Advanced Synthesis & Catalysis
10.1002/adsc.202000230
radical reacts with an alkyl iodide in a radical relay
process to provide an alkyl radical, which can attack
an alkene to afford a stabilized benzyl radical. Then
the benzyl radical reacts with the copper(II) species
solvent was removed under reduced pressure in a rotary
evaporator and the residue was purified by flash column
chromatography on silica gel (petroleum ether/EtOAc) to
afford the desired product.
(
III) to produce the asymmetric alkene
cyanoalkylation product and the regenerated active
LCu(I) catalyst. This process should be much faster
Acknowledgements
*
We thank the National Key R&D Program of China (Grant
No. 2017YFA0700103), the NSFC (Grant Nos. 21672213,
than I-atom abstraction from the fluoroalkyl iodide,
forming the ATRA product. Based on the proposed
catalytic cycle, LPO has significant roles in this highly
efficient radical asymmetric alkene cyanoalkylation.
21871258, 21922112), the Strategic Priority Research
Program of the Chinese Academy of Sciences (Grant No.
XDB20000000), the Haixi Institute of CAS (Grant No.
CXZX-2017-P01), and CAS-TWAS president program of the
UCAS for financial support. We also thank Yu-Ying Yang
from our institute for X-ray structure determinations.
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Scheme 3 Plausible mechanism
In summary, a novel copper-catalyzed radical
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Experimental Section
General procedure for Table 2: In a flame-dried Schlenk
tube equipped with a magnetic bar, (copper (I)-thiophene-2-
carboxylate (CuTc, 0.76 mg, 2 mol %) and L9 (1.7 mg, 2.4
[
mol %) were dissolved in CH
was stirred at rt for 20 min. Then diacyl peroxide (119 mg,
.5 equiv), styrene (21.2 mg, 0.2 mmol, 1.0 equiv),
fluoroalkyl iodide (141.2 mg, 2 equiv) and TMSCN (31 mg,
.5 equiv) were added. The reaction mixture was stirred
vigorously at rt for 3-4 h. After the reaction was completed,
the solvent was removed under reduced pressure in a rotary
evaporator, and the residue was purified by flash column
chromatography on silica gel (petroleum ether/EtOAc =
2
Cl
2
(1.0 mL), and the mixture
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1
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2
0:1) to give the desired product.
General procedure for Table 3: To a 25 mL flame-dried
Schlenk tube outfitted with a magnetic bar, CuTc (0.76 mg,
2
mol %), L9 (1.7 mg, 2.4 mol %), and DMF/toluene (0.5
mL:1.5 mL) were added and stirred at rt for 20 min. Then
diacyl peroxide (119 mg, 1.5 equiv), styrene (21.2 mg, 1.0
equiv), alkyl iodide (2 equiv) and TMSCN (31 mg, 1.5
equiv) were added and the reaction mixture was stirred
vigorously at rt for 3-4 h. After the reaction was completed,
2
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4
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