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COMMUNICATION
time for the the formation of α-ketoesters and propargyl
alcohols. Furthermore, the obvious isotopic effect (kH/kD value
of 6.14 determined by 1H NMR, see SI for detail) was observed
in the alkynylation of alcohols, implying that H-atom transfer is
the rate-determining step during the formation of propargyl
alcohols. On the other hand, although we cannot know
whether the formation of product F is derived from the
coupling of A and C, F failed to convert to 3aa under optimized
reaction conditions. Furthermore, we still do not understand
the relationship between the wavelength of the blue LED light
source and the homolysis of bromoalkynes.
4
Shaikh and B. König, Acc. Chem. Res., 2016, 49, 1566; (b) J.-R.
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Conclusions
In conclusion, we developed a catalyst and additive-free coupling
reactions of bromoalkynes and alcohols for the synthesis of α-
ketoesters and propargyl alcohols. This visible-light-promoted
chemoselective transformation was controlled by changing the
reaction atmosphere. N2 favoured propargyl alcohols formations via
a direct C−C coupling process, whereas an O2 atmosphere resulted
in the generation of α-ketoesters through oxidation of the C≡C/C−C
coupling pathway. The advantages of this chemoselective
photopromoted-synthetic platform include the use of a simple
procedure without the addition of catalysts or additives or the need
for harsh conditions. Further studies on visible-light promoted
reactions using bromoalkynes as precursors are underway in our
laboratory.
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(a) J. C. Tellis, C. B. Kelly, D. N. Primer, M. Jouffroy, N. R. Patel
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Conflicts of interest
The authors declare no competing financial interest.
9
Acknowledgements
We gratefully acknowledge the National Natural Science
Foundation of China (21772062, 21572078 and 21402061), the 10 For selected examples about synthesis of α-ketoesters: (a) K.
Scientific Research Project of Anhui Provincial Education
Department (KJ2015TD002) and the Natural Science Foundation of
Anhui (1708085MB45) for financial support of this work.
Furukawa, H. Inada, M. Shibuya and Y. Yamamoto, Org. Lett.,
2016, 18, 4230; (b) L. Liu, L. Du, D. Zhang-Negrerie, Y. Du and K.
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