Regioselective intramolecular Markovnikov and anti-Markovnikov hydrofunctionalization of alkenes: Via photoredox catalysis

Article abstract of DOI:10.1039/c9cc05902d

Highly regioselective Markovnikov hydrofunctionalization of alkenes was successfully realized via photoredox catalysis by introducing a urea group and fine tuning the hydrogen atom transfer catalysts. The anti-Markovnikov hydroamination of alkenes was also achieved with high yields and stereoselectivities in this work.

Full text of DOI:10.1039/c9cc05902d

View Article Online
View Journal
ChemComm
Chemical Communications
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: H. Wang, Y. Man,
Y. Xiang, K. Wang, N. Li and B. Tang, Chem. Commun., 2019, DOI: 10.1039/C9CC05902D.
Volume 54
This is an Accepted Manuscript, which has been through the
Number
January 2018
Pages 1-112
1
4
Royal Society of Chemistry peer review process and has been
accepted for publication.
ChemComm
Chemical Communications
rsc.li/chemcomm
Accepted Manuscripts are published online shortly after acceptance,
before technical editing, formatting and proof reading. Using this free
service, authors can make their results available to the community, in
citable form, before we publish the edited article. We will replace this
Accepted Manuscript with the edited and formatted Advance Article as
soon as it is available.
You can find more information about Accepted Manuscripts in the
Information for Authors.
Please note that technical editing may introduce minor changes to the
text and/or graphics, which may alter content. The journal’s standard
Terms & Conditions and the Ethical guidelines still apply. In no event
shall the Royal Society of Chemistry be held responsible for any errors
or omissions in this Accepted Manuscript or any consequences arising
from the use of any information it contains.
ISSN 1359-7345
COMMUNICATION
S. J. Connon, M. O. Senge et al.
Conformational control of nonplanar free base porphyrins:
towards bifunctional catalysts of tunable basicity
rsc.li/chemcomm

Please do not adjust margins
Page 1 of 5
ChemComm
View Article Online
DOI: 10.1039/C9CC05902D
COMMUNICATION
Regioselective Intramolecular Markovnikov and Anti-
Markovnikov Hydrofunctionalization of Alkenes via Photoredox
Catalysis
Received 00th January 20xx,
Accepted 00th January 20xx
Hongyu Wang,† Yunquan Man,† Yanan Xiang, Kaiye Wang, Na Li* and Bo Tang*
DOI: 10.1039/x0xx00000x
R'
R''
R'
Highly regioselective Markovnikov hydrofunctionalization of
alkenes was successfully realized via photoredox catalysis by
introducing a urea group and fine tuning the hydrogen atom
transfer catalysts. The anti-Markovnikov hydroamination of
alkenes was also achieved with high yields and stereoselectivities
in this work.
Cyclization
HAT
Nu
R''
Previous Work
Nu
Path a
C
D
Anti-Markovnikov Product
R'
R'
R''
visible light
Nu
Nu
R''
The regioselective hydrofunctionalization of alkenes (HFA)
represents an important strategy for the construction of high
value-added molecules from feedstock materials with high
atomic efficiency.1 Over the past decades, extensive efforts
have been focused on the development of regioselective HFA
reactions via nobel metals and organocatalysts.2 In particular,
great advances have been made regarding the carbonylations,3
hydrocyanation,4 hydroamination,5 hydroxylation6 and
hydroboration of alkenes.7 Despite the great importance of HFA
reactions, “controlling the regioselectivity” is still a challenging
topic in organic synthesis.
Recently, photoredox catalysis has become a powerful tool
for constructing functionalized molecules, which also has wide
applications in anti-Markovnikov HFA reactions employing a
dual catalyst system including a photocatalyst and hydrogen
atom transfer catalyst.8 Generally, a radical process was
B
A
Path b
R'
R''
R'
Nu
Cyclization
HAT
Nu
R''
This work
F
E
Markovnikov Product
Scheme 1. Photocatalyzed Markovnikov and anti-Markovnikov reactions. HAT: hydrogen
atom transfer; Nu: nucleophile.
and environmentally benign strategy for the generation of anti-
Markovnikov adducts.9 Although great advances have been
made regarding anti-Markovnikov HFA via photoredox catalysis,
minimal attentions has been focused on Markovnikov HFA
reactions through photocatalysis. In light of the advantages of
photoredox catalysis in organic synthesis, it is highly desirable
to develop new methods to realize regioselective Markovnikov
and anti-Markovnikov HFA reactions under visible light; this
development would greatly expand the applications of
photoredox catalysis in HFA reactions.
Based on the catalytic mechanism (Scheme 1, Path a), the
functionalization of the alkenes first occurred via a cyclization
process, that can be attributed to the properties of the radical
intermediate C. Generally, this radical should be stabilized by
electron-donating groups. We anticipated that if the HAT
progress finished first, we would obtain cation intermediate E
and then achieve a consequent cyclization process, and
Markovnikov HFA reactions would be successfully realized
(Scheme 1, Path b). Therefore, studies on the hydrogen transfer
catalysts and suitable nucleophiles are important for realizing
the above hypothesis. Recently, our group has focused on the
applications of nitrogen radical cations in organic synthesis via
involved
in
the
photocatalytic
reactions.
Taking
oneintramolecular HFA reaction as an example (Scheme 1, Path
a), a cation radical intermediate B was first generated via the
oxidation of A by the excited photocatalyst, then the cyclization
reaction proceeded, yielding the radical intermediate C. After a
hydrogen atom transfer process, the desired product D was
furnished. Compared with traditional noble-metals catalysis for
HFA reactions, photoredox catalysis provides a sustainable, mild
a. College of Chemistry, Chemical Engineering and Materials Science, Key
Laboratory of Molecular and Nano Probes, Ministry of Education, Collaborative
Innovation Centre of Functionalized Probes for Chemical Imaging in Universities of
Shandong, Institute of Molecular and Nano Science, Shandong Normal University,
Jinan, 250014 (P.R. China). E-mail: lina@sdnu.edu.cn; tangb@sdnu.edu.cn.
† The authors contributed equally to this work.
Electronic Supplementary Information (ESI) available: Experimental details, NMR
data and supplementary figures. See DOI: 10.1039/x0xx00000x
Please do not adjust margins

Please do not adjust margins
ChemComm
Page 2 of 5
COMMUNICATION
Journal Name
Table 1. Screening the reaction conditions.a
of photocatalysts and temperature were primaVriielwy AertxicplelOonrleinde
(Table 1, entry 12-15), and photocatalystDIOaIn: 1d0l.o10w39t/eCm9CpCe0r5a9t0u2rDe
were favourable for high yields in this method.
Me
Me
Me
Under the optimized conditions, the scope of the
Markovnikov hydroxylation reactions continued to be
investigated (Table 2). Different substituents on the urea were
carefully investigated, electron-withdrawing groups are more
favourable for the Markovnikov reaction (see Supporting
Information for more details). For substrate 1b, 88% yield was
obtained. The introduction of different substituents in the
cyclohexane ring were tolerated well, with high yields such as
methyl, t-Bu and phenyl (Table 2, entries 2-7). Moreover,
trisubstituted cyclopentene and cycloheptane were also tested,
and the spiro adducts 2i and 2j were obtained at yields of 78%
and 75% respectively. Subsequently, trisubstituted cyclohexene
1k was examined, which could furnish the five membered ring
2k at a yield of 79%. Furthermore, linear alkene 1l was tolerated
to provide the cyclization product 2l at an excellent yield (80%
yield).
To explain the importance of thiols to the hydrogen atom
transfer process, we tested the intramolecular hydroamination
via tuning the electronic properties of thiols. After carefully
screening the conditions of the reactions (see Supporting
Information for more details), we found that the reaction can
be successfully realized using 4-CF3C6H4SH under room
temperature (81% yield for cis-3a). In particular, excellent
diastereoselectivity was obtained with >20:1 d.r.. The structure
of 3a was confirmed by X-ray crystallographic analysis.11 For the
best conditions, different substituents in the ring continued to
be explored. As shown in Table 2, all the anti-Markovnikov
hydroamination products could be produced with good to
excellent yields and high diastereoselectivities. All the results
illustrated that the Markovnikov and anti-Markovnikov
reactions could be realized via tuning the electronic properties
of hydrogen atom transfer catalysts and reaction temperature.
To expand the applications of the catalytic method, the gram-
scale experiment was then tested. As shown in Scheme 2a, the
reaction can be performed using 3 mmol of 1a with 71% yield.
We primarily investigated the applications of the method in the
late stage functionalization of stanolone. Intramolecular
hydroxylation and hydroamination of the alkene were well
tolerated with high yields (75% yield for 2o, and 63% yield for
3o).
NH
N
O
BF4
N
O
Me
I
(5 mol%)
NH
N
H
4-MeOPhSH (20 mol%)
CHCl3, N2,blue LED, -15 o
F3C
C
CF3
F3C
CF3
2a
: CCDC 1936148
2a
1a
Entry
1
2
3
4
5
6
7
8
Variations from standard conditions
None
Yield (2a)
84%
NR
No light
No photocatalyst
No 4-MeOC6H4SH
NR
NR
CH2Cl2, instead of CHCl3
ClCH2CH2Cl, instead of CHCl3
CH3CN, instead of CHCl3
DMF, instead of CHCl3
4-EtC6H4SH, instead of 4-MeOC6H4SH
4-CF3C6H4SH, instead of 4-MeOC6H4SH
2,4,6-i-Pr3C6H2SH, instead of 4-MeOC6H4SH
[Ru(bpy)3Cl2].6H2O, instead of I
[Ir(ppy)2(dtbbpy)]PF6, instead of I
r.t., instead of -15 C
57%
65%
trace
NR
72%
26%
23%
NR
9
10
11
12
13
14
15
NR
52%
72%
0 C, instead of -15 C
aUnless otherwise noted, all the reactions were carried out with 1a (0.1 mmol) in
the presence of 4-MeOC6H4SH (20 mol%) catalysed by I (5 mol%) at -15 oC. For
more details about the experimental procedures, see the Supporting Information.
photoredox catalysis, and found that urea groups exhibited
excellent properties for controlling the regioselectivities via
hydrogen binding interactions.10 Considering the excellent
properties of urea groups, these groups might be ideal
nucleophiles for exploring the Markovnikov HFA reaction. In
addition, to accelerate the HAT process, strong electron-
donating HAT catalysts are needed in the HFA reactions.
Initially, the Markovnikov reaction of 1a was examined under
photocatalytic conditions. As shown in Table 1, a Z-isomer 2a
can be obtained at 84% yield catalysed by Fukuzumi catalyst Ι
under visible light. Furthermore, the structure of the spiro
product 2a was confirmed by X-ray crystallographic analysis.11
Subsequently, control experiments were examined including
photocatalysts, blue light or 4-MeOC6H4SH (Table 1, entries 2-
4). However, no product was formed when the reaction was
carried out without any of these factors, which illustrated that
the reaction was a photocatalysed Markovnikov HFA reaction.
Furthermore, the influences of solvents continued to be
investigated, while the reactions could be performed in
chlorinated solvents such as CH2Cl2 and ClCH2CH2Cl with low
yield. However, no products were obtained when the reaction
was carried out in other polar solvents (CH3CN and DMF) (Table
1, entries 5-8). Then hydrogen atom transfer (HAT) catalysts
were explored with regard to explaining the effects of hydrogen
atom donors. Electron-poor thiols (4-CF3C6H4SH) were
detrimental to the reaction, and only low yields were obtained.
2,4,6-i-Pr3C6H2SH was unfavourable for the yield because of the
bulky steric influence of this complex. Moreover, the influences
To gain insight into the mechanism of the reaction, certain
control experiments were performed. When the N-H of the urea
was protected with benzyl group 1a’ or methyl group 1a’’,
complex mixtures were observed under the optimized
conditions. Replacing the urea groups with amides was
detrimental to the reaction via photoredox catalysis (trace for
2p, 24% yield for 2q), so the nucleophilicity of the urea was
important for the Markovnikov reaction. Based on the results
and previous works, a possible mechanism was proposed as
shown in Scheme 3b. The alkenes 1 was first oxidized by the
excited photocatalyst to produce the radical cation
intermediate L, which then proceeded via a hydrogen atom
2 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Please do not adjust margins
Page 3 of 5
ChemComm
View Article Online
DOI: 10.1039/C9CC05902D
COMMUNICATION
Table 2. Intramolecular anti-Markovnikov hydroamination of alkene via photocatalysis.
O
R'
R'
O
G
Condition B
Condition A
R''
N
N
G
O
G
N
H
R''
N
N
H
H
R''
NH
2
R'
G: 3,5-(CF3)2C6H3
Substrate
1
3
Entry
1
Condition A
Condition B
Substrate
Entry
5
Condition A
Condition B
O
N
Me
O
N
G
N
HN
N
HN
N
NH
H
G
N
O
NH
O
HN
O
Me
O
H
HN
Me
G
3a
G
, 81% yield, > 20:1 d.r.
G
1f
2f
, 69% yield
G
3f
, 50% yield, > 20:1 d.r.
2a
, G = 3,5-(CF3)2C6H3
84% yield
, G = 4-CNC6H4
88% yield
1a,
1b
G = 3,5-(CF3)2C6H3
O
O
N
, G = 4-CNC6H4
2b
HN
N
6
NH
O
O
G
N
H
O
CCDC 1936149
N
HN
G
O
1g
G
2g
, 89% yield
3g
, 47% yield, > 20:1 d.r.
Me
O
HN
N
Me
O
G
NH
2
3
4
O
O
N
O
O
O
G
N
O
HN
HN
H
HN
G
NH
7
8
9
G
Me
O
O
N
G
O
O
2c
1c
, 80% yield
3c
, 68% yield, 14:1 d.r.
O
HN
G
1h
1i
t-Bu
, 55% yield, 17:1 d.r.
O
2h
, 85% yield
3h
N
HN
N
t-Bu
G
N
NH
O
H
O
HN
N
O
G
N
O
N
N
G
N
HN
G
H
H
G
H
t-Bu
G
1d
2d
3d, 57% yield, > 20:1 d.r.
, 75% yield
O
2i
, 78% yield
3i
, 67% yield, 7: 1 d.r.
O
O
Ph
N
O
HN
N
Ph
G
N
N
NH
G
N
G
H
HN
N
N
O
H
O
H
H
HN
G
G
N
Ph
G
3e
2e
, 58% yield, 10:1 d.r.
, 84% yield
1e
1j
2j
, 75% yield
3j
, 84% yield, > 20:1 d.r.
G
N
H
H
O
H
N
H
N
Condition A
N
O
Condition B
N
N
G
G
O
NH
, 79% yield
HN
G
, 55% yield, > 20:1 d.r.
O
O
1k
2k
Ph
3m
1m
1n
Bn
G
N
O
Condition A
G
O
O
G
N
H
N
N
Condition B
Me
Me
N
N
H
H
H
NH
, 80% yield
Me Me
HN
G
2l
1l
3n
,70% yield
aCondition A: all the reactions were carried out with 1 (0.1 mmol) in the presence of 4-MeOC6H4SH (20 mol%) catalyzed by I (5 mol%) at -15 oC. Condition B: all the
reactions were carried out with 1 (0.1 mmol) in the presence of 4-CF3C6H4SH (20 mol%) catalyzed by I (5 mol%) at r.t.. For more details about the experimental procedures,
see Supporting Infromation.
transfer process to furnish the cation intermediate M. temperature. We believe that these results provide a new
Subsequently, a cyclization reaction was performed to obtain perspective on the application of photoredox catalysis in the
the desired spiro products 2.
functionalization of alkenes. In addition, further studies on the
In summary, highly regioselective intramolecular mechanism of the highly regioselective hydrofunctionalization
Markovnikov and anti-Markovnikov hydrofunctionalization of of alkenes by photoredox catalysis are underway in our lab, and
alkenes was successfully developed via photoredox catalysis. will be reported in due course.
HAT catalysts and the urea groups played crucial roles in
Financial support from the National Natural Science
controlling the regioselectivities of these reactions. In which, Z- Foundation of China (21535004, 91753111, 21874086, and
isomers of spiro products were selectively prepared with high 21602125), and the Key Research and Development Program of
yields. Moreover, cis-stereoselective hydroamination of alkenes Shandong Province (2018YFJH0502) is gratefully acknowledged.
was realized via fine tuning of the HAT catalysts and reaction
Please do not adjust margins

Please do not adjust margins
ChemComm
Page 4 of 5
COMMUNICATION
Journal Name
Scheme 2. Gram-scale synthesis and applications of the Markovnikov reaction via
photoredox catalysis.
Chem. Commun. 2007, 3607; (d) J. Chen, Z. Lu. Org. Chem.
DOI: 10.1039/C9CC05902D
Thomas. Chem. Cat. Chem. 2015, 7, 190.
View Article Online
Front. 2018, 5, 260; (e) M. D. Greenhalgh, A. S. Jones, S. P.
a) Gram-Scale synthesis:
3
For selected reviews, see: (a) F. Hebrard, P. Kalck, Chem. Rev.
2009, 109, 4272; (b) L. Wu, Q. Liu, B. M. Jackstell. Angew.
Chem. Int. Ed. 2014, 53, 6310; (c) J. Dai, W. Ren, J. Li, Y. Shi.
Org. Chem. Front. 2018, 5, 561; for recent examples, see: (d)
X. Zhou, G. Zhang, B. Gao, H. Huang, Org. Lett. 2018, 20, 2208;
(e) T. Xu, F. Sha, H. Alper, J. Am. Chem. Soc. 2016, 138, 6629;
(f) H. Huang, C. Yu, Y. Zhang, Y. Zhang, P. S. Mariano, W. Wang,
J. Am. Chem. Soc. 2017, 139, 9799; (g) W. Ren, W. Chang, J.
Dai, Y. Shi, J. Li, Y. Shi, J. Am. Chem. Soc. 2016, 138, 14864.
(a) A. Bhunia, K. Bergander, A. Studer. J. Am. Chem. Soc. 2018,
140, 16353; (b) L. Bini, C. Müller, D. Vogt. Chem. Commun.
2010, 46, 8325; (c) X. Li, C. You, J. Yang, S. Li, D. Zhang, H. Lv,
X. Zhang, Angew. Chem. Int. Ed. 2019, 58, 10928; (d) G. Wang,
X. Xie, W. Xu, Y. Liu, Org. Chem. Front. 2019, 6, 2037; (e) P.
Orecchia, W. Yuan, M. Oestreich, Angew. Chem. Int. Ed. 2019,
58, 3579; (f) M. d. Greef, B. Breit, Angew. Chem. Int. Ed. 2009,
48, 551; (g) X. Fang, P. Yu, B. Morandi, Science 2016, 351, 832.
For selected reviews, see: (a) L. Huang, M. Arndt, K. Gooβen,
H. Heydt, L. J. Gooβen. Chem. Rev. 2015, 115, 2596; (b) K. D.
Hesp, M. Stradiotto. Chem. Cat. Chem. 2010, 2, 1192; (c) T. E.
Müller, K. C. Hultzsch, M. Yus, F. Foubelo, M. Tada. Chem. Rev.
2008, 108, 3795; (d) M. T. Pirnot, Y.-M. Wang, S. L. Buchwald,
Angew. Chem. Int. Ed. 2016, 55, 48; for recent examples, see:
(e) S. Guo, J. C. Yang, S. L. Buchwald, J. Am. Chem. Soc. 2018,
140, 15976; (f) S. W. Lardy, V. A. Schmidt, J. Am. Chem. Soc.
2018, 140, 12318; (g) D. Niu, S. L. Buchwald, J. Am. Chem. Soc.
2015, 137, 9716.
G
N
O
I
(5 mol%)
G
O
N
N
4-MeOPhSH (20 mol%)
CHCl3, N2,blue LED, -15 o
NH
H
H
1a
3 mmol, 1.14 g
G : 3,5-(CF3)2C6H3
b) Applications:
HO
C
2a
, 71% yield
1) ethylene glycol, TsOH, toluene
2) MeI, NaH, CH2Cl2, 50 o
Me
OMe
C
Me
H
3) 2M HCl, r.t.
H
H
Me
4
5
Me
4) NCCH2CO2H, NH4OAc, toluene
5) LiAlH4, THF
H
G
N
H
H
H
6) 3,5-CF3C6H3NCO, CH2Cl2
O
1o
Stanolone
OMe
Me
OMe
Me
Conditions A
Conditions B
Me
Me
G
H
H
HN
O
H
H
N
H
H
H
N
N
2o
, 75% yield
G
O
G : 3,5-(CF3)2C6H3
3o
, 63% yield
:
:
(5 mol%), 4-MeOC6H4SH (20 mol%), CHCl3, N2, Blue LED, - 15 oC
Conditions A
Conditions B
I
I
(5 mol%), 4-CF3C6H4SH (20 mol%), CHCl3, N2, Blue LED, r.t.
Scheme 3. Control experiments and the plausible catalytic mechanism.
a) Control experiments:
I
(5 mol%), 4-MeOC6H4SH (20 mol%)
Complex mixture
O
CHCl3, N2, Blue LED, - 15 o
C
Ar
1a',
R' = H, R'' = Bn
N
N
6
7
(a) L. Hintermann, Recent Developments in Metal-Catalyzed
Additions of Oxygen Nucleophiles to Alkenes and Alkynes. In
C-X Bond Formation; Vigalok, A.; Ed.; Springer Berlin
Heidelberg: Berlin, Heidelberg, 2010; pp 123-155; (b) P. T.
Marcyk, S. P. Cook, Org. Lett. 2019, 21, 1547; (c) C. S. Sevov, J.
F. Hartwig, J. Am. Chem. Soc. 2013, 135, 9303.
For selected reviews, see: (a) J.-B. Chen, A. Whiting, Synthesis
2018, 50, 3843; (b) J. V. Obligacion, P. J. Chirik, Nat. Rev. Chem.
2018, 2, 15; for recent examples, see: (c) J. Peng, J. H. Dochery,
A. P. Dominey, S. P. Thomas, Chem. Commun. 2017, 53, 4726;
(d) K. Duvvuri, K. R. Dewese, M. M. Parsutkar, S. M. Jing, M.
M. Mehta, J. C. Gallucci, T. V. RajanBabu, J. Am. Chem. Soc.
2019, 141, 7365; (e) G. Zhang, H. Zeng, J. Wu, Z. Yin, S. Zheng,
J. C. Fettinger, Angew. Chem. Int. Ed. 2016, 55, 14369; (f) A.
Bismuto, M. J. Cowley, S. P. Thomas, ACS Catal. 2018, 8, 2001;
(g) A. J. MacNair, C. R. P. Millet, G. S. Nichol, A. Ironmonger, S.
P. Thomas, ACS Catal. 2016, 6, 7217.
(a) K. A. Margrey, D. A. Nicewicz, Acc. Chem. Res. 2016, 49, 9,
1997; (b) E. C. Gentry, R. R. Knowles, Acc. Chem. Res. 2016, 49,
1546; (c) A. J. Musacchio, B. C. Lainhart, X. Zhang, S. G. Naguib,
T. C. Sherwood, R. R. Knowles, Science 2017, 355, 727; (d) Q.
Zhu, D. E. Graff, R. R. Knowles, J. Am. Chem. Soc. 2018, 140,
741; (e) S. T. Nguyen, Q. Zhu, R. R. Knowles, ACS Catal. 2019,
9, 4502; (f) D. J. Wilger, J.-M. M. Grandjean, T. R. Lammert, D.
A. Nicewicz, Nat. Chem. 2014, 6, 720; (g) T. M. Nguyen, N.
Manohar, D. A. Nicewicz, Angew. Chem. Int. Ed. 2014, 53,
6198; (h) D. A. Nicewicz, T. M. Nguyen, ACS Catal. 2014, 4,
355.
R'
R''
Ar : 3,5-(CF3)2C6H3
I
(5 mol%), 4-MeOC6H4SH (20 mol%)
Complex mixture
CHCl3, N2, Blue LED, - 15 o
C
1a'',
R' = Me, R'' = H
O
R
I
(5 mol%)
4-MeOPhSH (20 mol%)
CHCl3, N2,blue LED, -15 o
O
N
H
R
N
C
1p
1q
2p
2q
: R = 3,5-(CF3)2
: R = 4-MeO
: R = 3,5-(CF3)2, trace
: R = 4-MeO, 24% yield
b) Possible mechanism:
Ar'S
+ H+
+e-
Ar'SH
PC
Ar'S
HAT
hv
-
-
e
PC*
PC-
R'
R'
O
O
+e-
Ar
Ar
R''
Z
N
N
1
R''
N
N
H
H
H
H
8
M
L
R''
Z
R'
2
- H+
O
Ar
N
N
Ar : 3,5-(CF3)2C6H3
Ar' : 4-MeOC6H4
H
H
N
Conflicts of interest
The authors declare no competing financial interest.
9
(a) T. M. Nguyen, D. A. Nicewicz, J. Am. Chem. Soc. 2013, 135,
9588; (b) N. A. Romero, D. A. Nicewicz, J. Am. Chem. Soc. 2014,
136, 17024.
Notes and references
10 (a) H. Wang, Y. Man, K. Wang, X. Wan, L. Tong, N. Li, B. Tang,
Chem. Commun. 2018, 54, 10989; (b) H. Wang, Y. Ren, K.
Wang, Y. Man, Y. Xiang, N. Li, B. Tang, Chem. Commun. 2017,
53, 9644.
11 CCDC 1936148 (2a) and CCDC 1936149 (3a) contains the
supplementary crystallographic data for this paper.
1
V. P. Ananikov, I. P. Beletskaya, In Hydrofunctionalization; V.
P. Ananikov, M. Tanaka; Topics in Organometallic Chemistry;
Springer: Berlin, Heidelberg, 2013; pp 1-19.
(a) M. Beller, J. Seayad, A. Tillack, H. Jiao. Angew. Chem. Int.
Ed. 2004, 43, 3368; (b) C. Lin, L Shen. Chem. Cat. Chem. 2019,
11, 961; (c) C. Liu, C. F. Bender, X. Han, R. A. Widenhoefer.
2
4 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 5 of 5
ChemComm
View Article Online
DOI: 10.1039/C9CC05902D
Regioselective
Intramolecular
Markovnikov
and
Anti-Markovnikov
Hydrofunctionalization of Alkenes via Photoredox Catalysis
Hongyu Wang,† Yunquan Man,† Yanan Xiang, Kaiye Wang, Na Li* and Bo Tang*
Me
Me
Me
CF3
BF4
N
Me
O
(5 mol%)
p-MeOPhSH (20 mol%)
CHCl3, N2,blue LED, -15 o
N
N
CF3
H
C
84% yield
Markovnikov Product
Me
O
Me
Me
NH
N
H
N
NH
O
BF4
N
CF3
F3C
Me
(5 mol%)
p-CF3PhSH (20 mol%)
CHCl3, N2,blue LED, r.t.
CF3
F3C
81% yield, > 20:1 d.r.
Anti-Markovnikov Product
Highly regioselective Markovnikov and anti-Markovnikov hydrofunctionalization of alkenes was
successfully realized via photoredox catalysis by introducing the urea group and fine tuning
hydrogen atom transfer catalysts.