Copper-Catalyzed Radical 1,2-Carbotrifluoromethylselenolation of Alkenes under Ambient Conditions

Article abstract of DOI:10.1021/acs.orglett.1c00436

We have described a copper-catalyzed radical 1,2-carbotrifluoromethylselenolation of alkenes using the readily available alkyl halides and (Me4N)SeCF3 salt. Critical to the success is the use of a proline-based N,N,P-ligand to enhance the reducing capabil

Full text of DOI:10.1021/acs.orglett.1c00436

pubs.acs.org/OrgLett
Letter
Copper-Catalyzed Radical 1,2-Carbotrifluoromethylselenolation of
Alkenes under Ambient Conditions
Jiao Yu, Ning-Yuan Yang, Jiang-Tao Cheng, Tian-Ya Zhan, Cheng Luan, Liu Ye, Qiang-Shuai Gu,
Zhong-Liang Li,* Guo-Qiang Chen,* and Xin-Yuan Liu*
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ABSTRACT: We have described a copper-catalyzed radical 1,2-
carbotrifluoromethylselenolation of alkenes using the readily available alkyl
halides and (Me4N)SeCF3 salt. Critical to the success is the use of a proline-
based N,N,P-ligand to enhance the reducing capability of copper for easy
conversion of diverse alkyl halides to the corresponding radicals via a single-
electron transfer process. The reaction features a broad substrate scope,
including various mono-, di-, and trisubstituted alkenes with many functional
groups.
lkenes are one of the most prevailing building blocks in
organic synthesis, and straightforward transformation of
Scheme 1. Radical 1,2-Trifluoromethylselenolation of
Alkenes
A
alkenes is a powerful tool to allow for the expedient synthesis
of complex molecules from simple feedstocks.1 Among
intensive research, the radical-initiated 1,2-difunctionalization
of alkenes to install two new chemical bonds at the vicinal
positions of alkenes has emerged as an appealing strategy due
to its high reactivity and good functional group tolerance.2
Since the CF3Se group shows promising lipophilicity and
electronic characteristics, which are beneficial to the develop-
ment of bioactive compounds,3 the CF3Se group might be
promising in pharmaceutical research. In this aspect, the
radical-initiated 1,2-carbotrifluoromethylselenolation of al-
kenes to introduce a trifluoromethylselenyl group4−6 as well
as an additional functional group has gained increasing interest
among chemists. Although this strategy has been realized in
several reports,7 they have to use either the trifluoromethyl
tolueneselenosulfate (TsSeCF3) reagent which needs tedious
synthesis7a,b or a stoichiometric amount of bpyCuSeCF3
complex (Scheme 1A).7c In addition, a high temperature or
light irradiation strategy should be utilized in order to initiate
the radical process (Scheme 1A).7 Therefore, a catalytic radical
1,2-carbotrifluoromethylselenolation of alkenes to provide a
number of β-functionalized SeCF3 compounds from readily
available trifluoromethylselenolation reagents and diverse
radical precursors under ambient conditions is highly desirable.
Our group has focused on the copper-catalyzed radical 1,2-
difunctionalization of alkenes to generate complex compounds
from readily available starting materials.8 During this course,
we found that a multidentate N,N,P-ligand could significantly
enhance the reducing capability of the copper catalyst, thus
easily converting the mildly oxidative alkyl halides to alkyl
radicals via a single-electron transfer (SET) process under
ambient conditions.8e Given that the (Me4N)SeCF3 salt is a
readily accessible and thermally stable trifluoromethyl-
selenolation reagent,9 we wondered whether a copper-
catalyzed radical 1,2-carbotrifluoromethylselenolation of al-
kenes could be achieved from (Me4N)SeCF3 and diverse alkyl
halides. However, the identification of a suitable ligand for
radical generation from various mildly oxidative alkyl halides
with copper catalyst is a challenging task.10 Herein, we describe
a copper/N,N,P-ligand catalysis for a radical 1,2-carbotrifluoro-
methylselenolation of alkenes from the readily available
(Me4N)SeCF3 salt and diverse alkyl halides under ambient
conditions (Scheme 1B).
Based on our assumption, we tried to initiate the alkene 1,2-
carbotrifluoromethylselenolation of 4-phenyl-substituted styr-
ene 1a, with (Me4N)SeCF3 2a and ICF2CO2Et 3a in the
Received: February 5, 2021
Published: February 24, 2021
https://dx.doi.org/10.1021/acs.orglett.1c00436
© 2021 American Chemical Society
Org. Lett. 2021, 23, 1945−1949
1945

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presence of 10 mol % Cu2O and 1.0 equiv of Cs2CO3 by
searching for a suitable ligand (Table 1). Bidentate ligands,
conditions (Table 1, entry 8). Control experiments were
conducted to investigate the sensitivity of the reaction.
Enhancing the reaction temperature to 60 °C dramatically
increased the reaction rate, and a 92% yield of 4 can be
obtained after 4 h (Table 1, entry 15). The exposure to
moisture or air conditions greatly affected the reaction
efficiency (Table 1, entries 16 and 17). The yield also
decreased in a dilute condition (Table 1, entry 18). When
Cu2O was reduced to 1 mol %, the reaction afforded almost no
product (Table 1, entry 19).
a
Table 1. Screening of Reaction Conditions
Having established the optimal reaction conditions, we next
investigated the scope of alkenes (Table 2). The arylated
a
Table 2. Substrate Scope of Alkenes
b
Entry
L
Base
[Cu]
Solvent
Yield (%)
1
2
3
4
5
6
7
8
L1
L2
L3
L4
L5
L6
L7
L8
L8
L8
L8
L8
L8
L8
L8
L8
L8
L8
L8
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Na2CO3
K3PO4
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cu2O
Cu2O
Cu2O
Cu2O
Cu2O
Cu2O
Cu2O
Cu2O
Cu2O
Cu2O
CuI
CuCN
Cu2O
Cu2O
Cu2O
Cu2O
Cu2O
Cu2O
Cu2O
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
THF
0
trace
trace
0
0
0
0
87
84
5
9
10
11
12
13
14
15
16
17
18
7
86
11
78
92
15
0
DCM
c
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
d
e
f
43
0
g
19
a
Reaction conditions: 1a (0.10 mmol), 2a (0.15 mmol), 3a (0.30
mmol), [Cu] (10 mol %), L (15 mol %), and base (1.0 equiv) in
b
solvent (1.5 mL) at room temperature for 48 h under argon. Yields
were determined by 19F NMR spectroscopy using PhCF3 as an
c
internal standard. Reaction was conducted at 60 °C (oil bath) for 4
d
e
h. H2O (3.0 equiv) was added. Reaction was performed under an air
f
g
atmosphere. Solvent (3.0 mL) was added. [Cu] (1 mol %) and L8
(1.5 mol %) were used.
such as bipyridine L1 and 1,10-phenanthroline ligands L2−L4
with electron-donating or -withdrawing groups, could not
afford the desired product 4 in a large amount (Table 1, entries
1−4). Further trials with the Xantphos ligand L5 and
tripyridine-tpye ligand L6 revealed that they were not effective
for the reaction (Table 1, entries 5 and 6). The N,N,P-ligand
L7, which was utilized in our previous 1,2-carboalkynylation
reaction,8e proved to be inapplicable in the 1,2-carbotrifluoro-
methylselenolation as well (Table 1, entry 7). We then tried
the proline-based N,N,P-ligand L8,11 and the reaction
proceeded smoothly to deliver the desired product 4 in 87%
yield (Table 1, entry 8). Further screening of different bases,
copper salts, and solvents led to the optimal reaction
conditions as follows: the reaction of 1a, 2a, and 3a in the
presence of 10 mol % Cu2O, 15 mol % L8, and 1.0 equiv of
Cs2CO3 in 1,4-dioxane gave rise to the carbotrifluoromethyl-
selenolation product 4 in 87% NMR yield under ambient
a
Reaction conditions: 1 (0.20 mmol), 2a (0.30 mmol), 3a (0.60
mmol), Cu2O (10 mol %), L8 (15 mol %), and Cs2CO3 (0.20 mmol)
in 1,4-dioxane (3.0 mL) at room temperature for 48 h under argon.
b
c
Reaction was performed on a gram scale and 2a (1 g) was used. 2,2-
Dimethyl-3-methylenedec-4-yne was used as the starting alkene.
d
CCl3CF3 was used as the radical precursor.
alkenes with electron-rich or -deficient substituents at the para,
meta, or ortho position of the aryl ring were applicable for the
reaction to provide 4−15 in 63−95% yields. The reaction
worked well on a gram scale, providing 4 with a slightly
decreased yield (66%). A wide range of functional groups are
well tolerated, such as the methoxyl (5−7), phenoxyl (8),
halide (10 and 11), cyano (12), and nitro (13) group. Besides,
the alkenes possessing a polycyclic aryl ring were also suitable
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for the reaction to generate 14 and 15 in excellent yields. For
the estrone-derived alkene substrate, the reaction afforded 16
as a diastereomeric mixture (dr = 1:1). Furthermore, the
alkenes containing heteroarenes, such as benzofuran and
quinoline, are also amenable to the reaction to give 17 and
18 in good yields. In addition to the monosubstituted alkenes,
the 1,1-disubstituted alkenes proceeded smoothly under the
standard reaction conditions to furnish 19 in 86% yield.
Moreover, the 1,2-disubstituted and trisubstituted alkenes also
underwent the reaction to give rise to 20 and 21 with good
diastereoselectivity, albeit in moderate yields. Notably, the
reactions were not limited to arylated alkenes. For example, the
electron-rich enamine was a viable substrate to deliver 22 in
44% yield. The electron-deficient alkene also worked well to
provide the corresponding product 23 in 53% yield.
Interestingly, the 1,4-carbotrifluoromethylselenolation was
observed in the case of the 1,3-enyne substrate to furnish the
allene product 24. A preliminary trial with (Me4N)SCF3 2b as
the nucleophile under the otherwise identical conditions
demonstrated that the protocol was also applicable for the
alkene 1,2-carbotrifluoromethylthiolation to provide the SCF3-
containing products 25 and 26 in good yields.
selenolation process to afford 27−29 in good yields under
the otherwise identical conditions. Further, CCl3CF3 was also a
suitable radical precursor for the reaction to provide 30−32 in
76−90% yields. In addition, tert-butyl α-bromoisobutyrate was
also a viable radical precursor, though the desired products
33−35 were formed in slightly lower yields. Notably, the
radical precursors were not limited to alkyl halides and the
Togni’s reagent 3e was also suitable for the reaction to deliver
36 in 34% yield.
In order to probe the possible mechanism, we performed the
control experiments. The reaction of the radical clock substrate
37 with 2a and 3a led to the radical addition/ring-opening/
nucleophile trapping product 38, clearly illustrating a radical
process (Scheme 2A). This is further demonstrated by the
Scheme 2. Mechanistic Study and Proposal
Encouraged by these results, we further focused on
expanding the scope of radical precursors (Table 3). C4F9I is
a
Table 3. Substrate Scope of Radical Precursors
radical inhibition experiment with (2,2,6,6-tetramethylpiper-
idin-1-yl)oxyl (TEMPO), which provided the TEMPO-
trapping product 39, and no desired product 4 was observed
(Scheme 2B). Based on these results, we proposed a plausible
reaction mechanism (Scheme 2C). Copper salt was first
transformed into active catalytic species I in the presence of
base and the ligand L8, which then reacted with (Me4N)SeCF3
to form the CuI Intermediate II.13 A SET process occurred
between the CuI complex II and alkyl halides to generate the
CuII complex III and the corresponding alkyl radical ·R4.10
Afterward, the ·R4 radical added to the alkenes 1 at the less
sterically hindered positions to form the alkyl radical
intermediate IV.8 The resulting radical species further reacted
with the CuII complex III to furnish the desired products and
release the CuI complex for the next catalytic cycle.14 With
alkyl bromide or iodide as the radical precursors, although we
cannot detect the bromide or iodide intermediate, the atom-
transfer process followed by substitution by the SeCF3 anion
could not be excluded.15
a
Reaction conditions: 1 (0.20 mmol), 2a (0.30 mmol), 3 (0.60
mmol), Cu2O (10 mol %), L8 (15 mol %), and Cs2CO3 (0.20 mmol)
in 1,4-dioxane (3.0 mL) at room temperature for 48 h under argon.
a cheap reagent which is used to introduce a C4F9 group into a
molecule, but its reactivity is slightly low and a photo-
irradiation protocol is necessary to initiate the generation of
the C4F9 radical species.12 Having the idea that the N,N,P-
ligand could enhance the reducing capability of copper catalyst,
we targeted C4F9I as the radical source. To our delight, it could
be successfully applied to the 1,2-carbotrifluoromethyl-
In summary, we have achieved a copper-catalyzed radical
1,2-carbotrifluoromethylselenolation of alkenes from the read-
ily available alkyl halides and (Me4N)SeCF3 salt, providing
expedient access to a range of SeCF3-containing compounds.
The utilization of a proline-based N,N,P-ligand is crucial to the
success in that it can greatly enhance the reducing capability of
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Notes
the copper catalyst to convert the mildly oxidative radical
precursors to the corresponding radicals via a SET process. A
wide array of mono-, di-, and trisubstituted alkenes and alkyl
halides are accommodated in the reaction.
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
Financial support from the National Natural Science
Foundation of China (Nos. 21801116, 22025103, and
21831002), Guangdong Provincial Key Laboratory of Catalysis
(No. 2020B121201002), Guangdong Innovative Program (No.
2019BT02Y335), Distinguished Young Talents in Higher
Education of Guangdong, China (2017KQNCX174), Shenz-
hen Special Funds (No. JCYJ20200109141001789), SUSTech
Special Fund for the Construction of High-Level Universities
(No. G02216303), and Research Start-Up Funding of SZU
(8530300000137 and 860000002110230). The authors
appreciate the assistance of SUSTech Core Research Facilities.
ASSOCIATED CONTENT
■
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* Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.orglett.1c00436.
Experimental procedures, characterization of com-
pounds (PDF)
AUTHOR INFORMATION
■
Corresponding Authors
REFERENCES
Zhong-Liang Li − Academy for Advanced Interdisciplinary
Studies and Department of Chemistry, Southern University of
Science and Technology, Shenzhen 518055, China;
Email: lizl@sustech.edu.cn
Guo-Qiang Chen − College of Chemistry and Environmental
Engineering, Shenzhen University, Shenzhen 518071, China;
Email: gqchen@szu.edu.cn
Xin-Yuan Liu − Shenzhen Grubbs Institute and Department of
Chemistry, Guangdong Provincial Key Laboratory of
Catalysis, Southern University of Science and Technology,
Shenzhen 518055, China; orcid.org/0000-0002-6978-
6465; Email: liuxy3@sustech.edu.cn
■
(1) For selected reviews, see: (a) Guo, H.-C.; Ma, J.-A. Catalytic
Asymmetric Tandem Transformations Triggered by Conjugate
Additions. Angew. Chem., Int. Ed. 2006, 45, 354−366. (b) Chemler,
S. R.; Fuller, P. H. Heterocycle Synthesis by Copper Facilitated
Addition of Heteroatoms to Alkenes, Alkynes and Arenes. Chem. Soc.
Rev. 2007, 36, 1153−1160. (c) McDonald, R. I.; Liu, G.; Stahl, S. S.
Palladium(II)-Catalyzed Alkene Functionalization via Nucleopallada-
tion: Stereochemical Pathways and Enantioselective Catalytic
Applications. Chem. Rev. 2011, 111, 2981−3019. (d) Nie, J.; Guo,
H.-C.; Cahard, D.; Ma, J.-A. Asymmetric Construction of Stereogenic
Carbon Centers Featuring a Trifluoromethyl Group from Prochiral
Trifluoromethylated Substrates. Chem. Rev. 2011, 111, 455−529.
(e) Dong, Z.; Ren, Z.; Thompson, S. J.; Xu, Y.; Dong, G. Transition-
Metal-Catalyzed C−H Alkylation Using Alkenes. Chem. Rev. 2017,
117, 9333−9403.
Authors
Jiao Yu − College of Chemistry and Environmental
Engineering, Shenzhen University, Shenzhen 518071, China;
College of Physics and Optoelectronic Engineering, Shenzhen
University, Shenzhen 518060, China; Shenzhen Grubbs
Institute and Department of Chemistry, Guangdong
Provincial Key Laboratory of Catalysis, Southern University
of Science and Technology, Shenzhen 518055, China
Ning-Yuan Yang − Shenzhen Grubbs Institute and
Department of Chemistry, Guangdong Provincial Key
Laboratory of Catalysis, Southern University of Science and
Technology, Shenzhen 518055, China
Jiang-Tao Cheng − Shenzhen Grubbs Institute and
Department of Chemistry, Guangdong Provincial Key
Laboratory of Catalysis, Southern University of Science and
Technology, Shenzhen 518055, China
Tian-Ya Zhan − Shenzhen Grubbs Institute and Department
of Chemistry, Guangdong Provincial Key Laboratory of
Catalysis, Southern University of Science and Technology,
Shenzhen 518055, China
Cheng Luan − Shenzhen Grubbs Institute and Department of
Chemistry, Guangdong Provincial Key Laboratory of
Catalysis, Southern University of Science and Technology,
Shenzhen 518055, China
Liu Ye − Academy for Advanced Interdisciplinary Studies and
Department of Chemistry, Southern University of Science and
Technology, Shenzhen 518055, China
Qiang-Shuai Gu − Academy for Advanced Interdisciplinary
Studies and Department of Chemistry, Southern University of
Science and Technology, Shenzhen 518055, China;
orcid.org/0000-0002-3840-425X
(2) For selected reviews, see: (a) Chu, L.; Qing, F.-L. Oxidative
Trifluoromethylation and Trifluoromethylthiolation Reactions Using
(Trifluoromethyl)trimethylsilane as a Nucleophilic CF3 Source. Acc.
Chem. Res. 2014, 47, 1513−1522. (b) Merino, E.; Nevado, C.
Addition of CF3 across Unsaturated Moieties: a Powerful Function-
alization Tool. Chem. Soc. Rev. 2014, 43, 6598−6608. (c) Charpentier,
J.; Fruh, N.; Togni, A. Electrophilic Trifluoromethylation by Use of
̈
Hypervalent Iodine Reagents. Chem. Rev. 2015, 115, 650−682.
(d) Zeng, Y.; Ni, C.; Hu, J. Recent Advances in the One-Step
Synthesis of Distally Fluorinated Ketones. Chem. - Eur. J. 2016, 22,
3210−3223. (e) Jiang, H.; Studer, A. Intermolecular Radical
Carboamination of Alkene. Chem. Soc. Rev. 2020, 49, 1790−1811.
(f) Ouyan, X.-H.; Song, R.-J.; Li, J.-H. Developments in the
Chemistry of α-Carbonyl Alkyl Bromides. Chem. - Asian J. 2018,
13, 2316−2332. (g) Lin, J.; Song, R.-J.; Li, J.-H. Recent Advances in
the Intermolecular Oxidative Difunctionalization of Alkenes. Chem.
Rec. 2019, 19, 440−451. (h) Wu, X.; Zhu, C. Radical-Mediated
Remote Functional Group Migration. Acc. Chem. Res. 2020, 53,
1620−1636. (i) Wu, X.; Wu, S.; Zhu, C. Radical-mediated
difunctionalization of unactivated alkenes through distal migration
of functional groups. Tetrahedron Lett. 2018, 59, 1328−1336.
(3) (a) Tan, K.-L.; Dong, T.; Zhang, X.-Q.; Zhang, C.-P. Oxidative
trifluoromethylselenolation of 1,3-dicarbonyls with [Me4N][SeCF3].
Org. Biomol. Chem. 2020, 18, 1769−1779. (b) Aufiero, M.; Sperger,
T.; Tsang, A. S.-K.; Schoenebeck, F. Highly Efficient C−SeCF3
Coupling of Aryl Iodides Enabled by an Air-Stable Dinuclear PdI
Catalyst. Angew. Chem., Int. Ed. 2015, 54, 10322−10326.
(4) For selected examples on nucleophilic trifluoromethyl-
selenolation reactions, see: (a) Chen, C.; Hou, C.; Wang, Y.; Hor,
T. S.; Weng, Z. Copper-Catalyzed Trifluoromethylselenolation of Aryl
and Alkyl halides: the Silver Effect in Transmetalation. Org. Lett.
2014, 16, 524−527. (b) Wang, Y.; You, Y.; Weng, Z. Alkynyl
Trifluoromethyl Selenide Synthesis via Oxidative Trifluoromethylse-
lenolation of Terminal Alkynes. Org. Chem. Front. 2015, 2, 574−577.
(c) Matheis, C.; Wagner, V.; Goossen, L. J. Sandmeyer-Type
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.orglett.1c00436
1948
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Org. Lett. 2021, 23, 1945−1949

Organic Letters
pubs.acs.org/OrgLett
Letter
Trifluoromethylthiolation and Trifluoromethylselenolation of
(Hetero)Aromatic Amines Catalyzed by Copper. Chem. - Eur. J.
2016, 22, 79−82. (d) Fang, W. Y.; Dong, T.; Han, J. B.; Zha, G. F.;
Zhang, C. P. Expeditious Trifluoromethylthiolation and Trifluor-
omethylselenolation of Alkynyl(phenyl)iodoniums by [XCF3](−) (X
= S, Se) Anions. Org. Biomol. Chem. 2016, 14, 11502−11509.
(5) For selected examples on electrophilic trifluoromethyl-
selenolation reactions, see: (a) Glenadel, Q.; Ismalaj, E.; Billard, T.
Benzyltrifluoromethyl (or Fluoroalkyl) Selenide: Reagent for Electro-
philic Trifluoromethyl (or Fluoroalkyl) Selenolation. J. Org. Chem.
2016, 81, 8268−8275. (b) Ghiazza, C.; Billard, T.; Tlili, A.
Trifluoromethyl- and Fluoroalkylselenolations of Alkynyl Copper(I)
Compounds. Chem. - Eur. J. 2017, 23, 10013−10016. (c) Massolo, E.;
Pirola, M.; Rossi, S.; Benincori, T. Metal-Free Alpha Trifluorome-
thylselenolation of Carbonyl Derivatives under Batch and Flow
Conditions. Molecules 2019, 24, 726.
(6) For selected examples on radical trifluoromethylselenolation
reactions, see: (a) Ghiazza, C.; Debrauwer, V.; Monnereau, C.;
Khrouz, L.; Médebielle, M.; Billard, T.; Tlili, A. Visible-Light-
Mediated Metal-Free Synthesis of Trifluoromethylselenolated Arenes.
Angew. Chem., Int. Ed. 2018, 57, 11781−11785. (b) Modak, A.;
Pinter, E. N.; Cook, S. P. Copper-Catalyzed, N-Directed Csp3−H
Trifluoromethylthiolation (−SCF3) and Trifluoromethylselenation
(−SeCF3). J. Am. Chem. Soc. 2019, 141, 18405−18410.
(7) (a) Lei, Y.; Yang, J.; Wang, Y.; Wang, H.; Zhan, Y.; Jiang, X.; Xu,
Z. Metal-Free Fluoroalkylfluoroalkylselenolation of Unactivated
Alkenes: Incorporation of Two Photoinduced Processes. Green
Chem. 2020, 22, 4878−4883. (b) Ghiazza, C.; Monnereau, C.;
Khrouz, L.; Médebielle, M.; Billard, T.; Tlili, A. New Avenues in
Radical Trifluoromethylselenylation with Trifluoromethyl Toluenese-
lenosulfonate. Synlett 2019, 30, 777−782. (c) Zhang, B. S.; Gao, L. Y.;
Zhang, Z.; Wen, Y. H.; Liang, Y. M. Three-Component Difluor-
oalkylation and Trifluoromethylthiolation/Trifluoromethylselenola-
tion of pi-Bonds. Chem. Commun. 2018, 54, 1185−1188.
Halides Using the Readily Available [Me4N][SeCF3] Salt. Org. Lett.
2017, 19, 3919−3922. (d) Han, Q.-Y.; Tan, K.-L.; Wang, H.-N.;
Zhang, C.-P. Organic Photoredox-Catalyzed Decarboxylative Tri-
fluoromethylselenolation of Aliphatic Carboxylic Acids with [Me4N]-
[SeCF3]. Org. Lett. 2019, 21, 10013−10017.
(10) (a) Patten, T. E.; Matyjaszewski, K. Copper(I)-Catalyzed Atom
Transfer Radical Polymerization. Acc. Chem. Res. 1999, 32, 895−903.
(b) Boyer, C.; Corrigan, N. A.; Jung, K.; Nguyen, D.; Nguyen, T.-K.;
Adnan, N. N. M.; Oliver, S.; Shanmugam, S.; Yeow, J. Copper-
Mediated Living Radical Polymerization (Atom Transfer Radical
Polymerization and Copper(0) Mediated Polymerization): From
Fundamentals to Bioapplications. Chem. Rev. 2016, 116, 1803−1949.
(11) Cao, Y.-X.; Dong, X.-Y.; Yang, J.; Jiang, S.-P.; Zhou, S.; Li, Z.-
L.; Chen, G.-Q.; Liu, X.-Y. A Copper-Catalyzed Sonogashira Coupling
Reaction of Diverse Activated Alkyl Halides with Terminal Alkynes
Under Ambient Conditions. Adv. Synth. Catal. 2020, 362, 2280−
2284.
(12) Guo, Q.; Wang, M.; Peng, Q.; Huo, Y.; Liu, Q.; Wang, R.; Xu,
Z. Dual-Functional Chiral Cu-Catalyst-Induced Photoredox Asym-
metric Cyanofluoroalkylation of Alkenes. ACS Catal. 2019, 9, 4470−
4476.
(13) Lefebvre, Q.; Pluta, R.; Rueping, M. Copper Catalyzed
Oxidative Coupling Reactions for Trifluoromethylselenolations−
Synthesis of R-SeCF3 Compounds Using Air Stable Tetramethylam-
monium Trifluoromethylselenate. Chem. Commun. 2015, 51, 4394−
4397.
(14) Matheis, C.; Wagner, V.; Goossen, L. J. Sandmeyer-Type
Trifluoromethylthiolation and Trifluoromethylselenolation of
(Hetero)Aromatic Amines Catalyzed by Copper. Chem. - Eur. J.
2016, 22, 79−82.
(15) See Supporting Information for control experiments. Liu, Z.;
Chen, H.; Lv, Y.; Tan, X.; Shen, H.; Yu, H.-Z.; Li, C. Radical
Carbofluorination of Unactivated Alkenes with Fluoride Ions. J. Am.
Chem. Soc. 2018, 140, 6169−6175.
(8) For one representative review of our group, see: (a) Li, Z.-L.;
Fang, G.-C.; Gu, Q.-S.; Liu, X.-Y. Recent Advances in Copper-
Catalysed Radical-Involved Asymmetric 1,2-Difunctionalization of
Alkenes. Chem. Soc. Rev. 2020, 49, 32−48. For selected examples, see:
(b) Lin, J. S.; Dong, X. Y.; Li, T. T.; Jiang, N. C.; Tan, B.; Liu, X. Y. A
Dual-Catalytic Strategy To Direct Asymmetric Radical Amino-
trifluoromethylation of Alkenes. J. Am. Chem. Soc. 2016, 138,
9357−9360. (c) Li, Z. L.; Li, X. H.; Wang, N.; Yang, N. Y.; Liu, X.
Y. Radical-Mediated 1,2-Formyl/Carbonyl Functionalization of
Alkenes and Application to the Construction of Medium-Sized
Rings. Angew. Chem., Int. Ed. 2016, 55, 15100−15104. (d) Lin, J.-S.;
Li, T.-T.; Liu, J.-R.; Jiao, G.-Y.; Gu, Q.-S.; Cheng, J.-T.; Guo, Y.-L.;
Hong, X.; Liu, X.-Y. Cu/Chiral Phosphoric Acid-Catalyzed Asym-
metric Three-Component Radical-Initiated 1,2-Dicarbofunctionaliza-
tion of Alkenes. J. Am. Chem. Soc. 2019, 141, 1074−1083. (e) Zeng,
Y.; Liu, X.-D.; Guo, X.-Q.; Gu, Q.-S.; Li, Z.-L.; Chang, X.-Y.; Liu, X.-
Y. Cu/Chiral Phosphoric Acid-Catalyzed Radical-Initiated Asymmet-
ric Aminosilylation of Alkene with Hydrosilane. Sci. China: Chem.
2019, 62, 1529−1536. (f) Dong, X. Y.; Cheng, J. T.; Zhang, Y. F.; Li,
Z. L.; Zhan, T. Y.; Chen, J. J.; Wang, F. L.; Yang, N. Y.; Ye, L.; Gu, Q.
S.; Liu, X. Y. Copper-Catalyzed Asymmetric Radical 1,2-Carboalky-
nylation of Alkenes with Alkyl Halides and Terminal Alkynes. J. Am.
Chem. Soc. 2020, 142, 9501−9509. (g) Cheng, Y.-F.; Liu, J.-R.; Gu,
Q.-S.; Yu, Z.-L.; Wang, J.; Li, Z.-L.; Bian, J.-Q.; Wen, H.-T.; Wang, X.-
J.; Hong, X.; Liu, X.-Y. Catalytic Enantioselective Desymmetrizing
Functionalization of Alkyl Radicals via Cu(i)/CPA Cooperative
Catalysis. Nat. Catal. 2020, 3, 401−410.
(9) (a) Tyrra, W.; Naumann, D.; Yagupolskii, Y. L. Stable
Trifluoromethylselenates(0), [A]SeCF3Synthesis, Characterizations
and Properties. J. Fluorine Chem. 2003, 123, 183−187. (b) Durr, A.
̈
B.; Fisher, H. C.; Kalvet, I.; Truong, K.-N; Schoenebeck, F. Divergent
Reactivity of a Dinuclear (NHC)Nickel(I) Catalyst versus Nickel(0)
Enables Chemoselective Trifluoromethylselenolation. Angew. Chem.,
Int. Ed. 2017, 56, 13431−13435. (c) Han, J. B.; Dong, T.; Vicic, D.
A.; Zhang, C. P. Nickel-Catalyzed Trifluoromethylselenolation of Aryl
1949
https://dx.doi.org/10.1021/acs.orglett.1c00436
Org. Lett. 2021, 23, 1945−1949