Decarboxylative Aminomethylation of Aryl- and Vinylsulfonates through Combined Nickel- and Photoredox-Catalyzed Cross-Coupling

Article abstract of DOI:10.1002/chem.201604452

A mild approach for the decarboxylative aminomethylation of aryl sulfonates by the combination of photoredox and nickel catalysis through C?O bond cleavage is described for the first time. A wide range of aryl triflates as well as aryl mesylates, tosylates and alkenyl triflates afford the corresponding products in good to excellent yields.

Full text of DOI:10.1002/chem.201604452

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Accepted Article
Title: Decarboxylative Aminomethylation of Arylsulfonates
Authors: Magnus Rueping
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COMMUNICATION
Decarboxylative Aminomethylation of Aryl- and Vinylsulfonates
through Combined Nickel and Photoredox Catalyzed Cross
Coupling
Lulu Fan, Jiaqi Jia, Hong Hou, Quentin Lefebvre and Magnus Rueping*
Abstract: A mild approach for the decarboxylative aminomethylation
of aryl sulfonates by the combination of photoredox and nickel
catalysis via C-O bond cleavage is described for the first time. A
wide range of aryl triflates as well as aryl mesylates, tosylates and
alkenyl triflates afford the corresponding products in good to
excellent yields.
be used as electrophilic cross-coupling partners in
photoredox/nickel dual catalysis. We considered this strategy
appealing because, if successful, it has important advantages
including the greater availability and easier accessibility of
phenyl derivatives compared to most aryl diazonium salts or aryl
halides.
With these considerations in mind, we initially examined the
photoredox catalyzed decarboxylative[11] aminomethylation of 2-
Over the past decades, transition-metal catalyzed cross-
coupling reactions were established as a powerful strategy to
form a variety of C-C and C-heteroatom bonds.[1] The well-
known coupling reactions (Suzuki-Miyaura, Negishi, Kumada,
Hiyama and Stille coupling) typically involve the reaction of
organic electrophiles such as aryl or vinyl halides with
organometallic nucleophiles including aryl or vinyl boronic
acids/esters, zinc halides, Grignard reagents, organosilanes or
stannanes. So far, numerous efforts have been made in this
flourishing area to provide various synthetic building blocks with
high functional group tolerance in an efficient manner.[2]
Whereas, extensive studies were concentrated on the
construction of C(sp2)-C(sp2) bonds, the formation of C(sp2)-
C(sp3) bonds, which is more demanding, is less explored.
Recently, visible-light photoredox catalysis has emerged as a
powerful tool to perform valuable transformations in synthetic
organic chemistry.[3] Moreover, the newly introduced dual
catalysis concept by combining photoredox with organo- and
transition-metal catalysis has shown even greater advantages in
addressing various challenges in organic synthesis.[4] In
particular, the use of photoredox/nickel dual catalysis approach
has received recently great attention for accomplishing
challenging targets.[5,6] Regarding the construction of C(sp2)-
C(sp3) bonds by means of photoredox/nickel dual catalysis
strategy, the electrophilic cross-coupling partners are so far
restricted to aryl and vinyl halides.[5-7]
naphthylpivalate
with
N-phenylglycine
using
various
nickel/phosphine complexes.[12] Unfortunately, no desired
product was detected. This may be due to the oxidative addition
step which we hoped to be possible with more activated phenol
derivatives. To our delight, when we carried out the dual
catalysis approach with the corresponding triflate 1a and N-
phenylglycine (2a) the desired cross-coupling product N-
(naphthalen-2-ylmethyl)aniline (3a) could be obtained.
Importantly the yield is highly depended on the ligands used and
phosphine ligands provided the best results (see supporting
information for details). In fact this is the first example in which
metal-phosphine complexes have been successfully applied in a
dual photoredox and metal catalyzed cross coupling reaction.
Given that many chiral phosphines are available the
development of further asymmetric reactions should be feasible.
Table 1. Optimization of reaction conditions.[a]
OTf
Ir(dFCF3(ppy))2(dtbbpy)PF6
Ni(OTf)2
Ph
N
H
+
Ph
H
N
CO2H
P(4-MeO-Ph)3, Cs2CO3
3a
2a
1a
MeCN, blue LEDs, rt, 21 h
Entry
Variation from the standard conditions
Yield (%)[b]
1
2
3
4
5
None
98(84)
87
In recent years, the use of phenol derivatives as electrophiles in
nickel-catalyzed cross-coupling reactions via C(sp2)-O bond
cleavage has attracted the attention of many organic chemists
including our group.[8-10a-c] During our continuous studies on
nickel catalysis, we questioned whether phenol derivatives could
NiCl2·glyme as Ni catalyst
Ni(cod)2 as Ni catalyst
Ni(cod)2 as Ni catalyst, DMF as solvent
77
35
Ni(cod)2 as Ni catalyst, dtbbpy as ligand, DMF
as solvent
5
6
7
8
9
No photocatalyst
No Ni catalyst
No P(4-MeO-Ph)3
In the dark
0
0
0
0
[*]
Dr. L. Fan, M.Sc. J. Qi, Dr. H. Hou, Dr. Q. Lefebvre, Prof. Dr. M.
Rueping
Institute of Organic Chemistry, RWTH Aachen University
Landoltweg 1, 52074 Aachen (Germany)
E-mail: magnus.rueping@rwth-aachen.de
Prof. Dr. M. Rueping
King Abdullah University of Science and Technology (KAUST),
KAUST Catalysis Center (KCC), Thuwal, 23955-6900 (Saudi
Arabia); E-mail: magnus.rueping@Kaust.edu.sa
[a] Standard conditions: 1a (0.1 mmol), 2a (0.2 mmol), MeCN (0.1 M),
Ir(dFCF3(ppy))2(dtbbpy)PF6 (1 mol %), Ni(OTf)2 (10 mol %), P(4-MeO-Ph)3 (25
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COMMUNICATION
mol %), Cs2CO3 (2 equiv.), blue LEDs, rt, 21 h. [b] Yields determined by 1H
NMR using 1,3,5-trimethoxybenzene as internal standard, isolated yield in
parentheses. bpy = 2,2’-bipyridine, dtbbpy = 4,4’-di-tert-butyl-2,2’-bipyrididyl,
cod = 1,5-cyclooctadiene.
Similarly, the para-fluorophenyl triflate (1g) with an electron-
withdrawing substituent reacted as well and afforded the product
3g in 87% yield. Moreover, other functionalized triflates like 1h
and 1i with nitrile and methyl ester substituents were tolerated
well in the reaction, providing the products 3h and 3i in excellent
yields. In addition, the sesamol derived triflate 1j reacted
smoothly with 2a to afford the desired product 3j in 77% yield.
The 5,6,7,8-tetrahydro-2-napthol derived triflate 1k provided the
product 3k in a good yield of 69%. However, ortho-allylphenyl
triflate 1l proved to be less favoured substrate, giving the
desired product 3l in 49% yield only, probably due to steric
hindrance. To our delight, the estrone derived triflate 1m reacted
well to deliver the desired product 3m in 82% yield.
After optimizing various reaction parameters, the desired
product 3a was obtained in 98% yield if 1 mol % of the Ir-
photocatalyst in combination with the Ni(OTf)2 complex was
employed at room temperature under irradiation with blue LEDs
(Table 1). All other reaction parameters tested including the use
of other nickel complexes, photocatalysts or solvents resulted in
a decreased yield of 3a. Control experiments demonstrated that
in the absence of photocatalyst, Ni-catalyst, phosphine ligand,
base or light, no reaction occurred, indicating that each
component is crucial for this transformation.
With the optimized reaction conditions in hand, we next explored
the substrate scope of this new aminomethylation reaction with
respect to aryl triflates (Table 2). The photoredox/nickel dual
catalytic transformation showed very good tolerance towards a
variety of phenol derived triflates. For example, phenyl triflate
(1b) reacted with N-phenylglycine (2a) to give the desired
product N-benzylaniline (3b) in 94% yield. The substituted
phenyl triflates 1c-e, which possess electron-donating groups in
the para- or meta-position of the phenyl ring gave the
corresponding aniline products 3c-e in excellent yields of 94% to
97%.
The scope of the reaction with respect to α-amino moiety is
summarized in Table 3. The para- and ortho-substituted N-
phenylglycines reacted with phenyl triflate (1b) to afford the
corresponding aniline products 4a-c in good to high yields.
Similarly, substrates with electron-withdrawing groups, such as
methylester and trifluoromethyl underwent the reaction well to
give the desired products 4d and 4e in 72% and 76% yield,
respectively. In addition, halogenated N-phenylglycines were
tolerated as well under the described reaction conditions,
providing the benzyl protected aniline products 4f-h in good
yields. Notably, the additional bromide and chloride rests could
be used in further cross-coupling reaction to construct another
carbon-carbon or carbon-heteroatom bond.
Table 2. Substrate scope of aryl triflates in photoredox/Ni-catalyzed cross-
coupling reactions.[a]
OTf
Table 3. Substrate scope of aminomethylation cross coupling reaction.[a]
Ir(dFCF3(ppy))2(dtbbpy)PF6
Ph
Ni(OTf)2
N
+
Ir(dFCF3(ppy))2(dtbbpy)PF6
OTf
H
H
R
Ni(OTf)2
P(4-MeO-Ph)3,Cs2CO3
Ar
N
CO2H
Ph
+
1
N
Ph
R
3
MeCN, blue LEDs, rt, 24 h
H
H
2a
P(4-MeO-Ph)3,Cs2CO3
N
CO2H
Me
1b
Ar
MeCN, blue LEDs, rt, 24 h
4
2
Ph
N
N
H
H
3c, 97%
3e, 94%
3b, 94%
Me
Ph
Ph
N
4a, 95%
4c, 83%
4b, 78%
Ph
Ph
Ph
Ph
N
H
H
Ph
Ph
Me
Ph
Me
N
H
N
3d, 95%
H
CO2Me
OMe
CF3
Br
MeO
4d, 72%
4f, 81%
N
N
H
Ph
H
N
H
N
3g, 87%
3f, 93%
H
Ph
F
F
4e, 76%
N
H
Ph
Ph
N
Ph
Ph
Ph
H
N
H
N
3h, 95%
3i, 95%
3k, 69%
H
NC
Cl
MeO2C
N
H
4g, 51%
4i, 62%
N
H
4h, 60%
4j, 92%
Ph
Me
H
O
O
N
N
H
H
3j, 77%
O
N
Allyl
H
Ph
N
H
Ph
Ph
H
N
3l, 49%
H
3m, 82%[b]
N
H
Ph
[a] Reaction conditions: 1b (0.1 mmol),
2 (0.2 mmol), MeCN (0.1 M),
Ir(dFCF3(ppy))2(dtbbpy)PF6, (1.5 mol %), Ni(OTf)2 (10 mol %), P(4-MeO-Ph)3
(22 mol %), Cs2CO3 (2 equiv.), blue LEDs, rt, 24 h isolated yields.
[a] Reaction conditions: 1a (0.1 mmol), 2a (0.2 mmol), MeCN (0.1 M),
Ir(dFCF3(ppy))2(dtbbpy)PF6 (1.5 mol %), Ni(OTf)2 (10 mol %), P(4-MeO-Ph)3
(22 mol %), Cs2CO3 (2 equiv.), blue LEDs, rt, 24 h, isolated yields. [b] 48 h.
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Ph
N
The 1-naphthylglycine was also a compatible substrate and the
desired product 4i was obtained with a slightly lower yield of
62%. However, the indole derived acid could afford the product
N-benzylindole 4j in an excellent yield of 92%.
H
R
3n, R = Br, 0%
3o, R = Cl, 81%
H
N
CO2H
+
In addition to the substrates mentioned above, we were
interested in whether our catalytic system could be applied to
the alkenyl triflates which are readily accessible from ketones
(Scheme 1a). To our delight, when the alkenyl triflate 5 was
applied under the standard reaction conditions, the desired
product 6 was isolated in 43% yield. Additionally, when the
relatively unreactive electrophilic 2-naphthyl mesylate (7a) and
tosylate (7b) were subjected to the conditions using 1 mol%
photocatalyst, the corresponding cross-coupling product 3a was
obtained in 71% and 63% yield, respectively (Scheme 1b).
OTf
Ph
R
2a
H
N
standard
(1)
Ph
+
Ph
conditions
OTf
8, 8% (R = Br)
0% (R = Cl)
+
N
1n, R = Br
1o, R = Cl
H
H
N
Ph
9, 50% (R = Br)
10% (R = Cl)
Scheme 2. Nickel/photoredox catalyzed cross coupling of aryl chlorides,
bromides and triflates.
A plausible mechanism for the photoredox/Ni-catalyzed cross-
coupling of α-amino acids with aryl sulfonates is proposed in
Figure 1 and is in agreement with a previously conduced study
by Molander and Kozlowski.6o One electron oxidation of α-amino
acid 2a by the excited state IrIII* generates the radical cation,
followed by deprotonation and decarboxylation to give radical
2a’, which subsequently undergoes radical addition to Ni0 D to
deliver the NiI intermediate E. The oxidative addition of aryl
triflate 1 to E produces the NiIII intermediate F. Subsequently,
reductive elimination of F delivers the cross-coupling product 3
and NiI species G, which undergoes one electron reduction by IrII
to regenerate Ni0 along with the ground state photocatalyst IrIII,
restarting then the catalytic cycles.
Scheme 1. Extension of the Nickel/photoredox catalyzed cross coupling; (a)
Aminomethylation of alkenlytriflates; (b) use of mesylates and tosylates.
(Hetero)Aryl bromides and chlorides have been reported to be
good electrophiles previously.[5] Hence, we were interested in
the relative reactivity of aryl halides and triflates in our cross-
coupling reaction using a photoredox catalyst and the Ni/P(4-
MeO-Ph)3 complex. For this purpose, we subjected the para-
bromo- and para-chloro phenyltriflates (1n and 1o) to the
standard reaction conditions (eq. 1, scheme 2)). The reaction of
1n with 2a occurred mainly at both triflate and bromide sites
providing the bis-alkylated product 9 in 50% yield along with the
triflate product 8 in 8% yield. In the case of para-chloro
phenyltrifalte (1o), the reaction occurred mainly for the triflate,
providing 3o in 81% yield. In this case, product 8 was not
detected, however, product 9 was obtained in 10% yield. These
results suggest that: 1) the reactivity of phenylbromide might be
relatively higher than phenyltriflate under our reaction conditions;
2) aryl triflates could be alternative cross-coupling partners when
aryl bromides are difficult to prepare; 3) the reactivity of chloride
in 1o indicates that our photoredox/Ni-P(4-MeO-Ph)3 system can
also be applied to aryl chlorides, which was not described to
date.
Figure 1. Proposed mechanism for the aminomethylation of arylsulfonates.
In conclusion, we have developed a mild decarboxylative
aminomethylation of aryl- and vinyl sulfonates using
a
combination of visible light photoredox and nickel catalysis via a
C-O bond cleavage procedure for the first time. The reaction has
broad substrate scope and aryl- triflates, mesylates, tosylates
and alkenyl triflates can be applied to give the desired
aminoalkylated products and benzyl protected anilines in good
to excellent yields. The reaction conditions, allowing the cross-
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presence of various functional groups, are rather mild and can
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arenes if needed. Furthermore, we demonstrate that phosphine
complexes can be used in the dual catalytic procedure calling for
the development of combined metal and photoredox catalyzed
asymmetric reactions, a research goal which we are currently
pursuing.
Acknowledgments
The research leading to these results has received funding from
the European Research Council under the European Union's
Seventh Framework Programme (FP/2007-2013) / ERC Grant
Agreement no. 617044 (SunCatChem).
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Keywords: photoredox catalysis • nickel catalysis • cross-
coupling • amino acid • decarboxylation
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Entry for the Table of Contents (Please choose one layout)
Layout 2:
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L. Fan, J. Jia, H. Hou, Q. Lefebvre, M.
Rueping*
Page No. – Page No.
Decarboxylative Aminomethylation of
Aryl- and Vinlysulfonates through
Combined Nickel and Photoredox
Catalyzed Cross Coupling
A mild approach for the decarboxylative aminomethylation of aryl sulfonates by the
combination of photoredox and nickel catalysis via C-O bond cleavage is described.
A variety of aryl triflates, mesylates, tosylates and alkenyl triflates react with α-
amino acids to afford the corresponding aminomethylated products in good to
excellent yields.
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