An Effective Synthesis of Acid-Sensitive
Epoxides via Oxidation of Terpenes and Styrenes Using Hydrogen Peroxide
under Organic Solvent-Free Conditions

Yoshihiro Kon; Houjin Hachiya; Yutaka Ono; Tomohiro Matsumoto; Kazuhiko Sato

doi:10.1055/s-0030-1258467

PAPER

An Effective Synthesis of Acid-Sensitive Epoxides via Oxidation of Terpenes and Styrenes Using Hydrogen Peroxide under Organic Solvent-Free Conditions

Yoshihiro Kon, Houjin Hachiya, Yutaka Ono, Tomohiro Matsumoto, Kazuhiko Sato*
National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba Central 5 Higashi 1-1-1, Tsukuba, Ibaraki 305-8565, Japan
Fax: +81(29)8614578; e-Mail: k.sato@aist.go.jp;

Abstract

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Abstract

An efficient epoxidation process for various terpenes and styrenes using a hydrogen peroxide-tungsten catalytic system with organic solvent- and halide-free conditions was developed. In the presence of the catalytic system, Na₂WO₄, PhP(O)(OH)₂, and [Me(n-C₈H₁₇)₃N]HSO₄, and under weak acidic conditions, hydrogen peroxide successfully epoxidized α-pinene to α-pinene oxide in 95% selectivity at 91% conversion, while the previously published conditions utilizing NH₂CH₂P(O)(OH)₂ as a promoter provided no epoxide.

Key words

oxidation - catalysis - epoxides - terpenoids - styrenes

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References

1a Ullmann’s Encyclopedia of Industrial Chemistry 5th ed., Vol. A9: Gerhartz W. Yamamoto YS. Kaudy L. Rounsaville JF. Schulz G. Wiley-VCH; Weinheim: 1987. p.531

1b Kirk-Othmer Encyclopedia of Chemical Technology 4th ed., Vol. 9: Kroschwitz JI. Howe-Grant M. Wiley; New York: 1994. p.377

1c Kirk-Othmer Encyclopedia of Chemical Technology 4th ed., Vol. 9: Kroschwitz JI. Howe-Grant M. Wiley; New York: 1994. p.730

2 Larock RC. In Comprehensive Organic Transformations 2nd ed.: Wiley; New York: 1999. p.915

3a Strukul G. In Catalytic Oxidations with Hydrogen Peroxide as Oxidant Kluwer Academic Publishers; Dordrecht: 1992.

3b Jones CW. In Applications of Hydrogen Peroxide and Derivatives Royal Society of Chemistry; Cambridge: 1999.

4a Trost BM. Science 1991, 254: 1471

4b Sheldon RA. Chem. Ind. 1992, 903

For recent reviews, see:

5a Applied Homogeneous Catalysis with Organometallic Compounds 2nd ed.: Cornils B. Herrmann WA. Wiley-VCH; Weinheim: 2002.

5b Lane BS. Burgess K. Chem. Rev. 2003, 103: 2457

5c Grigoropoulou G. Clark JH. Elings JA. Green. Chem. 2003, 5: 1

5d Modern Oxidation Methods Bäckvall J.-E. Wiley-VCH; Weinheim: 2004.

5e Mizuno N. Yamaguchi K. Kamata K. Coord. Chem. Rev. 2005, 249: 1944

6a Payne GB. Williams PH. J. Org. Chem. 1959, 24: 54

6b Venturello C. Alneri E. Ricci M. J. Org. Chem. 1983, 48: 3831

6c Ishii Y. Yamawaki K. Ura T. Yamada H. Yoshida T. Ogawa M. J. Org. Chem. 1988, 53: 3587

7a Sato K. Aoki M. Ogawa M. Hashimoto T. Noyori R. J. Org. Chem. 1996, 61: 8310

7b Sato K. Aoki M. Ogawa M. Hashimoto T. Panyella D. Noyori R. Bull. Chem. Soc. Jpn. 1997, 70: 905

7c Noyori R. Aoki M. Sato K. Chem. Commun. 2003, 1977

For recent examples of heterogeneous catalysts, see:

8a van der Waal JC. Rigutto MS. van Bekkum H. Appl. Catal., A 1998, 167: 331

8b Skrobot FC. Valente AA. Neves G. Rosa I. Rocha J. Cavaleiro JAS. J. Mol. Catal. A: Chem. 2003, 201: 211

8c de S. E. Silva JM. Vinhado FS. Mandelli D. Schuchardt U. Rinaldi R. J. Mol. Catal. A: Chem. 2006, 252: 186

8d Eimer GA. Díaz I. Sastre E. Casuscelli SG. Crivello ME. Herrero ER. Perez-Pariente J. Appl. Catal., A 2008, 343: 77

8e Feliczak-Guzik A. Nowak I. Catal. Today 2009, 142: 288

8f Levecque P. Poelman H. Jacobs P. De Vos D. Sels B. Phys. Chem. Chem. Phys. 2009, 11: 2964

8g Bonon AJ. Mandelli D. Kholdeeva OA. Barmatova MV. Kozlov YN. Shul’pin GB. Appl. Catal., A 2009, 365: 96

8h Qi B. Lu X.-H. Zhou D. Xia Q.-H. Tang Z.-R. Fang S.-Y. Pang T. Dong Y.-L. J. Mol. Catal. A: Chem. 2010, 322: 73

For recent examples of polyoxometalate complexes, see:

9a Villa de P AL. Sels BF. De Vos DE. Jacobs PA. J. Org. Chem. 1999, 64: 7267

9b Kamata K. Kotani M. Yamaguchi K. Hikichi S. Mizuno N. Chem. Eur. J. 2007, 13: 639

9c Maksimchuk NV. Kovalenko KA. Arzumanov SS. Chesalov YA. Melgunov MS. Stepanov AG. Fedin VP. Kholdeeva OA. Inorg. Chem. 2010, 49: 2920

For recent examples of homogeneous catalysts, see:

10a Sakaguchi S. Nishiyama Y. Ishii Y. J. Org. Chem. 1996, 61: 5307

10b Battioni P. Renaud JP. Bartoli JF. Reina-Artiles M. Fort M. Mansuy D. J. Am. Chem. Soc. 1988, 110: 8462

10c Lane BS. Vogt M. DeRose VJ. Burgess K. J. Am. Chem. Soc. 2002, 124: 11946

10d Woitiski CB. Kozlov YN. Mandelli D. Nizova GV. Schuchardt U. Shul’pin GB. J. Mol. Catal. A: Chem. 2004, 222: 103

10e Grigoropoulou G. Clark JH. Tetrahedron Lett. 2006, 47: 4461

10f Mandelli D. Steffen RA. Shul’pin GB. React. Kinet. Catal. Lett. 2006, 88: 165

11a Rüschgen KM. Warwel S. Org. Lett. 1999, 1: 1025

11b Salles L. Brégeault J.-M. Thouvenot R. Surf. Chem. Catal. 2000, 3: 183

For recent examples, see:

12a Quenard M. Bonmarin V. Gelbard G. Tetrahedron Lett. 1987, 28: 2237

12b Al-Ajlouni AM. Espenson JH. J. Am. Chem. Soc. 1995, 117: 9243

12c Rudolph J. Reddy KL. Chiang JP. Sharpless KB. J. Am. Chem. Soc. 1997, 119: 6189

12d Zuwei X. Ning Z. Yu S. Kunlan L. Science 2001, 292: 1139

12e Grigoropoulou G. Clark JH. Elings JA. Green Chem. 2003, 5: 1

12f Yang X. Gao S. Xi Z. Org. Process Res. Dev. 2005, 9: 294

12g Tse MK. Klawonn M. Bhor S. Döbler C. Anilkumar G. Hugl H. Mägerlein W. Beller M. Org. Lett. 2005, 7: 987

12h Yeung H.-L. Sham K.-C. Tsang C.-S. Lau T.-C. Kwong H.-L. Chem. Commun. 2008, 3801

12i Matsumoto K. Oguma T. Katsuki T. Angew. Chem. Int. Ed. 2009, 48: 7432

13a Sienel G. Rieth R. In Ullmann’s Encyclopedia of Industrial Chemistry 6th ed., Vol. 12: Wiley-VCH; Weinheim: 2003. p.279

13b Eggersdorfer M. In Ullmann’s Encyclopedia of Industrial Chemistry 6th ed., Vol. 35: Wiley-VCH; Weinheim: 2003. p.653

13c Swift KAD. Top. Catal. 2004, 27: 143

13d Corma A. Iborra S. Velty A. Chem. Rev. 2007, 107: 2411

13e Bicas JL. Dionísio AP. Pastore GM. Chem. Rev. 2009, 109: 4518

14a Rudakov GA. Ivanova LS. Pisareva TN. Borovskaya AG. Gidroliz. Lesokhim. Prom-st 1975, 4: 7 ; Chem. Abstr. 1975, 83, 193517u

14b Kaminska J. Schwegler MA. Hoefnagel AJ. Van Bekkum H. Recl. Trav. Chim. Pays-Bas 1992, 111: 432

14c Carr G. Dosanjh G. Millar AP. Whittaker D. J. Chem. Soc., Perkin Trans. 2 1994, 1419

15a Villa de P AL. De Vos DE. Montes de C C. Jacobs PA. Tetrahedron Lett. 1998, 39: 8521

15b Sakamoto T. Pac C. Tetrahedron Lett. 2000, 41: 10009

15c Saladino R. Neri V. Pelliccia AR. Mincione E. Tetrahedron 2003, 59: 7403

15d Saladino R. Andreoni A. Neri V. Crestini C. Tetrahedron 2005, 61: 1069

16 Recently, an effective method for syntheses of terpene oxides with MTO catalyzed H₂O₂ oxidation with pyrazole and imidazole additive under organic solvent-free conditions was reported: Yamazaki S. Org. Biomol. Chem. 2010, 8: 2377

17a Hibbert H. Burt CP. J. Am. Chem. Soc. 1925, 47: 2240

17b Böeseken J. Blumberger JSP. Recl. Trav. Chim. Pays-Bas 1925, 44: 90

18 Kon Y. Ono Y. Matsumoto T. Sato K. Synlett 2009, 1095

19a Duncan DC. Chambers RC. Hecht E. Hill CL.
J. Am. Chem. Soc. 1995, 117: 681

19b Gelbard G. Raison F. Roditi-Lachter E. Thouvenot R. Ouahab L. Grandjean D. J. Mol. Catal. A: Chem. 1996, 114: 77

20 Kolehmainen E. Laihia K. Heinänen M. Rissanen K. Fröhlich R. Korvola J. Mänttäri P. Kauppinen R. J. Chem. Soc., Perkin Trans. 2 1993, 641

21 Kopperman HL. Hallcher RC. Riehl SrA. Carlson RM. Caple R. Tetrahedron 1976, 32: 1621

22 Pigulevskii GV. Adrova NA. Zh. Obshch. Khim. 1957, 27: 136 ; Chem. Abstr. 1957, 51, 12874i

23 Pouchert CJ. Behnke J. The Aldrich Library of ^¹³C and ^¹ H FT NMR Spectra 1st ed., Vol. 1: Aldrich Chemical Co.; Milwaukee: 1993. p.377C

24a Baig MA. Banthorpe DV. Carr G. Whittaker D.
J. Chem. Soc., Perkin Trans. 2 1989, 1981

24b Robinson PL. Barry CN. Kelly JW. Evans SA. J. Am. Chem. Soc. 1985, 107: 5210

25 Rodriguez J. Dulcere J.-P. J. Org. Chem. 1991, 56: 469

26a Morizawa Y. Kanakura A. Yamamoto H. Hiyama T. Nozaki H. Bull. Chem. Soc. Jpn. 1984, 57: 1935

26b Steinreiber A. Mayer SF. Faber K. Synthesis 2001, 2035

27 Pouchert CJ. Behnke J. The Aldrich Library of ^¹³ C and ^¹ H FT NMR Spectra 1st ed., Vol. 1: Aldrich Chemical Co.; Milwaukee: 1993. p.379A

28 Pouchert CJ. Behnke J. The Aldrich Library of ^¹³ C and ^¹ H FT NMR Spectra 1st ed., Vol. 1: Aldrich Chemical Co.; Milwaukee: 1993. p.380A

29 Feng JP. Shi ZF. Li Y. Zhang JT. Qi XL. Chen J. Cao XP. J. Org. Chem. 2008, 73: 6873

30 Garcia-Bosch I. Ribas X. Costas M. Adv. Synth. Catal. 2009, 351: 348

31 Piccinini A. Kavanagh SA. Connon PB. Connon SJ. Org. Lett. 2010, 12: 608

32 Pedragosa-Moreau S. Morisseau C. Zylber J. Archelas A. Baratti J. Furstoss R. J. Org. Chem. 1996, 61: 7402

33 Robinson MWC. Davies AM. Buckle R. Mabbett I. Taylor SH. Graham AE. Org. Biomol. Chem. 2009, 7: 2559

34 Kang B. Kim M. Lee J. Do Y. Chang S. J. Org. Chem. 2006, 71: 6721