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
1a </A>
Gutsche CD.
Calixarenes
Royal
Society of Chemistry;
Cambridge:
1989.
1b </A>
Gutsche CD.
Aldrichimica Acta
1995,
28:
1
1c </A>
Böhmer V.
Angew. Chem., Int. Ed. Engl.
1995,
34:
713
1d </A>
Gutsche CD.
Calixarenes Revisited
Royal
Society of Chemistry;
Cambridge:
1998.
1e </A>
Calixarenes
2001
Asfari Z.
Böhmer V.
Harrowfield J.
Vicens J.
Kluwer Academic
Publishers;
Dordrecht:
2001.
2 </A>
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.
p-tert- butylcalixarenes 1a , 1c , and 1d on a ca. 100 g scale are available,
see:
3a </A>
Gutsche CD.
Iqbal M.
Org. Synth.
1989,
68:
234
3b </A>
Gutsche CD.
Dhawan B.
Leonis M.
Stewart D.
Org. Synth.
1989,
68:
238
3c </A>
Munch JH.
Gutsche CD.
Org.
Synth.
1989,
68:
243
3d </A> For the preparation of 1b see:
Stewart DR.
Gutsche CD.
Org. Prep. Proced.
Int.
1993,
25:
137
3e </A> For large calix[n]arenes
(n >9) see:
Stewart DR.
Gutsche CD.
J. Am. Chem. Soc.
1999,
121:
4136
<A NAME="RA30401ST-4">4 </A> For a review on the synthesis of
calixarenes via the stepwise and fragment condensation methods,
see:
Böhmer V.
Liebigs Ann.
Recl
1997,
2019
5a </A>
Tabatabai M.
Vogt W.
Böhmer V.
Tetrahedron
Lett.
1990,
31:
3295
5b </A>
Sartori G.
Maggi R.
Bigi F.
Arduini A.
Pastorio A.
Porta C.
J. Chem. Soc., Perkin Trans. 1
1994,
1657
5c </A>
Sartori G.
Bigi F.
Porta C.
Maggi R.
Mora R.
Tetrahedron
Lett.
1995,
36:
2311
5d </A>
Grüttner C.
Böhmer V.
Vogt W.
Thondorf I.
Biali SE.
Grynszpan F.
Tetrahedron
Lett.
1994,
35:
6267
5e </A>
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 </A>
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 </A>
Bergamaschi M.
Bigi F.
Lanfranchi M.
Maggi R.
Pastorio A.
Pellinghelli MA.
Peri F.
Porta C.
Sartori G.
Tetrahedron
1997,
53:
3037
5h </A>
Tsue H.
Enyo K.
Hirao K.
Org.
Lett.
2000,
2:
3071
<A NAME="RA30401ST-6">6 </A> For a review on the hydroxyl replacement
in calixarenes see:
Biali SE.
Isr.
J. Chem.
1997,
37:
131
<A NAME="RA30401ST-7">7 </A>
Zuaretz N.
Golan O.
Biali SE.
J.
Org. Chem.
1991,
56:
2444
<A NAME="RA30401ST-8">8 </A>
Abel J.
Berichte
1892,
25:
3477
9a </A>
Pummerer R.
Cherbuliez E.
Berichte
1914,
47:
2957
9b </A>
Shearing EA.
Smiles S.
J. Chem.
Soc.
1937,
1931
10a </A> 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 </A> For a review see:
Ward RS.
Chem. Brit.
1973,
9:
444
<A NAME="RA30401ST-11">11 </A>
Müller E.
Mayer R.
Narr B.
Rieker A.
Scheffler K.
Justus
Liebigs Ann. Chem.
1961,
645:
25
<A NAME="RA30401ST-12">12 </A>
Meier H.
Schneider H.-P.
Rieker A.
Hitchcock PB.
Angew. Chem., Int.
Ed. Engl.
1978,
17:
121
13a </A>
Morita Y.
Agawa T.
Kai Y.
Kanehisa N.
Kasai N.
Nomura E.
Taniguchi H.
Chem. Lett.
1989,
1349
13b </A>
Morita Y.
Agawa T.
Kai Y.
Nomura E.
Taniguchi H.
J. Org.
Chem.
1992,
57:
3658
13c </A>
Reddy PA.
Kashyap RP.
Watson WH.
Gutsche CD.
Isr.
J. Chem.
1992,
32:
89
13d </A>
Grynszpan F.
Dinoor N.
Biali SE.
Tetrahedron
Lett.
1991,
32:
1909
13e </A>
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 </A>
Reddy PA.
Gutsche CD.
J.
Org. Chem.
1993,
58:
3245
<A NAME="RA30401ST-14">14 </A> 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 </A>
Neri P.
Bottino A.
Cunsolo F.
Piatelli M.
Gavuzzo E.
Angew. Chem. Int. Ed.
1998,
37:
166
15b </A>
Bottino A.
Cunsolo F.
Piatelli M.
Garozzo D.
Neri P.
J.
Org. Chem.
1999,
64:
8018
16a </A>
Litwak AM.
Grynszpan F.
Aleksiuk O.
Cohen S.
Biali SE.
J. Org. Chem.
1993,
58:
393
16b </A> 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 </A> See also:
Grynszpan F.
Aleksiuk O.
Biali SE.
Pure Appl. Chem.
1996,
68:
1249
<A NAME="RA30401ST-17">17 </A>
Wang W.-G.
Zhang W.-C.
Huang Z.-T.
J.
Chem. Res., Synop.
1998,
462
<A NAME="RA30401ST-18">18 </A>
Agbaria K.
Biali SE.
J. Am. Chem. Soc.
2001,
123:
12495
<A NAME="RA30401ST-19">19 </A>
Aleksiuk O.
Grynszpan F.
Biali SE.
J.
Chem. Soc., Chem. Commun.
1993,
11
<A NAME="RA30401ST-20">20 </A>
Georghiou PE.
Ashram M.
Clase HJ.
Bridson JN.
J. Org. Chem.
1998,
63:
1819
21a </A>
Yamato T.
Matsumoto J.
Sato M.
Fujita K.
Nagano Y.
J.
Chem. Res., Synop.
1997,
74
21b </A>
Yamato T.
Matsumoto J.
Fujita K.
J.
Chem. Soc., Perkin Trans. 1
1998,
123
22a </A>
Grynszpan F.
Biali SE.
J.
Org. Chem.
1996,
61:
9512
22b </A>
Aleksiuk O.
Cohen S.
Biali SE.
J.
Am. Chem. Soc.
1995,
117:
9645
23a </A>
Yamato T.
Hasegawa K.
Saruwatari Y.
Doamekpor LK.
Chem.
Ber.
1993,
126:
1435
23b </A>
O’Sullivan P.
Böhmer V.
Vogt W.
Paulus EF.
Jakobi RA.
Chem. Ber.
1994,
127:
427
23c </A> 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
<A NAME="RA30401ST-24">24 </A>
Agbaria K.
Aleksiuk O.
Biali SE.
Böhmer V.
Frings M.
Thondorf I.
J. Org. Chem.
2001,
66:
2891
25a </A>
Ohseto F.
Murakami H.
Araki K.
Shinkai S.
Tetrahedron
Lett.
1992,
33:
1217
25b </A>
Grynszpan F.
Aleksiuk O.
Biali SE.
J.
Org. Chem.
1994,
59:
2070
<A NAME="RA30401ST-26">26 </A>
Katagiri H.
Iki N.
Hattori T.
Kabuto C.
Miyano S.
J. Am. Chem.
Soc.
2001,
123:
779
<A NAME="RA30401ST-27">27 </A>
Aleksiuk O.
Grynszpan F.
Biali SE.
J.
Org. Chem.
1993,
58:
1994
28a </A>
Kasturi TR.
Jayaram SK.
Pragnacharyulu PVP.
Sattigeri JA.
Reddy GM.
Kumar KA.
Tetrahedron
1993,
49:
113
28b </A>
Kasturi TR.
Kumar KA.
Pragnacharyulu PVP.
Tetrahedron
1993,
49:
125
28c </A>
Kasturi TR.
Kumar KA.
Pragnacharyulu PVP.
Sridevi G.
Tetrahedron
1993,
49:
135
<A NAME="RA30401ST-29">29 </A>
Van Gelder JM.
Aleksiuk O.
Biali SE.
J.
Org. Chem.
1996,
61:
8419
<A NAME="RA30401ST-30">30 </A>
Van Gelder JM.
Brenn J.
Thondorf I.
Biali SE.
J. Org. Chem.
1997,
62:
3511
<A NAME="RA30401ST-31">31 </A>
Dean FM.
Locksley HD.
J. Chem. Soc.
1963,
393
<A NAME="RA30401ST-32">32 </A>
Yamato T.
Hideshima C.
Prakash GKS.
Olah GA.
J. Org.
Chem.
1991,
56:
3192
33a </A>
Aleksiuk O.
Biali SE.
Tetrahedron
Lett.
1993,
34:
4857
33b </A> 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 </A>
Vol’eva VB.
Belostotskaya JS.
Ershov VV.
Russ. Chem.
Bull.
1996,
45:
744
34b </A>
Belostotskaya IS.
Vol’eva VB.
Komissarova NL.
Ershov VV.
Russ. Chem. Bull.
1996,
45:
987
35a </A>
Cafeo G.
Giannetto M.
Kohnke FH.
La Torre GL.
Parisi MF.
Menzer S.
White AJP.
Williams DJ.
Chem.-Eur.
J.
1999,
5:
356
35b </A>
Black DC.
Craig DC.
Kumar N.
Rezaie R.
Tetrahedron
1999,
55:
4803
<A NAME="RA30401ST-36">36 </A>
Agbaria K.
Biali SE.
J. Org. Chem.
2001,
66:
5482
<A NAME="RA30401ST-37">37 </A>
Carey FA.
Tremper HS.
J. Org. Chem.
1971,
36:
758
<A NAME="RA30401ST-38">38 </A>
Agbaria K.
Wöhnert J.
Biali SE.
J. Org. Chem.
2001,
66:
7059
<A NAME="RA30401ST-39">39 </A>
Middleton WJ.
J.
Org. Chem.
1975,
40:
574
40a </A>
Hammond GB.
de Mendonca DJ.
J.
Fluorine Chem.
2000,
102:
189
40b </A>
Gree D.
Gree R.
Boukerb A.
Laabassi M.
Tetrahedron Lett.
1997,
38:
6209
<A NAME="RA30401ST-41">41 </A>
Görmar G.
Seiffarth K.
Schultz M.
Zimmerman J.
Flämig G.
Macromol.
Chem.
1990,
191:
81
<A NAME="RA30401ST-42">42 </A>
Klenke B.
Näther C.
Friedrichsen W.
Tetrahedron
Lett.
1998,
39:
8967
<A NAME="RA30401ST-43">43 </A>
Middel O.
Greff Z.
Taylor NJ.
Verboom W.
Reinhoudt DN.
Snieckus V.
J. Org. Chem.
2000,
65:
667
<A NAME="RA30401ST-44">44 </A>
Scully DA.
Hamilton TM.
Bennett JL.
Org. Lett.
2001,
3:
2741
<A NAME="RA30402ST-45">45 </A>
Simaan S.
Agbaria K.
Biali SE.
J.
Org. Chem.
2002,
67:
6136
