Green Functional Group Transformations
by Supported Ruthenium Hydroxide Catalysts

Kazuya Yamaguchi; Noritaka Mizuno

doi:10.1055/s-0030-1258565

ACCOUNT

Green Functional Group Transformations by Supported Ruthenium Hydroxide Catalysts

Kazuya Yamaguchi, Noritaka Mizuno*
Department of Applied Chemistry, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan
Fax: +81(3)58417220; e-Mail: tmizuno@mail.ecc.u-tokyo.ac.jp;

Abstract

Alle Artikel dieser Rubrik

Abstract

This account summarizes our recent research on green functional group transformations using easily prepared supported ruthenium hydroxide catalysts [Ru(OH)_x/support, support = Al₂O₃, TiO₂, or Fe₃O₄]. Various kinds of functional group transformations, e.g. the oxidation (oxidative dehydrogenation) of alcohols and amines, hydrogen-transfer reactions, such as racemization and reduction, and the hydration of nitriles, can be promoted by the concerted activation of the substrates (including alcohols, amines, and nitriles) by the Lewis acid and Brønsted base sites on the Ru(OH)_x/support catalyst. In addition, we have successfully developed three novel catalytic transformations with the Ru(OH)_x/support catalysts: (1) the oxygenation of primary amines to give amides, (2) the direct oxidative synthesis of nitriles from primary alcohols and ammonia, and (3) the N-alkylation of ammonia (or its surrogates) with alcohols to produce symmetrically substituted tertiary or secondary amines. The catalyses for these transformations are truly heterogeneous, and the catalysts retrieved after the transformations can be reused with retention of their high catalytic performance.

1 Introduction

2 Preparation and Characterization of Supported Ruthenium Hydroxide Catalysts

3 Oxidation of Alcohols and Amines

4 Hydration of Nitriles

5 Oxygenation of Primary Amines To Give Amides

6 Direct Oxidative Synthesis of Nitriles from Primary Alcohols and Ammonia

7 N-Alkylation of Ammonia with Alcohols To Give Tertiary or Secondary Amines

8 Conclusion

Key words

concerted activation - Lewis acids - Brønsted bases - heterogeneous catalysis - ruthenium hydroxide

Volltext

Referenzen

References

1a Whyman R. Applied Organometallic Chemistry and Catalysis Oxford University Press; London: 2001.

1b Bornils B. Herrmann WA. Applied Homogeneous Catalysis with Organometallic Compounds 2nd ed., Vol. 1: Wiley-VCH; Weinheim: 2002.

2 Hagen J. Industrial Catalysis: A Practical Approach Wiley-VCH; Weinheim: 1999.

3a Sheldon RA. van Bekkum H. Fine Chemicals through Heterogeneous Catalysis Wiley-VCH; Weinheim: 2001.

3b Mizuno N. Modern Heterogeneous Oxidation Catalysis Wiley-VCH; Weinheim: 2009.

4a Anastas PT. Warner JC. Green Chemistry: Theory and Practice Oxford University Press; London: 1998.

4b Sheldon RA. Green Chem. 2000, 2: G1

4c Anastas PT. Bartlett LB. Kirchhoff MM. Williamson TC. Catal. Today 2000, 55: 11

5a Leadbeater NE. Marco M. Chem. Rev. 2002, 102: 3217

5b Lu Z. Linder E. Mayer HA. Chem. Rev. 2002, 102: 3543

5c Wight AP. Davis ME. Chem. Rev. 2002, 102: 3589

5d De Vos DE. Dams M. Sels BF. Jacobs PA. Chem. Rev. 2002, 102: 3615

5e Corma A. García H. Chem. Rev. 2002, 102: 3837

6a Yamaguchi K. Mizuno N. New J. Chem. 2002, 26: 974

6b Kamata K. Yonehara K. Sumida Y. Yamaguchi K. Hikichi S. Mizuno N. Science 2003, 300: 964

6c Nakagawa Y. Kamata K. Kotani M. Yamaguchi K. Mizuno N. Angew. Chem. Int. Ed. 2005, 44: 5136

6d Kamata K. Yamaguchi S. Kotani M. Yamaguchi K. Mizuno N. Angew. Chem. Int. Ed. 2008, 47: 2407

6e Kamata K. Nakagawa Y. Yamaguchi K. Mizuno N. J. Am. Chem. Soc. 2008, 130: 15304

6f Kikukawa Y. Yamaguchi S. Nakagawa Y. Uehara K. Uchida S. Yamaguchi K. Mizuno N. J. Am. Chem. Soc. 2008, 130: 15872

6g Ishimoto R. Kamata K. Mizuno N. Angew. Chem. Int. Ed. 2009, 48: 8900

6h Kamata K. Hirano T. Kuzuya S. Mizuno N. J. Am. Chem. Soc. 2009, 131: 6997

7a Yamaguchi K. Mizuno N. Angew. Chem. Int. Ed. 2002, 41: 4538

7b Yamaguchi K. Mizuno N. Angew. Chem. Int. Ed. 2003, 42: 1479

7c Yamaguchi K. Mizuno N. Chem. Eur. J. 2003, 9: 4353

7d Yamaguchi K. Kim JW. He JL. Mizuno N. J. Catal. 2009, 268: 343

8 Kim JH. Britten J. Chin J. J. Am. Chem. Soc. 1993, 115: 3618

9a Yamaguchi K. Koike T. Kotani M. Matsushita M. Shinachi S. Mizuno N. Chem. Eur. J. 2005, 11: 6574

9b Kim JW. Koike T. Kotani M. Yamaguchi K. Mizuno N. Chem. Eur. J. 2008, 14: 4104

9c Yamaguchi K. Koike T. Kim JW. Ogasawara Y. Mizuno N. Chem. Eur. J. 2008, 14: 11480

10 Yamaguchi K. Matsushita M. Mizuno N. Angew. Chem. Int. Ed. 2004, 43: 1576

11 Kamata K. Kasai J. Yamaguchi K. Mizuno N. Org. Lett. 2004, 6: 3577

12 Matsushita M. Kamata K. Yamaguchi K. Mizuno N. J. Am. Chem. Soc. 2005, 127: 6632

13 Kim JW. Yamaguchi K. Mizuno N. J. Catal. 2009, 263: 205

14 Kim JW. Yamaguchi K. Mizuno N. Angew. Chem. Int. Ed. 2008, 47: 9249

15 Oishi T. Yamaguchi K. Mizuno N. Angew. Chem. Int. Ed. 2009, 48: 6286

16a He JL. Kim JW. Yamaguchi K. Mizuno N. Angew. Chem. Int. Ed. 2009, 48: 9888

16b Yamaguchi K. He JL. Oishi T. Mizuno N. Chem. Eur. J. 2010, 16: 7199

17 Briggs D. Seah MP. Practical Surface Analysis by Auger and X-ray Photoelectron Spectroscopy John Wiley & Sons; Chichester: 1983.

18a Fujiwara H. Ogasawara Y. Yamaguchi K. Mizuno N. Angew. Chem. Int. Ed. 2007, 46: 5202

18b Fujiwara H. Ogasawara Y. Kotani M. Yamaguchi K. Mizuno N. Chem. Asian J. 2008, 3: 1715

19a Katayama T. Kamata K. Yamaguchi K. Mizuno N. ChemSusChem 2009, 2: 59

19b Oishi T. Katayama T. Yamaguchi K. Mizuno N. Chem. Eur. J. 2009, 15: 7539

19c Yamaguchi K. Oishi T. Katayama T. Mizuno N. Chem. Eur. J. 2009, 15: 10464

20a Sheldon RA. Kochi JK. Metal Catalyzed Oxidations of Organic Compounds Academic; New York: 1981.

20b Hill CL. In Advances in Oxygenated Processes Vol. 1: Baumstark AL. JAI; London: 1988. p.1-30

20c Hudlicky M. Oxidations in Organic Chemistry, ACS Monograph Series American Chemical Society; Washington DC: 1990.

20d Arends IWCE. Sheldon RA. In Modern Oxidation Methods Bäckvall J.-E. Wiley-VCH; Weinheim: 2004. p.83-118

20e Murahashi S.-I. Komiya N. In Modern Oxidation Methods Bäckvall J.-E. Wiley-VCH; Weinheim: 2004. p.165-191

21a Mallat T. Baiker A. Chem. Rev. 2004, 104: 3037

21b Matsumoto T. Ueno M. Wang N. Kobayashi S. Chem. Asian J. 2008, 3: 196

22a Matsumoto M. Watanabe N. J. Org. Chem. 1984, 49: 3435

22b Zhan B.-Z. White MA. Sham T.-K. Pincock JA. Doucet RJ. Rao KVR. Robertson KN. Cameron TS. J. Am. Chem. Soc. 2003, 125: 2195

22c Bavykin DV. Lapkin AA. Plucinski PK. Friedrich JM. J. Catal. 2005, 235: 10

22d Yu H. Fu X. Zhou C. Peng F. Wang H. Yang J. Chem. Commun. 2009, 2408

23a Yamaguchi K. Mori K. Mizugaki T. Ebitani K. Kaneda K. J. Am. Chem. Soc. 2000, 122: 7144

23b Kaneda K. Mori K. Hara T. Mizugaki T. Ebitani K. Catal. Surv. Asia 2004, 8: 231

24a Dijksman A. Arends IWCE. Sheldon RA. Chem. Commun. 1999, 1591

24b Dijksman A. Marino-González A. Mairata i Payeras A. Arends IWCE. Sheldon RA. J. Am. Chem. Soc. 2001, 123: 6826

25 Hanyu A. Takezaki E. Sakaguchi S. Ishii Y. Tetrahedron Lett. 1998, 39: 5557

26 Nikaidou F. Ushiyama H. Yamaguchi K. Yamashita K. Mizuno N. J. Phys. Chem. C 2010, 114: 10873

27a Bäckvall J.-E. Chowdhury RL. Karlsson U. J. Chem. Soc., Chem. Commun. 1991, 473

27b Trost BM. Kulawiec RJ. Tetrahedron Lett. 1991, 32: 3039

27c Zassinovich G. Mestroni G. Gladiali S. Chem. Rev. 1992, 92: 1051

27d Trost BM. Kulawiec RJ. J. Am. Chem. Soc. 1993, 115: 2027

27e Slugovc C. Ruba E. Schmid R. Kirchner K. Organometallics 1999, 18: 4230

27f Markó IE. Gautier A. Tsukazaki M. Llobet A. Plantalech-Mir E. Urch CJ. Brown SM. Angew. Chem. Int. Ed. 1999, 38: 1960

27g Aranyos A. Csjernyik G. Szabó KJ. Bäckvall J.-E. Chem. Commun. 1999, 351

27h Martín-Matute B. Bogár K. Edin M. Kaynak FB. Bäckvall J.-E. Chem. Eur. J. 2005, 11: 5833

27i Ito M. Kitahara S. Ikariya T. J. Am. Chem. Soc. 2005, 127: 6172

27j Cadierno V. Francos J. Gimeno J. Nebra N. Chem. Commun. 2007, 2536

28 Kozhevnikov IV. Tarabanko VE. Matveev KI. Kinet. Katal. 1981, 22: 619

29 Sheldon RA. Wallau M. Arends IWCE. Schuchardt U. Acc. Chem. Res. 1998, 31: 485

30a Zhang J. Wang Y. Ji H. Wei Y. Wu N. Zuo B. Wang Q. J. Catal. 2005, 229: 114

30b Stevens PD. Li G. Fan J. Yen M. Gao Y. Chem. Commun. 2005, 4435

30c Lee J. Lee D. Oh E. Kim J. Kim Y.-P. Jin S. Kim H.-S. Hwang Y. Kwak JH. Park J.-G. Shin C.-H. Kim J. Hyeon T. Angew. Chem. Int. Ed. 2005, 44: 7432

30d Yoon T.-J. Kim JS. Kim BG. Yu KN. Cho M.-H. Lee J.-K. Angew. Chem. Int. Ed. 2005, 44: 1068

30e Mori K. Kanai S. Hara T. Mizugaki T. Ebitani K. Jitsukawa K. Kaneda K. Chem. Mater. 2007, 19: 1249

31 Kotani M. Koike T. Yamaguchi K. Mizuno N. Green Chem. 2006, 8: 735

32a Sharpless KB. Akashi K. Oshima K. Tetrahedron Lett. 1976, 17: 2503

32b Kanemoto S. Matsubara S. Takai K. Oshima K. Utimoto K. Nozaki H. Bull. Chem. Soc. Jpn. 1988, 61: 3607

32c Markó IE. Giles PR. Tsukazaki M. Chellé-Regnaut I. Urch CJ. Brown SM. J. Am. Chem. Soc. 1997, 119: 12661

32d Lenz R. Ley SV. J. Chem. Soc., Perkin Trans. 1 1997, 3291

33 Connors KA. Chemical Kinetics: The Study of Reaction Rates in Solution Wiley-VCH; New York: 1990.

34 Pàmies O. Bäckvall J.-E. Chem. Eur. J. 2001, 7: 5052

35a Bakac A. J. Am. Chem. Soc. 1997, 119: 10726

35b Wick DD. Goldberg KI. J. Am. Chem. Soc. 1999, 121: 11900

35c Thyagarajan S. Incarvito CD. Rheingold AL. Theopold KH. Chem. Commun. 2001, 2198

35d Denney MC. Smythe NA. Cetto KL. Kemp RA. Goldberg KI. J. Am. Chem. Soc. 2006, 128: 2508

35e Keith JM. Muller RP. Kemp RA. Goldberg KI. Goddard WA. Oxgaard J. Inorg. Chem. 2006, 45: 9631

35f Look JL. Wick DD. Mayer JM. Goldberg KI. Inorg. Chem. 2009, 48: 1356

36a Larock RC. Comprehensive Organic Transformations 2nd ed.: Wiley-VCH; New York: 1999.

36b Smith MB. Organic Synthesis 2nd ed.: McGraw-Hill; New York: 2002.

37 Smith MB. March J. March’s Advanced Organic Chemistry: Reactions, Mechanisms, and Structure 6th ed.: John Wiley & Sons; Hoboken / NJ: 2007.

38a Opsahl R. In Encyclopedia of Chemical Technology Vol. 2: Kroschwitz JI. John Wiley & Sons; New York: 1991. p.346-356

38b Mascharak PK. Coord. Chem. Rev. 2002, 225: 201

38c Ingvosersen K. Kamphuis J. In Enzyme Catalysis in Organic Synthesis Vol. 1: Drauz K. Waldman H. VCH; Weinheim: 1995. p.365-392

39a Breslow R. Fairweather R. Keana J. J. Am. Chem. Soc. 1967, 89: 2135

39b Breno KL. Pluth MD. Tyler DR. Organometallics 2003, 22: 1203

39c Murahashi S.-I. Sasao S. Saito E. Naota T. J. Org. Chem. 1992, 57: 2521

39d Ghaffar T. Parkins AW. Tetrahedron Lett. 1995, 36: 8657

39e Mori K. Yamaguchi K. Mizugaki T. Ebitani K. Kaneda K. Chem. Commun. 2001, 461

39f Oshiki T. Yamashita H. Sawada K. Utsunomiya M. Takahashi K. Takai K. Organometallics 2005, 24: 6287

39g Mitsudome T. Mikami Y. Mori H. Arita S. Mizugaki T. Jitsukawa K. Kaneda K. Chem. Commun. 2009, 3258

40a Yamada YMA. Takeda K. Takahashi H. Ikegami S. J. Org. Chem. 2003, 68: 7733

40b Polshettiwar V. Varma RS. Chem. Eur. J. 2009, 15: 1582

41 Tanaka K. Yoshifuji S. Nitta Y. Chem. Pharm. Bull. 1988, 36: 3125

42a Miller JS. Manson JL. Acc. Chem. Res. 2001, 34: 563

42b Magnus P. Scott DA. Fielding MR. Tetrahedron Lett. 2001, 42: 4127

43a Iida S. Togo H. Tetrahedron 2007, 63: 8274

43b Mori N. Togo H. Synlett 2005, 1456

43c Iida S. Togo H. Synlett 2007, 407

43d Yamazaki S. Yamazaki Y. Chem. Lett. 1990, 571

43e McAllister GD. Wilfred CD. Taylor RJK. Synlett 2002, 1291

43f Chen F.-E. Li Y.-Y. Jia H.-Q. Synthesis 2002, 1804

44a Brown BR. The Organic Chemistry of Aliphatic Nitrogen Compounds Oxford University Press; New York: 1994.

44b Salvatore RN. Yoon CH. Jung KW. Tetrahedron 2001, 57: 7785

45a Hamid MHSA. Slatford PA. Williams JMJ. Adv. Synth. Catal. 2007, 349: 1555

45b Grigg R. Mitchell TRB. Sutthivaiyakit S. Tongpenyai T. J. Chem. Soc., Chem. Commun. 1981, 611

45c Watanabe Y. Tsuji Y. Ohsugi Y. Tetrahedron Lett. 1981, 22: 2667

46a Valotl F. Fachel F. Jacquot R. Spagnol M. Lemairel M. Tetrahedron Lett. 1999, 40: 3689

46b Nagaraju N. Kuriakose G. New J. Chem. 2003, 27: 765

46c Hollmann D. Tillack A. Jackstell R. Beller M. Chem. Asian J. 2007, 2: 403

46d Fujita K.-I. Enoki Y. Yamaguchi R. Tetrahedron 2008, 64: 1943

46e Blank B. Madalska M. Kempe R. Adv. Synth. Catal. 2008, 350: 749

47 Roundhill DM. Chem. Rev. 1992, 92: 1

48a Surry DS. Buchwald SL. J. Am. Chem. Soc. 2007, 129: 10354

48b Yamaguchi R. Kawagoe S. Asai C. Fujita K.-I. Org. Lett. 2008, 10: 181

48c Ohtani B. Osaki H. Nishimoto S. Kagiya T. Tetrahedron Lett. 1986, 27: 2019

49a Yamaguchi K. Fujiwara H. Ogasawara Y. Kotani M. Mizuno N. Angew. Chem. Int. Ed. 2007, 46: 3922

49b Ogasawara Y. Uchida S. Yamaguchi K. Mizuno N. Chem. Eur. J. 2009, 15: 4343