Visible-Light-Driven Iron-Promoted Thiocarboxylation of Styrenes and Acrylates with CO2

Article abstract of DOI:10.1002/anie.201707862

The first thiocarboxylation of styrenes and acrylates with CO₂ was realized by using visible light as a driving force and catalytic iron salts as promoters. A variety of important β-thioacids were obtained in high yields. This multicomponent reaction proceeds in an atom- and redox-economical manner with broad substrate scope under mild reaction conditions. Notably, high regio-, chemo-, and diasteroselectivity are observed. Mechanistic studies indicate that a radical pathway can account for the unusual regioselectivity.

Full text of DOI:10.1002/anie.201707862

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Accepted Article
Title: Visible light-driven and Iron-promoted Thiocarboxylation of
Styrenes and Acrylates with CO2
Authors: Jian-Heng Ye, Meng Miao, He Huang, Si-Shun Yan, Zhu-Bao
Yin, Wen-Jun Zhou, and Da-Gang Yu
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Angewandte Chemie International Edition
10.1002/anie.201707862
COMMUNICATION
Visible light-driven and Iron-promoted Thiocarboxylation of
Styrenes and Acrylates with CO2
Jian-Heng Ye, Meng Miao, He Huang, Si-Shun Yan, Zhu-Bao Yin, Wen-Jun Zhou, and Da-Gang Yu*
Dedicated to Professor Chen-Ho Tung on the occasion of his 80th birthday.
Abstract: The first thiocarboxylation of styrenes and acrylates with
CO is realized by using visible light as a driving force and catalytic
possible to achieve a novel carboxylation with CO
stage, prior to the formation of other bonds. Employing a CO
radical anion might make such a tactic viable, as it can be
2
at the early
2
2
iron salts as promoters. A variety of important β-thioacids are
obtained in high yields. This multicomponent reaction proceeds in an
atom- and redox-economical way with broad substrate scope under
mild reaction conditions. Notably, high regio-, chemo- and diastero-
selectivity are observed. Mechanistic studies indicate that a radical
pathway can account for the unusual regioselectivity.
[7a]
reactive toward alkenes.
also highly challenging.
However, access to this species is
Therefore, novel reaction systems
[
11]
must be developed to resolve such a challenge.
It is well known that iron–sulfur proteins can serve as
interesting redox catalysts involving electron transfer and CO
fixation. Inspired by research concerning the „iron–sulfur world‟
2
[
12]
As a ubiquitous, nontoxic and sustainable one-carbon (C1)
hypothesis, we considered it would be highly appealing to use
building block, CO
synthesis. Among various transformations, utilization of CO
2
has gained considerable attention in organic
simple thiols and iron salts in carboxylation with CO
2
. β-
[1]
[2]
Thioacids and derivatives are important motifs in many bioactive
2
[
13]
as a C1 source to synthesize carboxylic acids is highly valuable,
as they are common structural motifs in bioactive molecules and
compounds,
but synthetic methods toward these motifs are
[
14]
limited. Encouraged by elegant works of Murakami, Jamison,
Iwasawa, He and Martin,
[
3]
[4-
[8,10,15]
useful synthons. Although great progress has been achieved,
we hypothesized that a system
6
]
most methods for C−C bond formation are based on two-
analogous to an iron-sulfur protein could accelerate the redox-
electron CO
2
activation. The single-electron reduction of CO
2
is
neutral difunctionalization of alkenes with CO
visible light (Scheme 1b).
2
and thiols under
rarely applied in organic synthesis, although it has been well
demonstrated in electro- and photo-chemistry. With great
efforts, Jamison recently reported an elegant amino acid
[
7]
synthesis involving single-electron reduction of CO
2
under
ultraviolet light by using continuous flow technique (Scheme
[
8]
1
a). However, such an activation mode has not been realized
with visible light or in batch. Herein, we report the first
thiocarboxylation of alkenes with CO , which is promoted by
visible light and catalytic iron salts (Scheme 1d). Importantly, the
unusual regioselectivity might result from addtition of a CO
2
2
radical anion to alkenes. Moreover, this redox-neutral reaction in
batch is mild, scalable, efficient and selective.
[
4]
[5]
Besides single bonds in electrophiles or nucleophiles,
unsaturated hydrocarbon counterparts, abundant and readily
available in industry, represent ideal platforms in carboxylation
[9]
with CO
2
.
Besides alkynes and allenes, alkenes have been
widely applied in the transition metal-catalyzed carboxylation
[
6]
with CO
these works are confined to hydrocarboxylation. The
carboxylative difunctionalization of alkenes with CO is highly
2
to provide alkyl carboxylic acids. However, most of
2
2
Scheme 1. Light-Driven Carboxylation with CO .
challenging and has not been investigated until very recently
Martin reported an elegant dicarbofunctionalization of styrenes
With this idea in mind, a three-component reaction involving
styrene 1a, p-toluenethiol 2a, and CO was examined (Table 1).
To our delight, the product 3aa was obtained in 94% yield using
blue LED and 5 mol% of FeCl at room temperature (entry 1).
[10]
2
with CO
functionalizations of alkenes are still limited to the carboxylation
with CO at the late stage of catalysis. We wondered if it was
2
(Scheme 1c).
Nevertheless, carboxylative
3
2
Notably, this reaction featured unusual regioselectivity in C−C
bond formation that contrasted with the well-demonstrated
[
6]
hydrocarboxylations of styrenes to afford phenylacetic acids.
[*]
J.-H. Ye, M. Miao, H. Huang, S.-S. Yan, Z.-B. Yin, Prof. Dr. W.-J.
Zhou, Prof. Dr. D.-G. Yu
Key Laboratory of Green Chemistry & Technology of Ministry of
Education, College of Chemistry, Sichuan University
Moreover, the chemo- and regioselectivity were excellent;
neither the hydrocarboxylative product nor another regioisomer
was not detected in this reaction. Control experiments
demonstrated the essential role of light and base (entries 2-3).
29 Wangjiang Road, Chengdu 610064 (P. R. China)
E-mail: dgyu@scu.edu.cn
Notably, the reaction still occurred without FeCl
3
in 32% yield
Supporting information for this article is given via a link at the end of
the document.
[
16]
(
entry 4).
Other kinds of transition metals and bases were
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Angewandte Chemie International Edition
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COMMUNICATION
studied to give lower yields (entries 5-10. Please see more
details in SI). The reactions with lower loading of iron salts (entry
While 1k-1n worked well, more sterically hindered substrate 1s
gave the desired product in only moderate yield. Notably, 1,1-
disubstituted styrenes 1t and 1u also exhibited good reactivity.
To our delight, β-substituted styrenes, which have rarely been
11) or shorter reaction time (entry 12) also afforded 3aa in
moderate to excellent yields, demonstrating the high efficiency.
2
explored in carboxylation with CO , were also tolerated and gave
the products 3va and 3wa with high diastereoselectivity.
Moreover, styrenes bearing heterocycles, such as pyrrole and
indole moieties (3xa-3za), were also suitable. To our delight,
acrylates 1aa and 1ab also showed high reactivity, generating
the desired products with excellent regioselectivity.
[
a]
Table 1. Optimization of the reaction conditions.
We then investigated the reactivity of different thiols. As
shown in Table 3, thiophenols bearing slightly electron-donating
substituents at the para position, such as 2c and 2d, showed
excellent reactivity. Thiophenols bearing not only stronger
electron-donating groups, such as methoxyl (2e), but also more
electronegative elements, such as F (2f), could afford the
desired products in good yields. The ester-containing substrate
[
b]
Entry
Alteration
Yield [%]
1
2
3
4
5
6
7
8
9
none
98 (94)
N.D.
N.D.
32
no light
no base
no FeCl
P) instead of FeCl
instead of FeCl
CuCl instead of FeCl
3
CoCl(Ph
3
3
3
10
2g also reacted smoothly. Both meta- and ortho-substituted
NiCl
2
3
3
< 5
thiophenols 2h-2j were suitable substrates. Additionally, di-
substituted thiophenols 2k and 2l were also compatible.
However, electron-deficient aryl thiols with CF , NO , or COOMe
3 2
group at the para position as well as benzylthiol 2m failed to give
the desired products.
25
MnBr(CO)
5
instead of FeCl
3
20
t
K
2
CO
3
instead of KO Bu
23
t
10
11
12
NEt
3
instead of KO Bu
< 5
1 or 0.1 mol % of FeCl
6 or 2 h
3
89, 48
[
a]
Table 3. Substrate scope of thiols.
90, 64
t
[
a] Reaction conditions: 1a (0.2 mmol), 2a (0.3 mmol), KO Bu (0.4 mmol),
FeCl
3
(0.01 mmol), DMA (2 mL), 1 atm of CO
2
, 30 W blue LED, rt, 12 h. [b]
1
Determined by crude H-NMR with CH
2
Br as internal standard. Isolated yield
2
is provided in parenthesis. N.D. = not detected.
With acceptable reaction conditions in hand (Table 1, entry 1),
we next investigated the substrate scope of alkenes. As shown
in Table 2, para-substituted styrenes bearing both electron-poor
and electron-rich arenes were effective to give products
3ba−3ea in good to excellent yields. In addition, meta and ortho-
substituted styrenes also exhibited good reactivities. Notably, o-
allyloxystyrene 1n underwent the reaction to afford the desired
product 3na with excellent chemoselectivity, indicating lower
[17]
reactivity of alkyl-substituted olefins.
Besides these,
arylethylenes with two or three substituents on the aryl ring were
also compatible, resulting in products 3oa−3sa with high yields.
[
a] The standard reaction condition (Table 1, entry 1), isolated yields. [b]
t
KO Bu (3.0 equiv), 2k (2.0 equiv).
[
a]
Table 2. Substrate scope of alkenes.
Concerning the mechanism, various control experiments were
conducted. We confirmed that the reaction could not work at
high temperature without light. Moreover, the disulfide, detected
as a byproduct with low yield in the reaction, was not the
reactive intermediate (Please see more details in SI). Since 2a’
t
can be used instead of 2a and KO Bu to give 3aa with 85% NMR
t
yield (Scheme 2a), KO Bu might serve mainly as a base to
deprotonate 2a and promote the formation of a Fe/S complex,
which might be the important photoredox catalyst and/or
[
18]
electron transfer promoter in this reaction.
As two bonds are formed, there are two possible ways to
initiate the difunctionalization of the alkene with either C−C or
C−S bond formation happening first (or simultaneously). If the
C−S bond is formed before the C−C bond, neither a radical nor
thiometallation process could account for the observed
regioselectivity. Therefore, difunctionalization of the alkene is
2
believed to start with C−C bond formation with CO . A possible
[
1
a] The standard reaction condition (Table 1, entry 1), isolated yields. [b] dr >
6:1, determined by H-NMR. [c] KO Bu (3.0 equiv), 2a (2.0 equiv), 24 h.
1
t
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Angewandte Chemie International Edition
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COMMUNICATION
alternate pathway involving Michael addition of 2a’ to cinnamic
acid 3aa’, was excluded by a control experiment (Scheme 2b).
alcohol 4, ester 5 and 6 as well as bioactive compounds and
drugs, including β-sulfonylhydroxamic acid derivative 7, 1-
thioflavanone 8, and thiazensim 9.
[
21]
In order to elucidate whether C−C bond formation occurs via a
two- or single-electron process, preliminary mechanistic studies
were surveyed. Although CO
the possibility of a two-electron process involving alkene serving
as a nucleophile and attacking CO is not favored, as electron-
2
is a carbon-based electrophile,
2
deficient acrylates reacted well. Moreover, the intermolecular
competition experiment (Scheme 2c) demonstrated that the
electron-poor styrene showed higher reactivity than the electron-
rich one, indicating that formation of
a benzylic cation
intermediate followed by trapping with thiolate 2a’ was unlikely.
Furthermore, addition of TEMPO could significantly inhibit the
thiocarboxylation (Scheme 2d). Finally,
a “radical clock”
substrate 1ac was applied to the standard reaction conditions to
provide the ring-opening product 3aca in 77% yield (Scheme 2e).
These results indicated that an alkyl radical might be involved.
Based on the strong reduction potential of the CO
2
radical anion
and the high regio- and
chemoselectivity observed in the thiocarboxylations of styrenes
and acrylates, we propose that a CO radical anion is first
0
[19]
(
E = –2.21 V versus SCE in DMF)
Scheme 3. Gram-scale reaction & synthetic applications.
2
generated via single-electron reduction by the excited Fe/S
complex (For more evidence from CV and UV-Vis experiments,
please see SI) under visible-light irradiation and then undergoes
addition to alkenes to give a stabilized alkyl radical (i.e., benzylic
radical). Trapping of this alkyl radical by a thiol radical, which
can be generated by single-electron transfer between reductive
thiolate and an oxidized form of Fe/S complex, followed by
acidification would provide the observed product. Further more
detailed mechanistic studies are currently under investigation.
In summary, we have developed the first thiocarboxylation of
styrenes and acrylates with CO
2
to generate important β-
thioacids efficiently with a novel visible light-driven and iron-
promoted system. Notably, unusual regioselectivity is observed.
This mild and redox-neutral process features broad substrate
scope, easy scalability and high selectivities, including regio-,
chemo- and diastero-selectivity. Mechanistic studies indicate
that the reaction most likely proceeds via a radical pathway.
Acknowledgements
We thank Prof. Ruben Martin (Institute of Chemical Research of
Catalonia) and Prof. Liang Deng (Shanghai Institute of Organic
Chemistry) for valuable discussion and suggestion. We thank
Prof. Jason J. Chruma (Sichuan University) for helpful
manuscript revisions. Financial support provided by the National
Natural Science Foundation of China (21502124, 21772129),
the “973” Project from the MOST of China (2015CB856600), the
“
1000-Youth Talents Program”, and the Fundamental Research
Funds for the Central Universities.
Keywords: carbon dioxide • iron • visible light • carboxylation •
thiophenol
[
[
1] M. Aresta, Carbon Dioxide as Chemical Feedstock; Wiley-VCH, Weinheim,
010.
2
2] a) T. Sakakura, J.-C. Choi, H. Yasuda, Chem. Rev. 2007, 107, 2365; b) K.
Huang, C.-L. Sun, Z.-J Shi, Chem. Soc. Rev. 2011, 40, 2435; c) M.
Cokoja, C. Bruckmeier, B. Rieger, W. A. Herrmann, F. E. Kühn, Angew.
Chem. Int. Ed. 2011, 50, 8510; d) Y. Tsuji, T. Fujihara, Chem. Commun.
2
012, 48, 9956; e) M. He, Y. Sun, B. Han, Angew. Chem. Int. Ed. 2013,
Scheme 2. Mechanistic studies.
52, 9620; f) M. Aresta, A. Dibenedetto, A. Angelini, Chem. Rev. 2014, 114,
At last, a gram-scale reaction was carried out to demonstrate
the easy scalability (Scheme 3a). The importance and utilty of
this method was validated by transformations of 3ab to γ-sulfide
1709; g) C. Maeda, Y. Miyazaki, T. Ema, Catal. Sci. Technol. 2014, 4,
1482; h) C. S. Yeung, V. M. Dong, Top. Catal. 2014, 57, 1342; i) Q. Liu, L.
This article is protected by copyright. All rights reserved.

Angewandte Chemie International Edition
10.1002/anie.201707862
COMMUNICATION
Wu, R. Jackstell, M. Beller, Nat. Commun. 2015, 6, 5933; j) Z. Zhang, T.
Ju, J.-H. Ye, D.-G. Yu, Synlett 2017, 28, 741.
Barba, Tetrahedron Lett. 2006, 47, 2171; c) A. Nomoto, Y. Kojo, G.
Shiino, Y. Tomisaka, I. Mitani, M. Tatsumi, A. Ogawa, Tetrahedron
Lett. 2010, 51, 6580.
[
3] a) A. Correa, R. Martín, Angew. Chem. Int. Ed. 2009, 48, 6201; b) D. Yu, S.
P. Teong, Y. Zhang, Coord. Chem. Rev. 2015, 293-294, 279; c) M.
Börjesson, T. Moragas, D. Gallego, R. Martin, ACS Catal. 2016, 6, 6739;
d) S. Wang, G. Du, C. Xi, Org. Biomol. Chem. 2016, 14, 3666; e) Q. Zhu,
L. Wang, C. Xia, C. Liu, Chin. J. Org. Chem. 2016, 36, 2813; f) G. Yuan,
C. Qi, W. Wu, H. Jiang, Curr. Opin. Green Sustain. Chem. 2017, 3, 22.
4] For an excellent review, see: a) Ref. 3c; For examples, see: b) A. Correa,
R. Martin, J. Am. Chem. Soc. 2009, 131, 15974; c) T. Fujihara, K. Nogi, T.
Xu, J. Terao, Y. Tsuji, J. Am. Chem. Soc. 2012, 134, 9106; d) T. León, A.
Correa, R. Martin, J. Am. Chem. Soc. 2013, 135, 1221; e) H. Tran-Vu, O.
Daugulis, ACS Catal. 2013, 3, 2417; f) T. Moragas, J. Cornella, R. Martin,
J. Am. Chem. Soc. 2014, 136, 17702; g) K. Nogi, T. Fujihara, J. Terao, Y.
Tsuji, Chem. Commun. 2014, 50, 13052; h) X. Wang, Y. Liu, R. Martin, J.
Am. Chem. Soc. 2015, 137, 6476; i) S. Zhang, W.-Q. Chen, A. Yu, L.-N.
He, ChemCatChem 2015, 7, 3972; j) K. Nogi, T. Fujihara, J. Terao, Y.
Tsuji, J. Org. Chem. 2015, 80, 11618; k) T. Mita, Y. Higuchi, Y. Sato,
Chem. Eur. J. 2015, 21, 16391; l) T. Moragas, M. Gaydou, R. Martin,
Angew. Chem. Int. Ed. 2016, 55, 5053; m) M. Börjesson, T. Moragas, R.
Martin, J. Am. Chem. Soc. 2016, 138, 7504; n) F. Juliá-Hernández, T.
Moragas, J. Cornella, R. Martin, Nature 2017, 545, 84.
[8] a) H. Seo, M. H. Katcher, T. F. Jamison, Nat. Chem. 2016, 9, 453. While
this manuscript was under revision, an elegant direct β-selective
2
hydrocarboxylation of styrenes with CO was reported by using UV light,
see: b) H. Seo, A. Liu, T. F. Jamison, J. Am. Chem. Soc. 2017,
doi:10.1021/jacs.7b05942.
[
[9] a) D. Walther, Coord. Chem. Rev. 1987, 79, 135; b) B. Yu, Z.-F. Diao, C.-X.
2
Guo, L.-N. He, J. CO Util. 2013, 1, 60; c) F. Juliá-Hernández, M.
Gaydou, E. Serrano, M. Gemmeren, R. Martin, Top. Curr. Chem.
2016, 374, 45; d) L. Zhang, Z. Hou, Curr. Opin. Green Sustain. Chem.
2017, 3, 17.
[10] V. R. Yatham, Y. Shen, R. Martin, Angew. Chem. Int. Ed. 2017, 56,
10915.
[11] V. Balzani, Electron Transfer in Chemistry; Wiley-VCH, 2001.
[12] a) M. K. Johnson, A. D. Smith, Iron−sulfurproteinsin: Encyclopedia of
Inorganic Chemistry, 2nd ed.; R. B. King, Ed.; Wiley-VCH, 2005; b) D.
Rickard, G. W. Luther, Chem. Rev. 2007, 107, 514.
[13] a) A. L. Fluharty, In The Chemistry of the Thiol Group; Patai, S., Ed.;
Wiley Interscience: New York, 1974; p 589, Part 2; b) R. A. Sheldon,
Chirotechnologies. In Industrial Synthesis of Optically Active Compounds;
Dekker: New York, 1993.
[
5] a) M. Shi, K. M. Nicholas, J. Am. Chem. Soc. 1997, 119, 5057; b) K. Ukai,
M. Aoki, J. Takaya, N. Iwasawa, J. Am. Chem. Soc. 2006, 128, 8706; c) H.
Ochiai, M. Jang, K. Hirano, H. Yorimitsu, K. Oshima, Org. Lett. 2008, 10,
[14] The methods are mainly limited to the 1,4 addition of thiols to various
substrates. For examples, see: a) G. Sharma, R. Kumar, A. K.
Chakraborti, Tetrahedron Lett. 2008, 49, 4272; b) S. Gao, C. Tseng, C. H.
Tsai, C.-F. Yao, Tetrahedron Lett. 2008, 64, 1955 and references therein.
[15] For a review, see: a) Y.-Y. Gui, W.-J. Zhou, J.-H. Ye, D.-G. Yu,
ChemSusChem 2017, 10, 1337; For examples, see: b) Y. Masuda, N.
Ishida, M. Murakami, J. Am. Chem. Soc. 2015, 137, 14063; c) N. Ishida,
Y. Masuda, S. Uemoto, M. Murakami, Chem. Eur. J. 2016, 22, 6524; d)
Ref. 6l; e) M.-Y. Wang, Y. Cao, X. Liu, N. Wang, L.-N. He, S.-H. Li, Green
Chem. 2017, 19, 1240; f) K. Shimomaki, K. Murata, R. Martin, N. Iwasawa,
J. Am. Chem. Soc. 2017, 139, 9467.
2681; d) C. S. Yeung, V. M. Dong, J. Am. Chem. Soc. 2008, 130, 7826; e)
J. Takaya, S. Tadami, K. Ukai, N. Iwasawa, Org. Lett. 2008, 10, 2697; f) T.
Ohishi, M. Nishiura, Z. Hou, Angew. Chem. Int. Ed. 2008, 47, 5792; g) L.
Zhang, J. Cheng, T. Ohishi, Z. Hou, Angew. Chem. Int. Ed. 2010, 49,
8670; h) I. I. F. Boogaerts, S. P. Nolan, J. Am. Chem. Soc. 2010, 132,
8858; i) I. I. F. Boogaerts, G. C. Fortman, M. R. L. Furst, C. S. J. Cazin, S.
P. Nolan, Angew. Chem. Int. Ed. 2010, 49, 8674; j) K. Nemoto, H.
Yoshida, N. Egusa, N. Morohashi, T. Hattori, J. Org. Chem. 2010, 75,
7855; k) H. Mizuno, J. Takaya, N. Iwasawa, J. Am. Chem. Soc. 2011, 133,
1251; l) K. Sasano, J. Takaya, N. Iwasawa, J. Am. Chem. Soc. 2013, 135,
10954; m) T. Suga, H. Mizuno, J. Takaya, N. Iwasawa, Chem. Commun.
2014, 50, 14360; n) Z. Xin, C. Lescot, S. D. Friis, K. Daasbjerg, T.
[16] We are not clear about exact reason yet, although the ICP-MS detection
demonstrated the presence of 0.0113 ppm iron in the reaction mixture
t
(Please see SI for details). Since compounds like KO Bu, p-toluenethiol,
Skrydstrup, Angew. Chem. Int. Ed. 2015, 54, 6862; o) W.-Y. Gao, H. Wu,
K. Leng, Y. Sun, S. Ma, Angew. Chem. Int. Ed. 2016, 55, 5472; p) A.
Banerjee, G. R. Dick, T. Yoshino, M. W. Kanan, Nature 2016, 531, 215; q)
S. Fenner, L. Ackermann, Green Chem. 2016, 18, 3804; r) J. Luo, S.
Preciado, P. Xie, I. Larrosa, Chem. Eur. J. 2016, 22, 6798.
and the solvent (DMA) in our system are all reductive species, single
2
electron reduction of CO may happen with proper reductive components
(such as thiolate) promoted by light. For example, see: M. E. González-
Núñez, M. Berton, R. Mello, ChemSusChem 2016, 9, 3397.
[17] Some alkyl substituted olefins were tested to give no or low conversion.
Please see SI for details.
[
6] a) C. M. Williams, J. B. Johnson, T. Rovis, J. Am. Chem. Soc. 2008, 130,
1
4936; b) J. Takaya, N. Iwasawa, J. Am. Chem. Soc. 2008, 130, 15254;
[18] a) K. S. Hagen, J. G. Reynolds, R. H. Holm, J. Am. Chem. Soc. 1981, 103,
4054; b) P. V. Rao, R. H. Holm, Chem. Rev. 2004, 104, 527; c) S. C. Lee,
W. Lo, R. H. Holm, Chem. Rev. 2014, 114, 3579. For iron sulfide-
c) H. Ohmiya, M. Tanabe, M. Sawamura, Org. Lett. 2011, 13, 1086; d) T.
Ohishi, L. Zhang, M. Nishiura, Z. Hou, Angew. Chem. Int. Ed. 2011, 50,
8114; e) M. D. Greenhalgh, S. P. Thomas, J. Am. Chem. Soc. 2012, 134,
2
catalyzed reduction of CO , see: d) A. Roldan, N. Hollingsworth, A.
1
1900; f) T. G. Ostapowicz, M. Schmitz, M. Krystof, J. Klankermayer, W.
Roffey, H.-U. Islam, J. B. M. Goodall, C. R. A. Catlow, J. A. Darr, W.
Bras, G. Sankar, K. B. Holt, G. Hogarth, N. H. de Leeuw, Chem.
Commun. 2015, 51, 7501; e) N. Y. Dzade, A. Roldan, N. H. de Leeuw,
J. Chem. Phys. 2015, 143, 094703; f) A. Roldan, N. H. de Leeuw,
Faraday Discuss. 2016, 188, 161.
Leitner, Angew. Chem. Int. Ed. 2013, 52, 12119; g) Q. Liu, L. Wu, I.
Fleischer, D. Selent, R. Franke, R. Jackstell, M. Beller, Chem. Eur. J.
2014, 20, 6888; h) L. Wu, Q. Liu, I. Fleischer, R. Jackstell, M. Beller, Nat.
Commun. 2014, 5, 3091; i) Y. Tani, T. Fujihara, J. Terao, Y. Tsuji, J. Am.
Chem. Soc. 2014, 136, 17706; j) J. Klankermayer, S. Wesselbaum, K.
Beydoun, W. Leitner, Angew. Chem. Int. Ed. 2016, 55, 7296; k) P. Shao,
S. Wang, C. Chen, C. Xi, Org. Lett. 2016, 18, 2050; l) K. Murata, N.
Numasawa, K. Shimomaki, J. Takaya, N. Iwasawa, Chem. Commun.
[19] B. R. Eggins, J. McNeill, J. Electroanal. Chem. Interfacial Electrochem.
1983, 148, 17.
[20] D. Canestrari, S. Lancianesi, E. Badiola, C. Strinna, H. Ibrahim, M. F. A.
Adamo, Org. Lett. 2017, 19, 918.
2
017, 53, 3098; m) X. Ren, Z. Zheng, L. Zhang, Z. Wang, C. Xia, K. Ding,
[21] a) S. Y. Dike, D. H. Ner, A. Kumar, Bioorg. Med. Chem. Lett. 1991, 1, 383;
b) C. Apfel, D. W. Banner, D. Bur, M. Dietz, T. Hirata, C. Hubschwerlen, H.
Locher, M. G. P. Page, W. Pirson, G. Rossé, J.-L. Specklin, J. Med.
Chem. 2000, 43, 2324.
Angew. Chem. Int. Ed. 2017, 56, 310.
[
7] a) D. A. Morgenstern, R. E. Wittrig, P. E. Fanwick, C. P. Kubiak, J.
Am. Chem. Soc. 1993, 115, 6470; b) M. D. Otero, B. Batanero, F.
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Angewandte Chemie International Edition
10.1002/anie.201707862
COMMUNICATION
J.-H. Ye, M. Miao, H. Huang, S.-S. Yan,
Z.-B. Yin, Prof. Dr. W.-J. Zhou, Prof. Dr.
D.-G. Yu*
Page No. – Page No.
Visible light-driven and Iron-
promoted Thiocarboxylation of
Styrenes and Acrylates with CO
2
The first thiocarboxylation of styrenes and acrylates with CO is realized to generate important β-
2
thioacids by using a novel visible light-driven and iron-promoted system. This multicomponent reaction
features broad substrate scope, mild reaction conditions, high regio-, chemo- and diastero-selectivity.
Mechanistic studies indicate that a radical pathway can account for the unusual regioselectivity.
This article is protected by copyright. All rights reserved.