Organic & Biomolecular Chemistry
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COMMUNICATION
Journal Name
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reductive reaction conditions, followed by the oxidative
cyclization with the trifluoromethyl-substituted alkenes to
generate A. The β-iodohydrin then reacts with the A to give a β-
hydroxyalkyl radical and a LNi(III) complex B through a single-
electron transfer. The addition of hydroxyalkyl radical to the
three-membered ring Ni(III) complex B to give a LNi(II) complex
C. Next, this Ni(II) species C undergoes β-fluorine elimination to
afford the corresponding products. Finally, the initial Ni(0)
complex is regenerated by reaction with the reducing agent.
DOI: 10.1039/D0OB00535E
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Wiles, J. P. Phelan and G. A. Molander, Chem. Commun., 2019, 55, 7599-
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3773; (h) Z. Lin, Y. Lan and C. Wang, Org. Lett., 2019, 21, 8316-8322; (i) J.-
L. Zeng, Y. Zhang, M.-M. Zheng, Z.-Q. Zhang, X.-S. Xue, F.-G. Zhang and J.-
A. Ma, Org. Lett., 2019, 21, 8244-8249; (j) L. Tang, Z.-Y. Liu, W. She and C.
Feng, Chem. Sci., 2019, 10, 8701-8705; (k) C. Li, J.-M. Yuan, W. Chen, Y.
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Conclusions
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(a) P. Crotti and M. Pineschi, in Aziridines and Epoxides in Organic Synthesis,
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Organic Synthesis, Wiley-VCH Verlag GmbH & Co. KGaA, 2006, pp. 37-71;
(e) B. Olofsson and P. Somfai, in Aziridines and Epoxides in Organic
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(a) M. Alam, C. Wise, C. A. Baxter, E. Cleator and A. Walkinshaw, Org.
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In summary, we have developed a nickel-catalyzed defluorinative
reductive cross-coupling of trifluoromethyl alkenes with epoxides.
Various substituted trifluoromethyl alkenes and epoxides were
found to be suitable reaction substrates. The reaction shows a high
degree of tolerance toward various sensitive functional groups.
This radical addition reaction has more excellent functional group
compatibility and higher yield over the previous Ni-catalyzed
reactions. It providied access to diverse array of functionalized
gem-difluoroalkene-containing alcohols, which are valuable
chemical feedstocks for synthetic chemistry and medicinal
chemistry. This study also provides a method for the modification
of complex organic molecules containing trifluoromethyl alkenes
or epoxides.
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This work was supported by the University Natural Science
Research Key Project of Anhui Province and Anhui Natural Science
Foundation.
Conflicts of interest
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12 (a) Y. Zhao and D. J. Weix, J. Am. Chem. Soc., 2013, 136, 48-51; (b) Y. Zhao
and D. J. Weix, J. Am. Chem. Soc., 2015, 137, 3237-3240.
There are no conflicts to declare.
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