\text{ Mn }^{{\rm IV}}\)-phenolate and \(\text{ Mn }^{{\rm III}}\)-phenoxyl radicals as an origin for unique reactivity Inorg. Chem. 47 1674CrossRefGoogle Scholar
  22. 22.
    Adam W, Mock-Knoblauch C, Saha-Möller C R and Herderich M 2000 Are \(\text{ Mn }^{{\rm IV}}\) species involved in Mn(Salen)-catalyzed Jacobsen–Katsuki epoxidations? A mechanistic elucidation of their formation and reaction modes by EPR spectroscopy, mass-spectral analysis, and product studies: Chlorination versus oxygen transfer J. Am. Chem. Soc. 122 9685CrossRefGoogle Scholar
  23. 23.
    Leto D F, Massie A A, Colmer H E and Jackson T A 2016 X-Band electron paramagnetic resonance comparison of mononuclear MnIV-oxo and MnIV-hydroxo complexes and quantum chemical investigation of MnIV zero-field splitting Inorg. Chem. 55 3272CrossRefGoogle Scholar
  24. 24.
    (a) Volz H and Müller W 1997 Isolation and characterization of a porphinatomanganese(IV) complex from the reaction of dichloro monoxide with 5,10,15,20-Tetrakis-(2,6-dichloropheny)porphinatomanganese(III) chloride [Mn(EDCPP)CI] Chem. Ber./Recueil 130 1099; (b) Chen F C, Cheng S H, Yu C H, Liu M H and Su O 1999 Electrochemical characterization and electrocatalysis of high valent manganese meso-tetrakis(N-methyl-2-pyridyl)porphyrin J. Electroanal. Chem. 474 52Google Scholar

Copyright information

© Indian Academy of Sciences 2018

Authors and Affiliations

  1. 1.Department of ChemistryIndian Institute of Technology BombayPowai, MumbaiIndia

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