Ruthenium-Catalyzed Isomerizations of Allylic and Propargylic Alcohols in Aqueous and Organic Media: Applications in Synthesis

Victorio Cadierno; Pascale Crochet; José Gimeno

doi:10.1055/s-2008-1072593

ACCOUNT

Ruthenium-Catalyzed Isomerizations of Allylic and Propargylic Alcohols in Aqueous and Organic Media: Applications in Synthesis

Victorio Cadierno, Pascale Crochet, José Gimeno*
Departamento de Química Orgánica e Inorgánica, Instituto Universitario de Química Organometálica ‘Enrique Moles’ (Unidad Asociada al CSIC), Facultad de Química, Universidad de Oviedo, Julián Claveria 8, 33006 Oviedo, Spain
Fax: +34(985)103446; e-Mail: jgh@uniovi.es;

Abstract

Alle Artikel dieser Rubrik

Abstract

Recent research work on ruthenium-catalyzed isomerizations of allylic and propargylic alcohols into carbonyl compounds is reviewed. Tandem processes based on these isomerization reactions are also included.

1 Introduction

2 Isomerizations of Allylic Alcohols

2.1 Redox Isomerization

2.2 The 1,3-Rearrangement

2.3 Tandem Processes

3 Isomerizations of Propargylic Alcohols

3.1 Meyer-Schuster and Rupe Rearrangements

3.2 Redox Isomerization

3.3 Tandem Processes

4 Conclusions and Outlook

Key words

ruthenium - isomerizations - alcohols - homogeneous catalysis - tandem reactions

Volltext

Referenzen

References

1a Trost BM. Science 1991, 254: 1471

1b Trost BM. Angew. Chem. Int. Ed. Engl. 1995, 34: 259

1c Trost BM. Acc. Chem. Res. 2002, 35: 695

1d Trost BM. Fredericksen MU. Rudd MT. Angew. Chem. Int. Ed. 2005, 44: 6630

2a Li C.-J. Chem. Rev. 1993, 93: 2023

2b Lubineau A. Auge J. Queneau Y. Synthesis 1994, 741

2c Li C.-J. Chan TH. Organic Reactions in Aqueous Media John Wiley & Sons; New York: 1997.

2d Lindström UM. Chem. Rev. 2002, 102: 2751

2e Li C.-J. Chem. Rev. 2005, 105: 3095

2f Andrade CKZ. Alves LM. Curr. Org. Chem. 2005, 9: 195

2g Li C.-J. Chen L. Chem. Soc. Rev. 2006, 35: 68

2h Herrerías CI. Yao X. Li Z. Li CJ. Chem. Rev. 2007, 107: 2546

2i Organic Reactions in Water Lindström UM. Blackwell; Oxford: 2007.

2j Li C.-J. Chan TH. Comprehensive Organic Reactions in Aqueous Media Wiley-VCH; Weinheim: 2007.

3a Bruneau C. Dixneuf PH. Chem. Commun. 1997, 507

3b Naota T. Takaya H. Murahashi S.-I. Chem. Rev. 1998, 98: 2599

3c Trost BM. Toste FD. Pinkerton AB. Chem. Rev. 2001, 101: 2067

3d Trnka TM. Grubbs RH. Acc. Chem. Res. 2001, 34: 18

3e Ritleng V. Sirlin C. Pfeffer M. Chem. Rev. 2002, 102: 1731

3f Ruthenium in Organic Synthesis Murahashi S.-I. Wiley-VCH; Weinheim: 2004.

3g Ruthenium Catalysts and Fine Chemistry Bruneau C. Dixneuf PH. Springer; Berlin: 2004.

For a thematic issue devoted to this topic, see:

3h Curr. Org. Chem. 2006, 10: 113-225

3i Bruneau C. Dixneuf PH. Angew. Chem. Int. Ed. 2006, 45: 2176

4a Wang ML. Li C.-J. Top. Organomet. Chem. 2004, 11: 321

4b Cadierno V. Crochet P. In Advances in Organometallic Chemistry Research Yamamoto K. Nova Science; New York: 2007. p.37-65

5a Anastas PT. Warner JC. Green Chemistry: Theory and Practice Oxford University Press; Oxford: 1998.

5b Anastas PT. Williamson TC. Green Chemistry: Frontiers in Benign Chemical Synthesis and Processes Oxford University Press; New York: 1998.

5c Matlack AS. Introduction to Green Chemistry Marcel Dekker; New York: 2001.

5d Lancaster M. In Handbook of Green Chemistry and Technology Clark JH. Macquarrie DJ. Blackwell; Oxford: 2002.

5e Lancaster M. Green Chemistry: An Introductory Text Royal Society of Chemistry; Cambridge: 2002. 10-27

5f Anastas PT. Kirchhoff MM. Acc. Chem. Res. 2002, 35: 686

5g Sheldon RA. Arends I. Hanefeld U. Green Chemistry and Catalysis Wiley-VCH; Weinheim: 2007.

For reviews on the catalytic isomerization of allylic alcohols, see:

6a van der Drift RC. Bouwman E. Drent E. J. Organomet. Chem. 2002, 650: 1

6b Uma R. Crévisy C. Grée R. Chem. Rev. 2003, 103: 27

Prior to our work, the hexaaquaruthenium(II) complex [Ru(H₂O)₆][OTs]₂ (OTs = p-toluenesulfonate) had proven to be an active catalyst for the isomerization of allylic alcohols and ethers in pure aqueous solution, see:

7a McGrath DV. Grubbs RH. Ziller JW. J. Am. Chem. Soc. 1991, 113: 3611

7b Karlen T. Ludi A. Helv. Chim. Acta 1992, 75: 1604

7c McGrath DV. Grubbs RH. Organometallics 1994, 13: 224

In addition, the catalytic systems mer-[RuCl₃(DMSO)(phen)] (DMSO = dimethyl sulfoxide, phen = 1,10-phenanthroline), cis,cis-[RuCl₂(DMSO)₂(phen)], and [Ru(acac)₃]/phen/PTSA (acac = acetylacetonate, PTSA = p-toluenesulfonic acid) had also been used for the isomerization of allylic alcohols in monophasic water/organic solvent mixtures, see:

7d van der Drift RC. Sprengers JW. Bouwman E. Mul WP. Kooijman H. Spek AL. Drent E. Eur. J. Inorg. Chem. 2002, 2147

7e Stunnenberg F. Niele FGH. Drent E. Inorg. Chim. Acta 1994, 222: 225

8a Cadierno V. Díez J. Gamasa MP. Gimeno J. Lastra E. Coord. Chem. Rev. 1999, 193-195: 147

8b Cadierno V. Gamasa MP. Gimeno J. Eur. J. Inorg. Chem. 2001, 571

8c Cadierno V. Gamasa MP. Gimeno J. Coord. Chem. Rev. 2004, 248: 1627

For examples, see:

9a Kalck P. Monteil F. Adv. Organomet. Chem. 1992, 34: 219

9b Herrmann WA. Kohlpaintner CW. Angew. Chem. Int. Ed. Engl. 1993, 32: 1524

9c Aqueous Organometallic Chemistry and Catalysis Horváth IT. Joó F. Kluwer; Dodrecht: 1995.

9d Aqueous-Phase Organometallic Catalysis: Concepts and Applications Cornils B. Herrmann WA. Wiley-VCH; Weinheim: 1998.

9e Hanson BE. Coord. Chem. Rev. 1999, 185-186: 795

9f Aqueous Organometallic Catalysis Horváth IT. Joó F. Kluwer; Dodrecht: 2001.

9g Pinault N. Bruce DW. Coord. Chem. Rev. 2003, 241: 1

Thematic issues of journals have been devoted to the catalytic applications of water-soluble organometallic compounds, see:

10a J. Mol. Catal. A: Chem. 1997, 116: 1-316

10b Catalysis Today 1998, 42: 371-478

10c Adv. Synth. Catal. 2002, 344: 219-451

11 A short account covering the synthesis and catalytic applications in water of platinum metals containing this ligand is available, see: Pringle PG. Smith MB. Platinum Met. Rev. 1990, 34: 74

12 Cadierno V. Crochet P. García-Garrido SE. Gimeno J. Dalton Trans. 2004, 3635

13 Cadierno V. Crochet P. García-Garrido SE. Gimeno J. Curr. Org. Chem. 2006, 10: 165

14 Cadierno V. García-Garrido SE. Gimeno J. Chem. Commun. 2004, 232

15 Bäckvall J.-E. Andreasson U. Tetrahedron Lett. 1993, 34: 5459

16 Uma R. Davies MK. Crévisy C. Grée R. Eur. J. Org. Chem. 2001, 3141

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

18a Trost BM. Kulawiec RJ. Tetrahedron Lett. 1991, 32: 3039

18b van der Drift RC. Vailati M. Bouwman E. Drent E. J. Mol. Catal. A: Chem. 2000, 159: 163

19 Cadierno V. García-Garrido SE. Gimeno J. Varela-Álvarez A. Sordo JA. J. Am. Chem. Soc. 2006, 128: 1360

TON values up to 3000 (TOF up to 36000 h^-1) have been reported for the isomerization of prop-2-en-1-ol into propionaldehyde using the complexes [RuCp(PR₃)(NCMe)₂][PF₆] (PR₃ = PPh₃, PCy₃) as catalysts, see:

20a Slugovc C. Rüba E. Schmid R. Kirchner K. Organometallics 1999, 18: 4230

TON values up to 6000 have also been reported for the isomerization of but-3-en-2-ol into butan-2-one using complex 7 as the catalyst and AgOTs as a co-catalyst (a TOF value >200000 h^-1 has been claimed):

20b

See ref. 18b TON values up to 17200 (TOF up to 18400 h^-1) have been reported for the isomerization of oct-1-en-3-ol into octan-3-one using the heterogeneous catalytic system Ru(OH)_x/Al₂O₃, see:

20c Yamaguchi K. Koike T. Kotani M. Matsushita M. Shinachi S. Mizuno N. Chem. Eur. J. 2005, 11: 6574

21 Crochet P. Díez J. Fernández-Zúmel MA. Gimeno J. Adv. Synth. Catal. 2006, 348: 93

22 For example, see: de Bellefon C. Caravieilhes S. Kuntz EG. C. R. Acad. Sci., Ser. IIc: Chim. 2000, 3: 607

23 Phillips AD. Gonsalvi L. Romerosa A. Vizza F. Peruzzini M. Coord. Chem. Rev. 2004, 248: 955

24 Díaz-Álvarez AE. Crochet P. Zablocka M. Duhayon C. Cadierno V. Gimeno J. Majoral JP. Adv. Synth. Catal. 2006, 348: 1671

25a Csabai P. Joó F. Organometallics 2004, 23: 5640

25b Fekete M. Joó F. Catal. Commun. 2006, 7: 783

25c Campos-Malpartida T. Fekete M. Joó F. Kathó . Romerosa A. Saoud M. Wojtków W. J. Organomet. Chem. 2008, 693: 468

26 Crochet P. Fernández-Zúmel MA. Gimeno J. Scheele M. Organometallics 2006, 25: 4846

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

28 Martín-Matute B. Bogár K. Edin M. Kaynak FB. Bäckvall J.-E. Chem. Eur. J. 2005, 11: 5832

29 Cherkaoui H. Soufiaoui M. Grée R. Tetrahedron 2001, 57: 2383

Some other catalytic systems are also able to isomerize trisubstituted allylic alcohols, although they require higher temperatures (70-120 °C) and/or longer reaction times:

30a