Selective Synthesis of 2-Aryl-2H- and 4-Aryl-4H-3,5-diformylpyrans from Acetal with Aromatic Aldehydes Catalyzed by Lewis Acids

Abstract

A selective method for 2-aryl-2H- and 4-aryl-4H-3,5-diformylpyrans synthesis from 1,1,3,3-tetramethoxypropane and aromatic aldehydes was developed using an FeCl₃ catalyst in MeOH-AcOH and an AlCl₃ catalyst in DMA-AcOH.

acetals - pyrans - aldehydes - Lewis acids - catalysis

References and Notes

For recent examples, see:

<A NAME="RU00611ST-1A">1a</A> Oepstad CL. Sliwka H.-R. Partali V. Eur. J. Org. Chem.  2010,  435 

<A NAME="RU00611ST-1B">1b</A> Fan X. Feng D. Qu Y. Zhang X. Wang J. Loiseau PM. Andrei G. Snoeck R. De Clercq E. Bioorg. Med. Chem. Lett.  2010,  20:  809 

<A NAME="RU00611ST-1C">1c</A> Aljarilla A. Plumet J. Heterocycles  2008,  76:  827 

<A NAME="RU00611ST-1D">1d</A> Lachance H. Marion O. Hall DG. Tetrahedron Lett.  2008,  49:  6061 

<A NAME="RU00611ST-1E">1e</A> Salit A.-F. Meyer C. Cossy J. Synlett  2007,  934 

<A NAME="RU00611ST-1F">1f</A> Li W. Wayne GS. Lallaman JE. Wittenberger SJ. J. Org. Chem.  2006,  71:  1725 

<A NAME="RU00611ST-1G">1g</A> Donner CD. Gill M. Tewierik LM. Molecules  2004,  9:  498 

<A NAME="RU00611ST-1H">1h</A> Tanaka S. Isobe M. Tetrahedron  1994,  50:  5633 

<A NAME="RU00611ST-1I">1i</A> Crawley GC. Briggs MT. Dowell RI. Edwards PN. Hamilton PM. Kingston JF. Oldham K. Waterson D. Whalley DP. J. Med. Chem.  1993,  36:  295 

<A NAME="RU00611ST-2A">2a</A> Zhang X.-M. Tu Y.-Q. Jiang Y.-J. Zhang Y.-Q. Fan C.-A. Zhang F.-M. Chem. Commun.  2009,  4726 

<A NAME="RU00611ST-2B">2b</A> Hoye TR. Danielson ME. May AE. Zhao H. Angew. Chem. Int. Ed.  2008,  47:  9743 

<A NAME="RU00611ST-3">3</A> Foroumadi A. Emami S. Sorkhi M. Nakhjiri M. Nazarian Z. Heydari S. Ardestani SK. Poorrajab F. Shafiee A. Chem. Biol. Drug Des.  2010,  75:  590 

<A NAME="RU00611ST-4A">4a</A> Shaabani A. Nejat FS. J. Chem. Res., Synop.  1998,  584 

<A NAME="RU00611ST-4B">4b</A> Amaresh RR. Perumal PT. Tetrahedron  1999,  55:  8083 

<A NAME="RU00611ST-4C">4c</A> Csihony S. Mika L. Vlád G. Barta K. Mehnert CP. Horváth IT. Collect. Czech. Chem. Commun.  2007,  72:  1094 ; and references therein

<A NAME="RU00611ST-5A">5a</A> Reichardt C. Yun K.-Y. Massa W. Schmidt RE. Liebigs Ann. Chem.  1985,  1987 

<A NAME="RU00611ST-5B">5b</A> Medvedeva AS. Pavlov DV. Mareev AV. Russ. J. Org. Chem.  2008,  44:  143 

<A NAME="RU00611ST-6">6</A> Maeda S. Obora Y. Ishii Y. Eur. J. Org. Chem.  2009,  4067 

<A NAME="RU00611ST-7A">7a</A> Tamaso K. Hatamoto Y. Sakaguchi S. Obora Y. Ishii Y. J. Org. Chem.  2007,  72:  3603 

<A NAME="RU00611ST-7B">7b</A> Tamaso K. Hatamoto Y. Obora Y. Sakaguchi S. Ishii Y. J. Org. Chem.  2007,  72:  8820 

<A NAME="RU00611ST-7C">7c</A> Maeda S. Horikawa N. Obora Y. Ishii Y. J. Org. Chem.  2009,  74:  9558 

<A NAME="RU00611ST-8">8</A> Cockerill AF. Harrison RG. In The Chemistry of Double-Bonded Functional Groups   Part 1:  Patai S. John Wiley and Sons; London: 1977.  p.277-285  

<A NAME="RU00611ST-9">9</A>

All the attempts to isolate or fully characterize the intermediates B, C, and D were unsuccessful. However, when the reaction of 1 and 2g was carried out at r.t. under the conditions as in Table  [²] , entry 7, the intermediate B for the formation of 3g was detected by GC and GC-MS analysis. HRMS (EI): m/z calcd for C₁₁H₇O₂F₃ [M]⁺: 228.0398; found: 228.0396.

<A NAME="RU00611ST-10">10</A> Oare DA. Heathcock CH. Top. Stereochem.  1989,  19:  227 

<A NAME="RU00611ST-11A">11a</A> Krishtal GV. Kulganek VV. Kucherov VF. Yanovskaya LA. Synthesis  1979,  107 

<A NAME="RU00611ST-11B">11b</A> Yamaguchi M. Yokota N. Minami T. J. Chem. Chem., Chem. Commun.  1991,  1088 

<A NAME="RU00611ST-12">12</A> Oare DA. Heathcock CH. Top. Stereochem.  1991,  20:  87