vessel received a CH2Cl2 (3 mL) solution of 2-bromoacetic acid
(0.57 g, 4 mmol) and diisopropylcarbodiimide, DIC (0.75 mL,
4.6 mmol), maintained at 0 ꢀC for 20 min. After 1 h of stirring
at room temperature, the beads were washed several time with
DMF and CH2Cl2 . The second vessel received NEt3 (0.8 mL,
5 mmol) and CH2Cl2 (6 ml), then 6-bromohexanoylchloride
(0.6 mL, 4 mmol) was slowly added to control the temperature
rise. After 2 h of stirring at room temperature the beads were
drained and washed with DMF and CH2Cl2 . For both vessels
the Kaiser test was negative.
All beads were mixed together and divided into 20 equiva-
lent portions (0.033 g, 0.033 mmol). Each vessel received
CH2Cl2 (1 mL), a specific amino alcohol (0.33 mmol) and
DIEA (0.5 mmol). After 15 h, the beads were drained and were
carefully washed with DMF and CH2Cl2 . Then a specific
tagging procedure was applied to each vessel. All the beads
were then mixed. The same experimental protocol used for the
synthesis of 1b-Rh was applied to these beads to generate the
forty member library.
References
1
(a) C. U. Pittman, Jr., in Comprehensive, Organometallic Chem-
istry, 1982, vol. 8, pp. 553–611; (b) O. Lavastre, P. Bebin,
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29–34.
2
3
R. B. Merrifield, J. Am. Chem. Soc., 1963, 85, 2149–2154.
P. Hodge and D. C. Sherrington, Polymer-Supported Reactions in
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4
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E. Atherton and R. C. Sheppard, Solid Phase Peptide Synthesis: A
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(a) A. Furka, F. Sebestyen, M. Asgedom and G. Dibo, Int. J.
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E. M. Hersh, V. J. Hruby, W. M. Kazmierski and R. J. Knapp,
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P. Murer, K. Lewandowski, F. Svec and J. M. J. Frechet, Chem.
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(a) S. B. Roscoe, J. M. J. Frechet, J. F. Walser and A. J. Dias,
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Preparation of the supported catalyst 7-Rh
2-Bromoacetic acid (0.117 g, 0.8 mmol) was reacted with DIC
(309 mL, 1.9 mmol) in CH2Cl2 at 0 ꢀC for 20 min. This solution
was added to beads I (0.138 mmol of –NH2 groups). After 1 h
at room temperature, the solution was drained and the beads
were carefully washed with DMF (2 ꢁ 30 min) then CH2Cl2
(2 ꢁ 10 min). The Kaiser test was negative. These beads were
reacted with H2NCH2CH2OCH2CH2NH2 (0.138 mL, 1.38
mmol) in the presence of DIEA (0.360 mL, 2.07 mmol) in
CH2Cl2 at room temperature for 16 h. The beads were care-
fully washed with DMF (1 h) then with CH2Cl2 . In a glove
box, PPh2Cl (80 mL, 0.44 mmol) in 3 mL of toluene was added
to these beads in the presence of triethylamine (190 mL, 1.24
mmol). After 4 h at room temperature, the solution was
drained and the beads were washed with toluene (1 h) and
CH3CN (15 min), then dried. 31P NMR of 7 (C6D6): d: 114
(OP); 63 (NP). [Rh(cod)Cl]2 (100 mg, 0.2 mmol) was reacted
with beads 7 in toluene (3 mL) for 4.5 h at room temperature,
then 1 ml of MeOH was added. After 1 h the solution was
drained and the orange beads 7-Rh were washed with toluene
31P NMR of 7-Rh (C6D6): d: 120 (br signal).
9
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Acknowledgements
Financial support from Elf Atochem and NIH GM 59417–03
is acknowledged. O. L. is grateful to the CNRS for a one year
(mise a disposition) Research Associate at UNC Chapel Hill.
J. M. is grateful to the David and Lucile Packard Foundation,
Glaxo-Smith-Kline (Scholars Award), Dow Chemical (Inno-
vation Recognition Program), and DuPont (Young Investi-
gator Program).
15 H. Brunner and U. Obermann, Chem. Ber., 1989, 499–507.
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G. Asouline, R. Kobayashi, M. Wigler and W. C. Still, Proc. Natl.
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18 S. R. Wilson and A. W. Czarnik, Combinatorial Chemistry:
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New J. Chem., 2002, 26, 745–749
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