O rP gl ea na is ce &d Bo i on mo to al e dc juu l sa tr mC haer mg i ins ts ry
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radical clock experiment was carried out and with
the system, the reaction furnished the ring-opening product
in 82% yield, further confirming the generation of a carbon-
centered radical via N-centered radical-initiated 1,5-hydrogen
atom transfer (Scheme 4b).
7 added into
DOI: 10.1039/D0OB00964D
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Scheme 5 Possible catalytic cycle.
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On the basis of observations mentioned above and previous
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With the addition of active Fe(II) catalyst, N-fluorosulfonamide
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3
For selected reviews of 1,5-HAT strategy, see: (a) J. Robertson,
A
would undergo single electron transfer (SET) with the iron and
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B
species
transfer,
δ-azido amine
C regioselectively. By iron-mediated redox azido
1
1-12
C
would be transformed into the final product of
D with concomitant regeneration of active Fe(II)
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,
6
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2
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Conclusions
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In summary, we have developed an aminyl radical-initiated
iron-catalyzed azidation of remote C(sp )-H bond with excellent
yield and broad substrate scope. This method has
demonstrated high catalytic reactivity, excellent regio-selective
control and low catalyst loading. Our radical relay strategy
offers highly regioselective functionalization of remote C(sp )-H
bonds, and provides an efficient way to synthesize δ-azido
amines. Mechanistic studies reveal that the selective cleavage
of inert remote C(sp )-H bond proceeds through a 1,5-HAT
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process. Further investigations on different functionalization of
3
remote C(sp )-H bonds are currently ongoing in our laboratory.
Conflicts of interest
The authors declare no competing financial interest.
4
For early examples on HLF reaction, see: (a) A. W. Hofmann,
Ber. Dtsch. Chem. Ges. 1883, 16, 558 (b) K. Lӧffler, C. Freytag,
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Acknowledgment
We gratefully acknowledge the National Science Foundation of
China (21971228, 21772187, 21522208) for financial support.
5
6
(a) Z. Li, Q. Wang, J. Zhu, Angew. Chem. Int. Ed. 2018, 57
,
1
3288; Angew. Chem. 2018, 130, 13472. (b) X. Bao, Q. Wang,
Notes and references
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| J. Name., 2012, 00, 1-3
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