Organic Letters
Letter
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Figure 3. Water tolerance of our photoinduced, benzyne click
reaction. Benzotriazole yields were obtained as above in acetonitrile
solution with increasing water percentage. Above 70% water, the
starting materials were insoluble. All reactions were executed on 15
mM (0.75 μM compound 1) scale at room temperature using an LED
light source (3 min irradiation) and 1 equiv of azide.
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out to the limit of solubility of compound 1 in an acetonitrile/
water solution.
We expect this transformation to be a valuable addition to
the click chemistry toolbox for those interested in the
spatiotemporal control that light-induced reactions offer.
Although further optimization is required, we are confident
that this chemistry will ultimately prove useful for applications
in both organic and aqueous environments. The straightforward
synthesis of compound 1 offers considerable potential for
incorporation of tethers, targeting agents, and fluorophores
onto the aromatic core. Lastly, development of alternative
azides that lead to fluorescent benzotriazoles upon photoclick
conjugation will further expand the possible applications of this
chemistry. Efforts aimed at all of these improvements are
currently ongoing in our laboratory.
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ASSOCIATED CONTENT
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S
* Supporting Information
Experimental procedures, characterization of compounds, raw
data for yield calculations. This material is available free of
AUTHOR INFORMATION
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Corresponding Author
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
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This work was supported by start-up funding from the
University of Massachusetts, Amherst (to N.A.S. and J.J.C.).
The authors would like to thank Mr. Thomas Sullivan
(Berkshire Community College) for assistance in assembly
and use of the LED light source.
2005
dx.doi.org/10.1021/ol500389t | Org. Lett. 2014, 16, 2003−2005