A New and Mild Heterogeneous Catalytic Decomposition of α-Diazo Carbonyl Compounds Using Montmorillonite or Zeolite

Abstract

A very mild method of decomposition of various α-diazo carbonyl compounds 1 in the presence of environmentally attractive solid acids such as montmorillonite K-10 or zeolite H-Y in a heterogeneous manner to furnish α-hydroxy/alkoxy ketones in very good yield is reported. Interestingly, novel bicycloalkane-1,3-diones and 3-furanones were obtained as unusual products in the case of aliphatic/alicyclic α-diazo carbonyl compounds.

diazo ketones - heterogeneous catalysts - hydroxy ketones - O-H insertion - montmorillonite - zeolite

References

1 Doyle MP. McKervey MA. Ye T. Modern Catalytic Methods for Organic Synthesis with Diazo Compounds. From Cyclopropanes to Ylides   Wiley-Interscience; New York: 1998

2a Padwa A. Top. Curr. Chem.  1997,  189:  121 

2b Padwa A. Hornbuckle SA. Chem. Rev.  1991,  91:  263 

2c Ye T. McKervey MA. Chem. Rev.  1994,  94:  1091 

2d Padwa A. Weingarten MD. Chem. Rev.  1996,  96:  223 

3a Miller DJ. Moody CJ. Tetrahedron  1995,  51:  10811 

3b Bulugahapitiya P. Landais Y. Parra-Rapado L. Planchenault D. Weber V. J. Org. Chem.  1997,  62:  1630 

3c Benati L. Nanni D. Spagnolo P. J. Chem. Soc., Perkin Trans. 1  1997,  457 

4 Regitz M. Mass G. Diazo Compounds-Properties and Synthesis   Academic Press; New York: 1986 p., 90 

5 Coppola GM. Synthesis  1984,  1021 

6 Perni RB. Synth. Commun.  1989,  19:  2383 

7a Patwardhan SA. Dev S. Synthesis  1974,  348 

7b Gupta SK. J. Org. Chem.  1976,  41:  2642 

7c Dann AE. Davis JB. Nagler J. J. Chem. Soc., Perkin Trans. 1  1979,  158 

7d Ballini R. Marziali P. Mozzicafreddo A. J. Org. Chem.  1996,  61:  3209 

8a Balogh M. Laszlo P. Organic Chemistry using Clay   Spinger-Verlag; New York: 1993

8b Ponde DE. Despande VH. Bulbule VJ. Sudalai A. Gajare AS. J. Org. Chem.  1998,  63:  1058 

9 Ponde DE. Borate HB. Sudalai A. Ravindranathan T. Deshpande VH. Tetrahedron Lett.  1996,  37:  4605 

10 Upadhya TT. Daniel T. Sudalai A. Ravindranathan T. Sabu KR. Synth. Commun.  1996,  26:  4539 

11 Asakura J.-I. Robins MJ. Asaka Y. Kim TH. J. Org. Chem.  1996,  61:  9026 

12 Lakshmi Kantham M. Lakshmi Shanthi P. Indian J. Chem. B.  1990,  35B:  260 

13 Sreekumar R. Rugmini P. Padmakumar R. Tetrahedron Lett.  1997,  38:  6557 ; and references cited therein

14 Van Herwijnen HWG. Brinker UH. J. Org. Chem.  2001,  66:  2874 

15 Muthusamy S. Babu SA. Gunanathan C. Jasra RV. Tetrahedron Lett.  2001,  42:  5113 

16 Muthusamy S. Babu SA. Gunanathan C. Suresh E. Dastidar P. Jasra RV. Tetrahedron  2000,  56:  6307 

17a Muthusamy S. Babu SA. Gunanathan C. Tetrahedron Lett.  2000,  41:  8839 

17b Muthusamy S. Gunanathan C. Babu SA. Tetrahedron Lett.  2001,  42:  523 

17c Muthusamy S. Babu SA. Gunanathan C. Suresh E. Dastidar P. Synlett  2001,  1407 

17d Muthusamy S. Babu SA. Gunanathan C. Suresh E. Dastidar P. Jasra RV. Tetrahedron  2001,  57:  7009 

18 Whitsell JK. Buchanan CM. J. Org. Chem.  1986,  51:  5443 

19a Trost BM. Ito H. Silcoff ER. J. Am. Chem. Soc.  2001,  123:  3367 

19b Hoffmann T. Zhong T. List B. Shabat D. Anderson J. Gramatikova S. Lerner RA. Barbas CF. J. Am. Chem. Soc.  1998,  120:  2768 

20 Muthusamy S. Babu SA. Gunanathan C. Synth. Commun.  2001,  31:  1205 

21 Elander M. Leander K. Rosenblom J. Ruusa E. Acta Chem. Scand.  1973,  27:  1907 

22

Typical Experimental Procedure: The clay/zeolite catalysts used in this work were activated at 200 °C for 3 h. To a solution containing α-diazo ketone 1a (100 mg) in commercial grade dichloromethane was added zeolite H-Y (175 mg) or montmorillonite clay K-10 (175 mg) and the mixture stirred at r.t. or ultrasonicated. Slow nitrogen evolution took place and the reaction mixture was followed by TLC until disappearance of starting material. The reaction mixture was then filtered, concentrated under reduced pressure and purified by silica gel column chromatography to afford product 2a. All novel compounds gave satisfactory spectral data consistent with their structures. Selected spectral data of 5-Hydroxy-4,4,5-trimethyldihydrofuran-3-one (8): colourless solid, mp 63-65 ºC; IR (KBr): 3372, 2998, 2978, 2913, 2934, 1744, 1704, 1471, 1453, 1396, 1121, 1039, 932, 851 cm^-1; ¹H NMR (200 MHz, CDCl₃): δ = 4.14, (d, 1 H, J = 16.6 Hz, OCH₂), 4.06 (d, 1 H, J = 16.6 Hz, OCH₂), 2.72 (s, 1 H, OH), 1.50 (s, 3 H, CH₃), 1.09 (s, 3 H, CH₃), 1.05 (s, 3 H, CH₃); ¹³C NMR (50.3 MHz, CDCl₃): δ = 16.5 (CH₃), 22.0 (CH₃), 22.3 (CH₃), 51.1 (quat-C), 67.9 (OCH₂), 107.4 (quat-C), 218.6 (C=O); MS: m/z = 144 [M⁺]; Anal. Calcd for C₇H₁₂O₃: C, 58.31; H, 8.39. Found: C, 58.40; H, 8.44. 2-Methoxy-1-(4-methoxyphenyl)ethanone (11d): colourless thick liquid; IR(neat): 3059, 2934, 2842, 1776, 1691, 1602, 1576, 1512, 1462, 1422, 1312, 1259, 1175, 1128, 1026 cm^-1; ¹H NMR (200 MHz, CDCl₃): δ = 7.93 (d, 2 H, J = 8.6 Hz, Arom-H), 6.93 (d, 2 H, J = 8.6 Hz, Arom-H), 4.65 (s, 2 H, OCH₂), 3.87 (s, 3 H, OCH₃), 3.50 (s, 3 H, OCH₃); ¹³C NMR (50.3 MHz, CDCl₃): δ = 55.9 (OCH₃), 59.8 (OCH₃), 75.5 (OCH₂), 114.0 (=CH), 130.6 (=CH), 133.2 (quat-C), 164.2 (quat-C), 195.1 (C=O); MS: m/z = 180 [M⁺]; Anal. Calcd for C₁₀H₁₂O₃: C, 66.65; H, 6.71. Found: C, 66.72; H, 6.65.