The Spirodienone Route for the Functionalization of Calixarenes

Abstract

Mild oxidation of calixarenes affords their spirodienone derivatives. These derivatives are useful synthetic intermediates for the selective functionalization of calixarenes. The presence of several functionalities (carbonyl, ether, diene) within the calix scaffold enables them to undergo a large number of synthetic transformations. The spirodienone calixarene derivatives have been utilized for the selective derivatization of two vicinal OH groups, the replacement of one or two OH groups, the formation of Ar-O-Ar bonds between neighboring aryl groups, the functionalization of the calix scaffold at the extraannular positions (via spirodienol derivatives), and the modification of the methylene groups.

• 1 Introduction

• 2 Spirodienone Calixarene Derivatives

• 3 Isomerism and Mutual Interconversion

• 4 Spirodienone Derivatives of Larger Calixarenes

• 5 Synthetic Applications of Spirodienone Calixarene Derivatives

• 5.1 Spirodienones as Protecting Groups

• 5.2 Selective Aminodehydroxylation of Calixarenes

• 5.3 Replacement of Two OH Groups by Methyls

• 5.4 Dehydration of Two Proximal Phenol Groups

• 5.5 Extraannular Modification of the Calix Scaffold: Spirodienol Calixarene Derivatives

• 5.6 The Spirodienone Route for Methylene Functionalization

• 6 Conclusions

Key words

calixarenes - macrocycles - spirodienone - synthesis - carbonyl

References

• For reviews on calixarenes see:
• 1a Gutsche CD. Calixarenes   Royal Society of Chemistry; Cambridge: 1989. 
• 1b Gutsche CD. Aldrichimica Acta  1995,  28:  1 
• 1c Böhmer V. Angew. Chem., Int. Ed. Engl.  1995,  34:  713 
• 1d Gutsche CD. Calixarenes Revisited   Royal Society of Chemistry; Cambridge: 1998. 
• 1e Calixarenes 2001   Asfari Z. Böhmer V. Harrowfield J. Vicens J. Kluwer Academic Publishers; Dordrecht: 2001. 
• Synthetic procedures for the preparation of the p-tert-butylcalixarenes 1a, 1c, and 1d on a ca. 100 g scale are available, see:
• 3a Gutsche CD. Iqbal M. Org. Synth.  1989,  68:  234 
• 3b Gutsche CD. Dhawan B. Leonis M. Stewart D. Org. Synth.  1989,  68:  238 
• 3c Munch JH. Gutsche CD. Org. Synth.  1989,  68:  243 
• 3d For the preparation of 1b see: Stewart DR. Gutsche CD. Org. Prep. Proced. Int.  1993,  25:  137 
• 3e For large calix[n]arenes (n >9) see: Stewart DR. Gutsche CD. J. Am. Chem. Soc.  1999,  121:  4136 
• 4 For a review on the synthesis of calixarenes via the stepwise and fragment condensation methods, see: Böhmer V. Liebigs Ann. Recl  1997,  2019 
• See for example:
• 5a Tabatabai M. Vogt W. Böhmer V. Tetrahedron Lett.  1990,  31:  3295 
• 5b Sartori G. Maggi R. Bigi F. Arduini A. Pastorio A. Porta C. J. Chem. Soc., Perkin Trans. 1  1994,  1657 
• 5c Sartori G. Bigi F. Porta C. Maggi R. Mora R. Tetrahedron Lett.  1995,  36:  2311 
• 5d Grüttner C. Böhmer V. Vogt W. Thondorf I. Biali SE. Grynszpan F. Tetrahedron Lett.  1994,  35:  6267 
• 5e Biali SE. Böhmer V. Cohen S. Ferguson G. Grüttner C. Grynszpan F. Paulus EF. Thondorf I. Vogt W. J. Am. Chem. Soc.  1996,  118:  12938 
• 5f Biali SE. Böhmer V. Columbus I. Ferguson G. Grüttner C. Grynszpan F. Paulus EF. Thondorf I. J. Chem. Soc., Perkin Trans 2  1998,  2261 
• 5g Bergamaschi M. Bigi F. Lanfranchi M. Maggi R. Pastorio A. Pellinghelli MA. Peri F. Porta C. Sartori G. Tetrahedron  1997,  53:  3037 
• 5h Tsue H. Enyo K. Hirao K. Org. Lett.  2000,  2:  3071 
• 6 For a review on the hydroxyl replacement in calixarenes see: Biali SE. Isr. J. Chem.  1997,  37:  131 
• 7 Zuaretz N. Golan O. Biali SE. J. Org. Chem.  1991,  56:  2444 
• 8 Abel J. Berichte  1892,  25:  3477 
• 9a Pummerer R. Cherbuliez E. Berichte  1914,  47:  2957 
• 9b Shearing EA. Smiles S. J. Chem. Soc.  1937,  1931 
• 10a See for example: Kasturi TR. Rajasekhar B. Raju GJ. Reddy GM. Sivaramakrishnan R. Ramasubbu N. Venkatesan K. J. Chem. Soc., Perkin Trans 1  1984,  2375 
• 10b For a review see: Ward RS. Chem. Brit.  1973,  9:  444 
• 11 Müller E. Mayer R. Narr B. Rieker A. Scheffler K. Justus Liebigs Ann. Chem.  1961,  645:  25 
• 12 Meier H. Schneider H.-P. Rieker A. Hitchcock PB. Angew. Chem., Int. Ed. Engl.  1978,  17:  121 
• For the preparation and reactions of calixquinones see for example:
• 13a Morita Y. Agawa T. Kai Y. Kanehisa N. Kasai N. Nomura E. Taniguchi H. Chem. Lett.  1989,  1349 
• 13b Morita Y. Agawa T. Kai Y. Nomura E. Taniguchi H. J. Org. Chem.  1992,  57:  3658 
• 13c Reddy PA. Kashyap RP. Watson WH. Gutsche CD. Isr. J. Chem.  1992,  32:  89 
• 13d Grynszpan F. Dinoor N. Biali SE. Tetrahedron Lett.  1991,  32:  1909 
• 13e Casnati A. Comelli E. Fabbi M. Bocchi V. Mori G. Uggozoli F. Manotii Lanfredi AM. Pochini A. Ungaro R. Recl. Trav. Chim. Pays-Bas  1993,  112:  384 
• 13f Reddy PA. Gutsche CD. J. Org. Chem.  1993,  58:  3245 
• 14 For a review on the oxidation and reduction of calixarenes see: Biali SE. In Calixarenes 2001   Asfari Z. Böhmer V. Harrowfield J. Vicens J. Kluwer Academic Publishers; Dordrecht: 2001.  p.266-279  
• 15a Neri P. Bottino A. Cunsolo F. Piatelli M. Gavuzzo E. Angew. Chem. Int. Ed.  1998,  37:  166 
• 15b Bottino A. Cunsolo F. Piatelli M. Garozzo D. Neri P. J. Org. Chem.  1999,  64:  8018 
• 16a Litwak AM. Grynszpan F. Aleksiuk O. Cohen S. Biali SE. J. Org. Chem.  1993,  58:  393 
• 16b For a review of our early work on the spirodienone derivatives of the calixarenes see: Aleksiuk O. Grynszpan F. Litwak MA. Biali SE. New J. Chem.  1996,  20:  473 
• 16c See also: Grynszpan F. Aleksiuk O. Biali SE. Pure Appl. Chem.  1996,  68:  1249 
• 17 Wang W.-G. Zhang W.-C. Huang Z.-T. J. Chem. Res., Synop.  1998,  462 
• 18 Agbaria K. Biali SE. J. Am. Chem. Soc.  2001,  123:  12495 
• 19 Aleksiuk O. Grynszpan F. Biali SE. J. Chem. Soc., Chem. Commun.  1993,  11 
• 20 Georghiou PE. Ashram M. Clase HJ. Bridson JN. J. Org. Chem.  1998,  63:  1819 
• For an example of a spirodienone derivative of a dihydroxymetacyclophane see:
• 21a Yamato T. Matsumoto J. Sato M. Fujita K. Nagano Y. J. Chem. Res., Synop.  1997,  74 
• 21b Yamato T. Matsumoto J. Fujita K. J. Chem. Soc., Perkin Trans. 1  1998,  123 
• 22a Grynszpan F. Biali SE. J. Org. Chem.  1996,  61:  9512 
• 22b Aleksiuk O. Cohen S. Biali SE. J. Am. Chem. Soc.  1995,  117:  9645 
• 23a Yamato T. Hasegawa K. Saruwatari Y. Doamekpor LK. Chem. Ber.  1993,  126:  1435 
• 23b O’Sullivan P. Böhmer V. Vogt W. Paulus EF. Jakobi RA. Chem. Ber.  1994,  127:  427 
• 23c For an analysis of the conformation of the spherand type calixarene see: Agbaria K. Biali SE. Böhmer V. Brenn J. Cohen S. Frings M. Grynszpan F. Harrowfield J. Sobolev AN. Thondorf I. J. Org. Chem.  2001,  66:  2900 
• 24 Agbaria K. Aleksiuk O. Biali SE. Böhmer V. Frings M. Thondorf I. J. Org. Chem.  2001,  66:  2891 
• 25a Ohseto F. Murakami H. Araki K. Shinkai S. Tetrahedron Lett.  1992,  33:  1217 
• 25b Grynszpan F. Aleksiuk O. Biali SE. J. Org. Chem.  1994,  59:  2070 
• 26 Katagiri H. Iki N. Hattori T. Kabuto C. Miyano S. J. Am. Chem. Soc.  2001,  123:  779 
• 27 Aleksiuk O. Grynszpan F. Biali SE. J. Org. Chem.  1993,  58:  1994 
• 28a Kasturi TR. Jayaram SK. Pragnacharyulu PVP. Sattigeri JA. Reddy GM. Kumar KA. Tetrahedron  1993,  49:  113 
• 28b Kasturi TR. Kumar KA. Pragnacharyulu PVP. Tetrahedron  1993,  49:  125 
• 28c Kasturi TR. Kumar KA. Pragnacharyulu PVP. Sridevi G. Tetrahedron  1993,  49:  135 
• 29 Van Gelder JM. Aleksiuk O. Biali SE. J. Org. Chem.  1996,  61:  8419 
• 30 Van Gelder JM. Brenn J. Thondorf I. Biali SE. J. Org. Chem.  1997,  62:  3511 
• 31 Dean FM. Locksley HD. J. Chem. Soc.  1963,  393 
• 32 Yamato T. Hideshima C. Prakash GKS. Olah GA. J. Org. Chem.  1991,  56:  3192 
• 33a Aleksiuk O. Biali SE. Tetrahedron Lett.  1993,  34:  4857 
• 33b For an additional study of the Nafion-H catalyzed de-tert-butylation of calixarenes see: Rha SG. Chang S.-K. J. Org. Chem.  1998,  63:  2357 
• 34a Vol’eva VB. Belostotskaya JS. Ershov VV. Russ. Chem. Bull.  1996,  45:  744 
• 34b Belostotskaya IS. Vol’eva VB. Komissarova NL. Ershov VV. Russ. Chem. Bull.  1996,  45:  987 
• For examples of furan- and benzofuran-based macrocycles see:
• 35a Cafeo G. Giannetto M. Kohnke FH. La Torre GL. Parisi MF. Menzer S. White AJP. Williams DJ. Chem.-Eur. J.  1999,  5:  356 
• 35b Black DC. Craig DC. Kumar N. Rezaie R. Tetrahedron  1999,  55:  4803 
• 36 Agbaria K. Biali SE. J. Org. Chem.  2001,  66:  5482 
• 37 Carey FA. Tremper HS. J. Org. Chem.  1971,  36:  758 
• 38 Agbaria K. Wöhnert J. Biali SE. J. Org. Chem.  2001,  66:  7059 
• 39 Middleton WJ. J. Org. Chem.  1975,  40:  574 
• See for example:
• 40a Hammond GB. de Mendonca DJ. J. Fluorine Chem.  2000,  102:  189 
• 40b Gree D. Gree R. Boukerb A. Laabassi M. Tetrahedron Lett.  1997,  38:  6209 
• 41 Görmar G. Seiffarth K. Schultz M. Zimmerman J. Flämig G. Macromol. Chem.  1990,  191:  81 
• 42 Klenke B. Näther C. Friedrichsen W. Tetrahedron Lett.  1998,  39:  8967 
• 43 Middel O. Greff Z. Taylor NJ. Verboom W. Reinhoudt DN. Snieckus V. J. Org. Chem.  2000,  65:  667 
• 44 Scully DA. Hamilton TM. Bennett JL. Org. Lett.  2001,  3:  2741 
• 45 Simaan S. Agbaria K. Biali SE. J. Org. Chem.  2002,  67:  6136 

2

Over the last number of years the calixarene family has been expanded to include other structurally related metacyclo-phanes derivatives such as the resorcinarenes and the thiacalixarenes.