Aerobic Oxidation of Alkenes to Esters of Vicinal Diols with a syn-Configuration Catalyzed by I₂ and the H₅PV₂Mo₁₀O₄₀ Polyoxometalate

Abstract

A new method for the synthesis of vicinal diols from ­alkenes has been developed. Reaction of molecular iodine in the presence of a polyoxometalate as oxidation catalyst under aerobic conditions in acetic acid solvent leads to the oxidative iodoacetoxyl­ation of an alkene, i.e. formation of a 1,2-iodoacetate. Further in situ substitution of the iodide by water yields the 1,2-diol monoacetate with a predominantly (ca. 4.5:1) cis-configuration. Further esterification under the reaction’s acidic conditions leads also to the cis-diacetate. The method may be valuable for the synthesis of cis-vicinal diols without use of toxic osmium catalysts.

Key words

aldehydes - arenes - electrophilic aromatic substitutions - oxidations - quinones

References

• 1a Beller M. Sharpless KB. Applied Homogeneous Catalysis with Organometallic Compounds   2nd ed., Vol. 3:  Cornils B. Herrmann WA. Wiley-VCH; Weinheim, Germany: 2002.  p.1149 
• 1b Donohoe TJ. Synlett  2002,  1223 
• 1c Severeyns A. de Vos DE. Jacobs PA. Top. Catal.  2002,  19:  125 
• 1d Sundermeier U. Döbler C. Beller M. Modern Oxidation Methods   Bäckvall JE. Wiley-VCH; Weinheim: 2004.  p.1 
• 2a Brinksma J. Schmieder L. van Vleit G. Boaron R. Hage R. de Vos DE. Alsters PL. Feringa BL. Tetrahedron Lett.  2002,  43:  2619 
• 2b de Vos DE. de Wildeman S. Sels BF. Grobet PJ. Jacobs PA. Angew. Chem. Int. Ed.  1999,  38:  980 
• 2c Fujita M. Costas M. Que L. J. Am. Chem. Soc.  2003,  125:  9912 
• 2d Costas M. Que L. Angew. Chem. Int. Ed.  2002,  41:  2179 
• 2e Ryu JY. Kim J. Costas M. Chen K. Nam W. Que L. Chem. Commun.  2002,  1288 
• 2f Costas M. Tipton AK. Chen K. Jo DH. Que L. J. Am. Chem. Soc.  2001,  123:  6722 
• 2g Herrmann WA. Marz D. Herdtweck E. Schäfer A. Wagner W. Kneuper H.-J. Angew. Chem., Int. Ed. Engl.  1987,  26:  462 
• 2h Shing TKM. Tai VW.-F. Tam EKW. Angew. Chem., Int. Ed. Engl.  1994,  33:  2312 
• 2i Shing TKM. Tam EKW. Tai VW.-F. Chung IHF. Jiang Q. Chem. Eur. J.  1996,  2:  50 
• 3a Corey EJ. Danheiser RL. Chandrasherkaran S. J. Org. Chem.  1976,  41:  260 
• 3b Balu N. Nayak SK. Banerij A. J. Am. Chem. Soc.  1996,  118:  5932 
• 3c McMurry JE. Rico JG. Tetrahedron Lett.  1989,  30:  1169 
• 4 Branytska OV. Neumann R. J. Org. Chem.  2003,  68:  9510 
• 5a Gunstone FD. In Advances in Organic Chemistry   Vol. 1:  Raphael RA. Taylor LC. Wynberg H. Interscience Publishers; New York: 1960.  p.103 
• 5b Haines AH. Methods for the Oxidation of Organic Compounds. Alkenes, Alkynes, and Arenes   Academic Press; London: 1985. 
• 5c Woodward RB. Brutcher FV. J. Am. Chem. Soc.  1958,  80:  209 
• 6 Diol formation (ditosylate derivatives) with hypervalent iodine species is also known. Confer: Hirt UH. Spingler B. Wirth T. J. Org. Chem.  1998,  63:  7674