Titanocene-Catalyzed Reductive Epoxide Opening: The Quest for Novel Hydrogen Atom Donors

Andreas Gansäuer; Andriy Barchuk; Doris Fielenbach

doi:10.1055/s-2004-831207

PAPER

Titanocene-Catalyzed Reductive Epoxide Opening: The Quest for Novel Hydrogen Atom Donors

Andreas Gansäuer*, Andriy Barchuk, Doris Fielenbach
Kekulé-Institut für Organische Chemie und Biochemie, Rheinische Friedrich-Wilhelms-Universität, Gerhard Domagk Str.1, 53121 Bonn, Germany
Fax: +49(228)734760; e-Mail: andreas@gansaeuer.de;

Abstract

All articles of this category

Abstract

Novel hydrogen atom donors for the reductive titanocene-catalyzed epoxide opening are presented. While the potentially attractive cyclopentadienes gave only moderate yields of the desired alcohols, substituted, nontoxic, and commercially available 1,4-cyclohexadienes, e.g. γ-terpinene, in combination with more elaborate catalysts gave better or similar results than the much more expensive and carcinogenic 1,4-cyclohexadiene. In the practically important reactions of Sharpless epoxides and their derivatives excellent levels of regioselectivity for the epoxide opening could be obtained. The toxic and unpleasant to handle tert-butyl thiol could be replaced while increasing the yields of the desired products.

Key words

epoxides - titanium - reductive ring opening - H-atom donors - γ-terpinene

Full Text

References

1a Giese B. Radicals in Organic Synthesis: Formation of Carbon-Carbon Bonds Pergamon Press; Oxford: 1986.

1b Motherwell WB. Crich D. Free Radical Chain Reactions in Organic Synthesis Academic Press; London: 1991.

1c Fossey J. Lefort D. Sorba J. Free Radicals in Organic Synthesis Wiley; New York: 1995.

1d Curran DP. Porter NA. Giese B. Stereochemistry of Radical Reactions VCH; Weinheim: 1996.

1e Linker T. Schmittel M. Radikale und Radikalionen in der Organischen Synthese Wiley-VCH; Weinheim: 1998.

2 For an excellent review on this topic, see: Baguley PA. Walton JC. Angew. Chem. Int. Ed. 1998, 37: 3073 ; Angew. Chem. 1998, 110, 3272

3a Kagan HB. Namy J.-L. Tetrahedron 1986, 42: 6573

3b Kagan HB. New. J. Chem. 1990, 14: 453

3c Soderquist JA. Aldrichimica Acta 1991, 24: 15

3d Molander GA. Chem. Rev. 1992, 92: 29

3e Molander GA. Harris CR. Chem. Rev. 1996, 96: 307

3f Skrydstrup T. Angew. Chem., Int. Ed. Engl. 1997, 36: 345 ; Angew. Chem. 1997, 109, 355

3g Molander GA. Harris CR. Tetrahedron 1998, 54: 3321

3h Krief A. Laval A.-M. Chem. Rev. 1999, 99: 745

4a Hasegawa E. Curran DP. Tetrahedron Lett. 1993, 34: 1717

4b Enemærke RJ. Daasbjerg K. Skrydstrup T. Chem. Commun. 1999, 343

4c Shabangi M. Kuhlman ML. Flowers RA. Org. Lett. 1999, 1: 2133

For recent reviews on the generation of epoxides, see:

5a Rao AS. In Comprehensive Organic Synthesis Vol. 7: Trost BM. Fleming I. Pergamon Press; Oxford: 1991. p.357-387

5b Meunier B. Chem. Rev. 1992, 92: 1411

5c Gansäuer A. Angew. Chem., Int. Ed. Engl. 1997, 36: 2591 ; Angew. Chem.; 1997, 109: 2701

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

6a Nugent WA. RajanBabu TV. J. Am. Chem. Soc. 1988, 110: 8561

6b RajanBabu TV. Nugent WA. J. Am. Chem. Soc. 1989, 111: 4525

6c RajanBabu TV. Nugent WA. Beattie MS. J. Am. Chem. Soc. 1990, 112: 6408

6d RajanBabu TV. Nugent WA. J. Am. Chem. Soc. 1994, 116: 986

For reviews, see:

7a Gansäuer A. Narayan S. Adv. Synth. Catal. 2002, 344: 465

7b Gansäuer A. Lauterbach T. Narayan S. Angew. Chem. Int. Ed. 2003, 42: 5556 ; Angew. Chem. 2003, 115, 5714

8a Fernández-Mateos A. Martin de la Nava E. Pascual Coca G. Ramos Silvo A. Rubio González R. Org. Lett. 1999, 1: 607

8b Ruano G. Grande M. Anaya J. J. Org. Chem. 2002, 67: 8243

8c Ruano G. Martiáñez J. Grande M. Anaya J. J. Org. Chem. 2003, 68: 2024

8d Anaya J. Fernández-Mateos A. Grande M. Martiáñez J. Ruano G. Rubio-González R. Tetrahedron 2003, 59: 241

8e Fernández-Mateos A. Burón LM. Clemente RR. Silvo AIR. González RR. Synlett 2004, 1011

9a Newcomb M. Curran DP. Acc. Chem. Res. 1988, 21: 206

9b Hawari JA. Engel PS. Griller D. Int. J. Chem. Kin. 1985, 15: 1215

9c Newcomb M. Park SU. J. Am. Chem. Soc. 1986, 108: 4132

10a Gansäuer A. Pierobon M. Bluhm H. Angew. Chem. Int. Ed. 1998, 37: 101 ; Angew. Chem. 1998, 110, 107

10b Gansäuer A. Bluhm H. Chem. Commun. 1998, 2143

10c Gansäuer A. Bluhm H. Pierobon M. J. Am. Chem. Soc. 1998, 120: 12849

10d Gansäuer A. Pierobon M. Synlett 2000, 1357

10e Gansäuer A. Pierobon M. Bluhm H. Synthesis 2001, 2500

10f Gansäuer A. Pierobon M. Bluhm H. Angew. Chem. Int. Ed. 2002, 41: 3206 ; Angew. Chem. 2002, 114, 3341

For examples of these reactions in radical chemistry, see the following reviews:

11a Renaud P. Gerster M. Angew. Chem. Int. Ed. 1998, 37: 2562 ; Angew. Chem. 1998, 110, 2704

11b Roberts BP. Chem. Soc. Rev. 1999, 28: 35

11c Sibi MP. Porter NA. Acc. Chem. Res. 1999, 32: 163

11d Gansäuer A. Bluhm H. Chem. Rev. 2000, 100: 2771

11e Sibi MP. Manyem S. Zimmermann J. Chem. Rev. 2003, 103: 3263

12a Gansäuer A. Lauterbach T. Bluhm H. Noltemeyer M. Angew. Chem. Int. Ed. 1999, 111: 2909 ; Angew. Chem. 1999, 111, 3112

12b Gansäuer A. Bluhm H. Lauterbach T. Adv. Synth. Catal. 2001, 343: 785

12c Gansäuer A. Bluhm H. Rinker B. Narayan S. Schick M. Lauterbach T. Pierobon M. Chem. Eur. J. 2003, 9: 531

12d Gansäuer A. Rinker B. Pierobon M. Grimme S. Gerenkamp M. Mück-Lichtenfeld C. Angew. Chem. Int. Ed. 2003, 42: 3687 ; Angew. Chem. 2003, 115, 3815

12e Gansäuer A. Rinker B. Ndene-Schiffer N. Pierobon M. Grimme S. Gerenkamp M. Mück-Lichtenfeld C. Eur. J. Org. Chem. 2004, 2337

13a Barrero AF. Cuerva JM. Herrador MM. Valdiva MV. J. Org. Chem. 2001, 66: 4074

13b Justicia J. Rosales A. Buñuel E. Oller-López JL. Valdivia M. Hadour A. Oltra JE. Barrero AF. Cárdenas DJ. Cuerva JM. Chem. Eur. J. 2004, 10: 1778

14a Bordwell FG. Cheng JP. Harrelson JA. J. Am. Chem. Soc. 1988, 110: 1229

14b Brocks JJ. Beckhaus H.-D. Beckwith ALJ. Rüchardt C. J. Org. Chem. 1998, 63: 1935

15 Gansäuer A. Rinker B. Barchuk A. Nieger M. Organometallics 2004, 23: 1168

16 Huang Q. Qian Y. Tang Y. Chen S. J. Organomet. Chem. 1988, 340: 179

17 Samuel E. J. Organomet. Chem. 1969, 19: 87

18 Howie RA. McQuillan GP. Thomson DW. Lock GA. J. Organomet. Chem. 1986, 303: 213

19a Wild FRWP. Zsolnai L. Huttner G. Brintzinger HH. J. Organomet. Chem. 1982, 232: 233

19b Collins S. Kuntz BA. Taylor NJ. Ward DG. J. Organomet. Chem. 1988, 342: 21

20a Cesarotti E. Kagan HB. Goddard R. Krüger C. J. Organomet. Chem. 1978, 162: 297

20b Gansäuer A. Bluhm H. Pierobon M. Keller M. Organometallics 2001, 20: 914

For recent reviews on the synthesis of these intermediates, see:

21a Katsuki T. In Comprehensive Asymmetric Catalysis Vol. 2: Jacobsen EN. Pfaltz A. Yamamoto H. Springer; Berlin: 1999. p.621-648

21b Johnson RA. Sharpless KB. In Catalytic Asymmetric Synthesis 2nd ed.: Ojima I. Wiley-VCH; Weinheim: 2000. p.231-286

22 For examples, see: Finan JM. Kishi Y. Tetrahedron Lett. 1982, 23: 2719

23 Still WC. Kahn A. Mitra A. J. Org. Chem. 1978, 43: 2923

24 Charlton JL. Williams GJ. Lypka GN. Can. J. Chem. 1980, 58: 1271

25 DeLuca MR. Magnus P. J. Chem. Soc., Perkin Trans. 1 1991, 2661

26 Clark TJ. Killian CM. Luthra S. Nile TA. J. Organomet. Chem. 1993, 462: 247

27 Söderberg BC. Åkerman B. Hall SS. J. Org. Chem. 1988, 53: 2925

28 Corey EJ. Chaykovsky M. J. Am. Chem. Soc. 1965, 87: 1353

29 Thijs L. Waanders PP. Stokkingreef EHM. Zwanenburg B. Recl. Trav. Chim. Pays-Bas 1986, 105: 332

30 Brunner H. Sicheneder A. Angew. Chem., Int. Ed. Engl. 1988, 27: 718 ; Angew. Chem. 1988, 100, 730

31 Kropp PJ. J. Am. Chem. Soc. 1973, 95: 4611

32 Kwart H. Conley RA. J. Org. Chem. 1973, 38: 2011

33 Namy JL. Boireau G. Abenhaim D. Bull. Soc. Chim. Fr. 1971, 3191

34 Depres JP. Greene AE. J. Org. Chem. 1984, 49: 928

35 Bew RE. J. Chem. Soc. 1966, 129

36 Prat D. Lett R. Tetrahedron Lett. 1986, 27: 707

37a Bonini C. Frederici C. Rossi L. Gigli G. J. Org. Chem. 1995, 60: 4803

37b Gorthey LA. Vairamani M. Djerassi C. J. Org. Chem. 1984, 49: 1511