Amphiphilic Block Polypeptide-Type Ligands for Micellar Catalysis in Water
COMMUNICATIONS
c) U. M. Lindstroem, in: Organic Reactions in Water,
Blackwell, Publishing Ltd., Oxford, UK, 2007; d) H. C.
Hailes, Org. Proc. Res. Devel. 2007, 11, 114.
be recycled several times without loss of activity. The
micelle formation is essential for the high catalytic ac-
tivity, as similar water-soluble catalysts showed very
low activity under the same reaction conditions. We
are currently exploring the scope of the new catalytic
systems.
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Experimental Section
General Experimental Procedures
All reactions were performed in ultrapure water (W
18 MOhm, <10 ppb TOC) obtained using Barnstead EASY-
pure II UF water purification system. Use of regular deion-
ized water gave comparable results. The reagents were pur-
chased from Sigma–Aldrich or Strem and used as received.
Complete experimental procedures are reported in the Sup-
porting Information.
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Conditions for Acetophenone Hydrogenation
All experiments were carried out in a 100-mL Fischer-Porter
high pressure glass reactor. The catalyst (0.9% mol) was dis-
solved in ultrapure water (3 mL) and 0.43 mmol (50 mL) of
acetophenone was added. The reactor was evacuated and
hydrogen gas introduced. The pressure was adjusted to
7 atm and the reaction mixture was stirred at room tempera-
ture for six hours. The product was extracted with diethyl
1
ether and analyzed by H NMR: d=7.37–7.25 (m, phenyl,
5H), 4.86 (q, J=6.5 Hz, CH-OH, 1H), 2.36 (s, OH, 1H),
1.46 (d, J=6.5 Hz, CH3, 3H). The reported yields are the
average of at least two runs using different catalyst batches.
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Conditions for ROMP of Norbornene
To
a Schlenk flask, containing norbornene (64.0 mg,
0.68 mmol) the catalyst (1%) in 5 mL of degassed water was
added via syringe. The reaction mixture was stirred at 508C
for 2 h. The flask was opened to air and the polymerization
was terminated by adding an excess of ethyl vinyl ether (100
equiv.). The contents were dissolved in THF and precipitat-
ed twice in water. The solids were filtered, washed with
water (20 mL), methanol (20 mL) and dried under vacuum
to yield poly(norbornene). The polymer was analyzed by
1H NMR spectroscopy and size exclusion chromatography
(THF) using polystyrene as reference.
[12] See for example, M. S. Kim, H. Hyun, Y. H. Cho, K. S.
Seo, W. Y. Jang, S. K. Kim, G. Khang, H. B. Lee,
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stra, Chem. Eur. J. 1999, 5, 2472–2482; b) T. Lamouille,
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[14] Pd-catalyzed ketone hydrogenations in organic media
also require relatively harsh reaction conditions: Y.-Q.
Wang, S.-M. Lu, Y.-G. Zhou, Org. Lett. 2005, 7, 3235–
3238.
Acknowledgements
We acknowledge the support from Israel Science Foundation.
References
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Adv. Synth. Catal. 2009, 351, 1499 – 1504
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