A New Practical Method for the Osmium-Catalyzed Dihydroxylation of Olefins­ using Bleach as the Terminal Oxidant

Abstract

A general procedure for the osmium-catalyzed dihydroxylation of various olefins using bleach as oxidant is reported for the first time. Aromatic and aliphatic olefins yield the corresponding cis-1,2-diols in the presence of dihydroquinine or dihydroquinidine derivatives (Sharpless ligands) with good to excellent chemo- and enantioselectivities under optimized pH conditions. In the presence of a small excess of bleach as reoxidant fast dihydroxylation takes place even at 0 °C. Under optimum reaction conditions it is possible to dihydroxylate terminal aliphatic and aromatic olefins as well as internal olefins. The low price of the oxidant and the simple handling of bleach make this dihydroxylation variant attractive for further applications.

Key words

asymmetric catalysis - dihydroxylation - homogenous catalysis - osmium - oxidations

References

• Worldwide production capacities for ethylene glycol in 1995: 9.7 Mio to/a; worldwide production of 1,2-propylene glycol in 1994: 1.1 Mio to/a:
• 1a Weissermel K. Arpe H.-J. Industrielle Organische Chemie   Wiley-VCH; Weinheim: 1998.  5th ed.. p.167 
• 1b Weissermel K. Arpe H.-J. Industrielle Organische Chemie   Wiley-VCH; Weinheim: 1998.  5th ed.. p.302 
• 2a Szmant HH. Organic Building Blocks of the Chemical Industry   Wiley; New York: 1989.  p.347 
• 2b Pohl G. Gaube H. In Ullmann’s Encyclopedia of Industrial Chemistry   Vol. A1:  VCH; Weinheim: 1985.  p.305-320  
• Reviews:
• 3a Schröder M. Chem. Rev.  1980,  80:  187 
• 3b Kolb HC. Van Nieuwenhze MS. Sharpless KB. Chem. Rev.  1994,  94:  2483 
• 3c Beller M. Sharpless KB. In Applied Homogeneous Catalysis   Cornils B. Herrmann WA. VCH; Weinheim: 1996.  p.1009-1024  
• 3d Kolb HC. Sharpless KB. In Transition Metals for Organic Synthesis   Vol. 2:  Beller M. Bolm C. VCH-Wiley; Weinheim: 1998.  p.219-242  
• 3e Marko IE. Svendsen JS. In Comprehensive Asymmetric Catalysis II   Jacobsen EN. Pfaltz A. Yamamoto H. Springer; Berlin: 1999.  p.713-787  
• 3f Bolm C. Hildebrand JP. Muniz K. In Catalytic Asymmetric Synthesis   VCH-Wiley; Weinheim: 2000.  2nd ed.. p.399-428  
• 4a Hentges SG. Sharpless KB. J. Am. Chem. Soc.  1980,  102:  4263 
• 4b Sharpless KB. Amberg W. Bennani YL. Crispino GA. Hartung J. Jeong K.-S. Kwong H.-L. Morikawa K. Whang Z.-M. Xu D. Zhang X.-L. J. Org. Chem.  1992,  57:  2768 
• 4c Periasamy M. Ramanathan CR. Kumar NS. Thirumalaikumar M. J. Chem. Res., Synop.  2001,  512 
• 4d Anderson MA. Epple R. Fokin VV. Sharpless KB. Angew. Chem. Int. Ed.  2002,  41:  472 
• 5a Nambu M. White JD. J. Chem. Soc., Chem. Commun.  1996,  1619 
• 5b Mori K. Takikawa H. Nishimura Y. Horikiri H. Liebigs Ann./Recueil  1997,  327 
• 5c Sinha SC. Sinha A. Sinha SC. Keinan E. J. Am. Chem. Soc.  1998,  120:  4017 
• 5d Trost BM. Calkins TL. Bochet CG. Angew. Chem., Int. Ed. Engl.  1997,  36:  2632 
• 5e Harris JM. Keranen MD. O’Doherty GA. J. Org. Chem.  1999,  64:  2982 
• 5f Corey EJ. Guzman-Perez A. Noe MC. J. Am. Chem. Soc.  1994,  116:  12109 
• 5g Corey EJ. Guzman-Perez A. Noe MC. J. Am. Chem. Soc.  1995,  117:  10805 
• 5h Corey EJ. Noe MC. Ting AY. Tetrahedron Lett.  1996,  37:  1735 
• 5i Song CJ. Jiang SD. Sing G. Synlett  2001,  1983 
• 5j Dominique R. Roy R. Tetrahedron Lett.  2002,  43:  395 
• 5k Fernandes RA. Bodas MS. Kumar P. Tetrahedron  2002,  58:  1223 
• 6a Gao Y, and Zepp CM. inventors; (to Sepracor Inc.) WO  9317150.  ; Chem. Abstr. 1994, 120, 119437
• 6b Anon . Chem. Eng. News  1994,  72(50):  41 
• 6c Torii S. Liu P. Tanak H. Chem. Lett.  1995,  319 
• 7a Bergstad K. Jonsson SY. Bäckvall J.-E. J. Am. Chem. Soc.  1999,  121:  10424 
• 7b Jonsson SY. Adolfsson H. Bäckvall J.-E. Org. Lett.  2001,  3:  3463 
• 8a Krief A. Colaux-Castillo C. Tetrahedron Lett.  1999,  40:  4189 
• 8b Krief A. Colaux-Casstillo C. Synlett  2001,  501 
• 9a Döbler C. Mehltretter G. Beller M. Angew. Chem., Int. Ed.  1999,  38:  3026 
• 9b Döbler C. Mehltretter GM. Sundermeier U. Beller M. J. Am. Chem. Soc.  2000,  122:  10289 
• 9c Döbler C. Mehltretter GM. Sundermeier U. Beller M. J. Organomet. Chem.  2001,  621:  70 
• 10a Cummins RW. inventors; (to FMC Corporation, New York) US Patent  3488394.  ; Chem. Abstr. 1970, 72, 100007
• 10b Cummins RW. inventors; (to FMC Corporation, New York) US Patent  3846478.  ; Chem. Abstr., 1975, 82, 72526
• Selected examples:
• 11a Li G. Chang H.-T. Sharpless KB. Angew. Chem., Int. Ed. Engl.  1996,  35:  451 
• 11b Curran DP. Ko S.-B. J. Org. Chem.  1994,  59:  6139 
• 11c Fang FG. Xie S. Lowery MW. J. Org. Chem.  1994,  59:  6142 
• 11d Whang Z.-M. Kolb HC. Sharpless KB. J. Org. Chem.  1994,  59:  5104 
• 11e Fisher AJ. Kerrigan F. Synth. Commun.  1998,  28:  2959 
• 12 Mehltretter GM. Döbler C. Sundermeier U. Beller M. Tetrahedron Lett.  2000,  41:  8083 
• 14 Beller M. Zapf A. Mägerlein W. Chem. Eng. Techn.  2001,  24:  575 
• 15 Berrisford DJ. Bolm C. Sharpless KB. Angew. Chem., Int. Ed. Engl.  1995,  34:  1059 
• 16 Jacobsen EN. Marko I. Mungall WS. Schröder G. Sharpless KB. J. Am. Chem. Soc.  1988,  110:  1968 
• 17 Wai JSM. Markó I. Svendsen JS. Finn MG. Jacobsen EN. Sharpless KB. J. Am. Chem. Soc.  1989,  111:  1123 
• 18 Kolb HC. Andersson PG. Sharpless KB. J. Am. Chem. Soc.  1994,  116:  1278 

13

TOF = mol product × mol catalyst^-1 × h^-1.