E
G. Zhou et al.
Letter
Synlett
As shown in Figure 3, there was not much difference be-
tween the solubilities of 4-iodoanisole in pure water and
the aqueous solution of carbohydrate-derived alkylamine
L5 from 70 to 85 °C. Surprisingly, at 90 °C, the mass of 4-io-
doanisole dissolved in the aqueous solution (a) increased
dramatically over the pure water (b). Thus, it was speculat-
ed that L5 could promote the solubility of 4-iodoanisole in
water at 90 °C. This increased solubility also explained why
the coupling of 4-iodoanisole gave better results at 90 °C
than at 70 and 80 °C (Table 1, entries 16–18). Once 4-iodo-
anisole comes in contact with L5, it is distributed between
bulk water and L5 depending on its polarity or charge.
Thus, in this in-water catalytic system, carbohydrate-de-
rived alkylamine L5 plays the role of chelating copper and
promoting the dissolution of 4-iodoanisole in water.
ment of Energy, National Nuclear Security Administration grant (DE-
NA 0001861 & DE-NA 0002630).
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References and Notes
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Figure 3 Solubility of 4-iodoanisole in two different solvents from 70
to 90 °C. (a) The aqueous solution of L5; (b) pure water.
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In summary, we have described a green and degradable
carbohydrate-derived alkylamine for copper-catalyzed Ull-
mann C–N coupling in water, without the presence of sur-
factant.33,34 Extensive works were performed by employing
various aryl iodides and N-nucleophiles as substrates. Mod-
erate to excellent yields are achieved in this in-water cata-
lytic system. Moreover, the in-water coupling strategy was
expanded successfully to the reaction of indoles with 4-io-
doanisole. By measuring the solubility, it is speculated that
the carbohydrate-based ligand formed an intermolecular
force together with water to increase the solubility of 4-io-
doanisole in water. This would eventually make the Ull-
mann C–N coupling of aryl halides with N-nucleophiles
more efficient in water.
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Funding Information
(17) (a) Mukhopadhyay, C.; Tapaswi, P. K.; Butcher, R. J. Org. Biomol.
Chem. 2010, 20, 4720. (b) Yong, F. F.; Teo, Y. C.; Tay, S. H.; Tan, Y.
H.; Lim, K. H. Tetrahedron Lett. 2011, 11, 1161. (c) Krause, N.
Curr. Opin. Green .Sustainable Chem. 2017, 18.
This research is sponsored by China National Key Research and inven-
tion program of the thirteenth Five-Year Plan (2017YFD0200707), the
Natural Science Foundation of China (21606104), the Opening Foun-
dation from Zhejiang Provincial Key Laboratory of Advanced Chemical
Engineering Manufacture Technology (ACEMT-17-03) and US Depart-
© Georg Thieme Verlag Stuttgart · New York — Synlett 2018, 29, A–F