Oxidative Preparation of Aromatic Orthocarboxylates from Aldehydes

Abstract

Aromatic orthocarboxylates are oxidatively synthesized in good yields from hydroxyacetals derived from the corresponding aromatic aldehydes. In situ generation of hydroxyacetal and successive oxidation by DDQ provides a one-pot preparation of aromatic orthocarboxylates from aldehydes.

Key words

orthoester - oxidation - acetal - aldehyde - one-pot reaction

References and Notes

• For reviews, see:
• 1a Greene TW. Wuts PGM. Protective Groups in Organic Synthesis   3rd ed.:  Wiley; New York: 1999.  p.437 
• 1b DeWolfe RH. Carboxylic Ortho Acid Derivatives   Academic Press; New York: 1970. 
• 1c DeWolfe RH. Synthesis  1974,  153 
• 1d Pindur U. Müller J. Flo C. Witzel H. Chem. Soc. Rev.  1987,  16:  75 
• 2 Wipf P. Tsuchimoto T. Takahashi T. Pure Appl. Chem.  1999,  71:  415 
• 3 Corey EJ. Raju N. Tetrahedron Lett.  1983,  24:  5571 
• 4a Liao S.-G. Chen H.-D. Yue J.-M. Chem. Rev.  2009,  109:  1092 
• 4b Stanoeva E. He W. De Kimpe N. Bioorg. Med. Chem.  2005,  13:  17 
• 4c Corey EJ. Kang M. Desai MC. Ghosh AK. Houpis IN. J. Am. Chem. Soc.  1988,  110:  649 
• 5a Wipf P. Aslan DC. J. Org. Chem.  2001,  66:  337 
• 5b Wipf P. Xu W. Kim H. Takahashi H. Tetrahedron  1997,  53:  16575 
• 5c Wipf P. Xu W. J. Org. Chem.  1993,  58:  5880 
• 6a McElvain SM. Nelson JW. J. Am. Chem. Soc.  1942,  64:  1825 
• 6b Shevchenko VI. Koval AA. Zh. Obshch. Khim.  1968,  38:  22 
• 7a McElvain SM. Nelson JW. J. Am. Chem. Soc.  1942,  64:  1825 
• 7b McElvain SM. J. Am. Chem. Soc.  1950,  72:  1661 
• 7c McElvain SM. Schroeder JP. J. Am. Chem. Soc.  1949,  71:  40 
• 7d McElvain SM. Stevens CL. J. Am. Chem. Soc.  1946,  68:  1917 
• 8a Arbusov AA. Yuldasheva EK. Dokl. Akad. Nauk SSSR  1950,  70:  231 
• 8b Stetter H. Reske E. Chem. Ber.  1970,  103:  639 
• 8c Hebky J. Collect. Czech. Chem. Commun.  1948,  13:  442 
• 9 Electrochemocal oxidation of acetals is reported, see: Scheeren JW. Goossens HJM. Top WH. Synthesis  1978,  283 
• 10 Rockendorf N. Sperling O. Lindhorst K. Aust. J. Chem.  2002,  55:  87 
• 12 Pieck JC. Kuch F. Grolle F. Linne U. Carell T. J. Am. Chem. Soc.  2006,  128:  1404 
• 13a Classon B. Garegg PJ. Samuelsson B. Acta Chem. Scand. Ser. B  1984,  38:  419 
• 13b Johansson R. Samuelsson B. J. Chem. Soc., Perkin Trans. 1  1984,  2371 
• 13c Georg GI. Mashava PM. Akgün E. Milstead MW. Tetrahedron Lett.  1991,  32:  3151 
• 13d Wang Y. Babirad SA. Kishi Y. J. Org. Chem.  1992,  57:  468 
• 14 Nishimura T. Onoue T. Ohe K. Uemura S. J. Org. Chem.  1999,  64:  6750 
• 15a Findlay JWA. Turner AB. J. Chem. Soc.  1971,  23 
• 15b Horita K. Yoshioka T. Tanaka T. Oikawa Y. Yonemitsu O. Tetrahedron  1986,  42:  3021 
• 15c Tanaka T. Oikawa Y. Hamada T. Yonemitsu O. Tetrahedron Lett.  1986,  27:  3651 
• 15d Oikawa Y. Tanaka T. Horita K. Yonemitsu O. Tetrahedron Lett.  1984,  25:  5397 
• 15e Oikawa Y. Yoshioka T. Yonemitsu O. Tetrahedron Lett.  1982,  23:  885 
• 16 PMB ethers are known to be oxidized by DDQ to afford acetals in the presence of alcohols, see: Ito Y. Ohnishi Y. Ogawa T. Nakahara Y. Synlett  1998,  1102 

11

We separated the diastereomers for the purpose of structural analysis of the major stereoisomers. This separation is surely unnecessary for the subsequent step.