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from the environment to the catalyst. It is not clear why Au@
ICRM(2) had substrate reactivity unobserved in conventional
gold catalysts. The catalyst, nonetheless, did appear to be
“optimized” for the five-membered-ring enol lactone: not only
was 3 (and 8) much more reactive than 6 and 7, but also the
five-membered-ring lactone was the only one showing no
hydrolysis under identical reaction conditions. The most
interesting finding was the role of carboxylic acid of 3 in the
catalytic reaction. When it was responsible for the (fast)
binding of the substrate and meantime was the exact group to
be converted in the catalysis, the entire system behaved like a
catalytic nanomachine: the ICRM pulled the substrate to the
catalytic center and the appropriately positioned gold cluster
turned it into the product, which preferred the nonpolar
environment instead of the ICRM core and was thus rapidly
released. The result was extremely high activity compared to
conventional gold catalysts (for similar reactions) and highly
unusual zero-order kinetics. We believe these features are not
unique with the Au@ICRMs. Similar designs potentially can
turn other conventional catalysts into artificial “enzymes”
having novel, useful, biomimetic functions.
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ASSOCIATED CONTENT
* Supporting Information
■
S
(11) Lee, L.-C.; Zhao, Y. Org. Lett. 2012, 14, 784−787.
Experimental details for the syntheses and additional figures.
This material is available free of charge via the Internet at
(12) (a) Genin, E.; Toullec, P. Y.; Antoniotti, S.; Brancour, C.;
̂
Genet, J.-P.; Michelet, V. J. Am. Chem. Soc. 2006, 128, 3112−3113.
(b) Harkat, H.; Weibel, J. M.; Pale, P. Tetrahedron Lett. 2006, 47,
6273−6276. (c) Toullec, P. Y.; Genin, E.; Antoniotti, S.; Genet, J. P.;
Michelet, V. Synlett 2008, 707−711. (d) Neatu
Toullec, P. Y.; Genet
H.-P.; Parvulescu, V. I.; Michelet, V. Chem.−Eur. J. 2008, 14, 9412−
9418. (e) Harkat, H.; Dembele, A. Y.; Weibel, J. M.; Blanc, A.; Pale, P.
-Mendivil, E.; Toullec, P.
̧ , F.; Li, Z.; Richards, R.;
, J.-P.; Dumbuya, K.; Gottfried, J. M.; Steinruck,
̈
AUTHOR INFORMATION
Corresponding Author
■
̂
̂
Tetrahedron 2009, 65, 1871−1879. (f) Tomas
́
Notes
Y.; Díez, J.; Conejero, S.; Michelet, V.; Cadierno, V. Org. Lett. 2012,
The authors declare no competing financial interest.
14, 2520−2523.
(13) We did not attempt to exclude moisture in the reaction because
the strongly hydrophilic ICRM core was likely to retain water
molecules. The residual moisture present in the solvent and the
starting material could also be responsible for the hydrolysis of the
product, as suggested by entry 11, Table 1.
ACKNOWLEDGMENTS
■
We thank the U.S. Department of Energy, Office of Basic
Energy Sciences (grant DE-SC0002142), for supporting the
research.
(14) Because the reduction of the aurate was induced by the bromide
counteranion in the ICRM core, an increase of W0 increased the
amount of surfactant and thus the bromide counterion available for the
reduction.
(15) Zheng, J.; Nicovich, P. R.; Dickson, R. M. Annu. Rev. Phys.
Chem. 2007, 58, 409−431.
(16) Zheng, J.; Zhang, C.; Dickson, R. M. Phys. Rev. Lett. 2004, 93,
077402.
(17) The larger cluster size of Au@ICRM(2) at W0 = 10 was evident
from its longer emission wavelength (496 nm) (Figure S4).
(18) It is not entirely clear to us why ICRM(2) gave so much better
results than ICRM(1). We suspect that the different functional groups
in the headgroup of the cross-linkable surfactant might be responsible.
ICRM(1), for example, utilized thiol in the cross-linking. If any
residual thiol (e.g., from singly reacted DTT) was left in the core, it
might greatly suppress the most active catalytic site. In our hands, 1
mol% externally added DTT completely shut down the catalysis.
(19) For some examples of related encapsulated catalysts, see:
(a) Vriezema, D. M.; Aragones, M. C.; Elemans, J.; Cornelissen, J.;
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(b) Akiyama, R.; Kobayashi, S. Chem. Rev. 2009, 109, 594−642.
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