Amphiphilic Resin-Supported Rhodium-Phosphine Catalysts
COMMUNICATIONS
EtOAc 1:1) to give hexamethyl benzenehexacarboxylate
Org. Chem. 1999, 64, 6921; d) H. Danjo, D. Tanaka, T.
Hayashi, Y. Uozumi, Tetrahedron 1999, 55, 14341.
(
7a) as a white solid; yield: 41 mg (57%).
[
4] a) Y. Uozumi, H. Danjo, T. Hayashi, Tetrahedron Lett.
1
998, 39, 8303 ± 8306; b) Y. Uozumi, K. Shibatomi, J. Am.
1
,4-Addition of ArB(OH) to Enones;[ General
15]
Chem. Soc. 2001, 123, 2919 ± 2920.
2
Procedure
[5] For examples of amphiphilic polymer-bound rhodium
complexes reported to date, see: a) D. E. Bergbreiter, Y.-
S. Li, Tetrahedron Lett. 1997, 38, 3703 ± 3706; b) A. N.
Ajjiou, H. Alper, J. Am. Chem. Soc. 1998, 120, 1466 ±
A Merrifield vessel was charged with 92 mg of resin-bound
complex (loading value: 0.16 mmol/g, 3 mol % Rh),
ArB(OH) (2.5 mmol), and 2 mL of distilled H Ounder a
3
2
2
1
468.
nitrogen atmosphere. To the mixture was added 8 (41 mL,
[
6] a) E. Bayer, W. Rapp, in Chemistry of Peptides and
Proteins, (Eds.: W. Voelter, E. Bayer, Y. A. Ovchinikov,
V. T. Iwanov), W. de Gruter, Berlin, 1986, Vol. 3, pp. 3;
b) W. Rapp, in Combinatorial Peptide and Nonpeptide
Libraries, (Ed.: G. Jung), VCH, Weinheim, 1996, pp. 425;
c) X. Du, R. W. Armstrong, J. Org. Chem. 1997, 62, 5678;
d) O. W. Gooding, S. Baudert, T. L. Deegan, K. Heisler,
J. W. Labadie, W. S. Newcomb, J. A. Porco, Jr., P.
Eikeren, J. Comb. Chem. 1999, 1, 113.
0.5 mmol), and the reaction mixture was shaken on a wrist-
action shaker at 25 8C for 24 h. The mixture was filtered and
the resin was extracted three times with chloroform (2 mL Â
10 min shaking). The combined extract was washed with
saturated NaHCO , then dried over Na SO and concentrated
under reduced pressure. The crude residue was chromato-
graphed on silica gel to give the 1,4-adduct 10.
3
2
4
[
7] For recent examples of rhodium-catalyzed hydroformy-
lation of alkenes with solid-supported catalysts, see: P.
Arya, G. Panda, N. V. Rao, H. Alper, S. C. Bourque,
L. E. Manzer, J. Am. Chem. Soc. 2001, 123, 2889 ± 2890,
and references cited therein.
Acknowledgements
This work was supported by a Grant-in Aid for Scientific
Research, the Ministry of Education, Japan. YU thanks the
RITE research program for partial financial support of this
work.
[8] For recent reviews on transition-metal-catalyzed [2 2
2
1
1
] cyclotrimerization, see: H.-W. Fr¸hauf, Chem. Rev.
997, 97, 523; M. Lautens, W. Klute, W. Tam, Chem. Rev.
996, 96, 49.
References and Notes
[
9] Hexafuctionalized benzenes have recently been gaining
[
1] For examples, see: a) P. T. Anastas, T. C. Williamson,
Eds.; Green Chemistry; ACS Symposium Series 626,
American Chemical Society: Washington, DC, 1996, and
references cited therein; b) C.-J. Li, T.-H. Chan, Organic
Reactions in Aqueous Media; Wiley, New York, 1997;
c) P. A. Grieco, (Ed.), Organic Synthesis in Water,
Kluwer Academic Publishers, Dordrecht, 1997;
d) W. A. Herrmann, C. W. Kohlpaintner, Angew. Chem.
Int. Ed. Engl. 1993, 32, 1524.
2] For recent reviews, see: a) B. A. Bunin, Combinatorial
Index, Academic Press, London, 1998; b) D. Obrecht,
J. M. Villalgordo, Solid-Supported Combinatorial and
Parallel Synthesis of Small-Molecular-Weight Compound
Libraries, Tetrahedron Organic Chemistry Series Vol. 17,
Elsevier, Oxford, 1998; c) F. Z. Dˆrwald, Organic Syn-
thesis on Solid Phase, Wiley-VCH, Weinheim, 2000;
d) D. E. De Vos, I. F. J. Vankelecom, P. A. Jacobs, (Eds.),
Chiral Catalyst Immobilization and Recycling, Wiley-
VCH, Weinheim, 2000.
use as a core molecule of benzene-based dendrimers; for
example, see: S. Hecht, J. M. J. Fre
¬
chet, J. Am. Chem.
Soc. 1999, 121, 4084 ± 4085.
[10] M. Sakai, H. Hayashi, N. Miyaura, Organometallics 1997,
16, 4229.
[11] For a recent review, see: T. Hayashi, Synlett 2001, SI, 879.
[12] We have recently reported that base-catalyzed 1,4-
addition (Michael reaction) in a single aqueous medium
using PS-PEG resin-anchored quaternary ammonium
hydroxides, see: K. Shibatomi, Y. Uozumi, Synlett 2000,
1643 ± 1645.
[13] Chemical Abstracts Registry numbers of all products
have been provided by the author: iso-5a, [93-53-8]; nor-
5a, [104-53-0]; iso-5b, [5405-83-4]; nor-5b, [20401-88-1];
iso-5c, [7786-29-0]; nor-5c, [124-19-6].
[14] Chemical Abstracts Registry numbers of all products
have been provided by the author: 7a, [6237-59-8]; 7b,
[992-04-1].
[15] Chemical Abstracts Registry numbers of all products
have been provided by the author: 10a, [2250-26-7]; 10b,
[3506-75-0]; 10c, [57132-19-1]; 12, [20795-53-3].
[
[
3] a) Y. Uozumi, H. Danjo, T. Hayashi, Tetrahedron Lett.
1
997, 38, 3557; b) Y. Uozumi, H. Danjo, T. Hayashi, J.
Org. Chem. 1999, 64, 3384; c) Y. Uozumi, T. Watanabe, J.
Adv. Synth. Catal. 2002, 344, 274 ± 277
277