Highly Chemoselective Iridium Photoredox and Nickel Catalysis for the Cross-Coupling of Primary Aryl Amines with Aryl Halides

Article abstract of DOI:10.1002/anie.201604429

A visible-light-promoted iridium photoredox and nickel dual-catalyzed cross-coupling procedure for the formation C?N bonds has been developed. With this method, various aryl amines were chemoselectively cross-coupled with electronically and sterically diverse aryl iodides and bromides to forge the corresponding C?N bonds, which are of high interest to the pharmaceutical industries. Aryl iodides were found to be a more efficient electrophilic coupling partner. The coupling reactions were carried out at room temperature without the rigorous exclusion of molecular oxygen, thus making this newly developed Ir-photoredox/Ni dual-catalyzed procedure very mild and operationally simple.

Full text of DOI:10.1002/anie.201604429

Angewandte
Communications
Chemie
International Edition: DOI: 10.1002/anie.201604429
German Edition: DOI: 10.1002/ange.201604429
Dual Catalysis
Highly Chemoselective Iridium Photoredox and Nickel Catalysis for
the Cross-Coupling of Primary Aryl Amines with Aryl Halides
Martins S. Oderinde,* Natalie H. Jones, Antoine Juneau, Mathieu Frenette, Brian Aquila,
Sharon Tentarelli, Daniel W. Robbins, and Jeffrey W. Johannes*
Abstract: A visible-light-promoted iridium photoredox and
nickel dual-catalyzed cross-coupling procedure for the forma-
À
tion C N bonds has been developed. With this method, various
aryl amines were chemoselectively cross-coupled with elec-
tronically and sterically diverse aryl iodides and bromides to
À
forge the corresponding C N bonds, which are of high interest
to the pharmaceutical industries. Aryl iodides were found to be
a more efficient electrophilic coupling partner. The coupling
reactions were carried out at room temperature without the
rigorous exclusion of molecular oxygen, thus making this
newly developed Ir-photoredox/Ni dual-catalyzed procedure
very mild and operationally simple.
T
he strategic combination of a photoredox catalyst with
a transition-metal cross-coupling catalyst in chemical syn-
thesis has seen a remarkable “renaissance” in recent years.[1]
The hallmark of this dual-catalytic platform is the systematic
modulation of transition-metal oxidation states by a photo-
redox catalyst through single-electron-transfer (SET) pro-
cesses.[2] This redox-controlled strategy has not only enabled
easy access to previously elusive reaction mechanisms, but
also enhanced the efficiency of known chemical transforma-
tions.[1–3] Cross-coupling conditions employed under dual
catalysis are generally very mild and bond formation proceeds
with exceptionally high chemoselectivity and remarkable
functional group tolerance,[1–3] thus inspiring our continued
interest in this new approach to cross-coupling.
Scheme 1. Photoredox/Ni dual-catalyzed coupling reactions involving
heteroatoms and aryl halides.
Aryl amines are highly valued motifs with important
structural, electronic, and mechanical properties in drug
molecules.[4] Transition-metal-catalyzed coupling of amines
with aryl halides (and pseudohalides) remains the most
versatile and direct method of synthesizing aryl amines, with
Pd catalysis as the most developed synthetic approach.[5]
Despite the tremendous advances that have been made in
bonds in a general fashion through Ni catalysis has proven
challenging. Decreased cost, highly chemoselective mediation
of radical reactions, and modular redox properties are key
advantages of Ni catalysis over Pd catalysis. By exploring the
modular redox properties of Ni, MacMillan and co-workers
À
developed an Ir-photoredox/Ni dual-catalyzed C O cross-
coupling method for the synthesis of aryl ethers (Sche-
Pd-catalyzed C N cross-coupling reactions, forging C N
me 1A).[3] Our group has also developed an Ir-photoredox/Ni
À
À
À
dual-catalyzed C S cross-coupling method, which gave access
to a large library of thioethers (Scheme 1B).[6] A remarkable
[*] Dr. M. S. Oderinde, N. H. Jones, Dr. B. Aquila, S. Tentarelli,
Dr. D. W. Robbins, Dr. J. W. Johannes
À
photoredox/Ni dual-catalyzed C P cross-coupling method
has also been developed by Xiao and co-workers (Sche-
me 1C).[2f] Similarly, Jamison and Tasker reported an elegant
photoredox/Ni dual-catalyzed annulation approach for the
synthesis of indolines (Scheme 1D).[2c]
Department of Chemistry (Oncology)
AstraZeneca Pharmaceuticals LP
35 Gatehouse Dr., Waltham, MA 02451 (USA)
E-mail: martins.oderinde@pfizer.com
jeffrey.johannes@astrazeneca.com
Although there are existing reports on Ni-catalyzed
methods for the amination of aryl halides, those conditions
often require high temperatures and either air-sensitive Ni0
sources or expensive NiII precursors with external reducing
agents, such as zinc dust, NaH, n-BuLi, or MeMgBr, which are
incompatible with many functional groups.[7] In addition, the
A. Juneau, Prof. M. Frenette
Dꢀpartement de Chimie
Universitꢀ du Quꢀbec ꢁ Montrꢀal, Case Postale 8888
Succursale Centre-Ville, Montrꢀal, Quebec, H3C 3P8 (Canada)
Supporting information and the ORCID identification number(s) for
the author(s) of this article can be found under http://dx.doi.org/10.
1002/anie.201604429.
À
mechanism of Ni-catalyzed C N coupling is poorly under-
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stood compared to its Pd counterpart. However, it is believed
lished the importance of light, the Ir catalyst, the Ni complex,
and Et3N for the success of the reaction (Table 1, entries 1–9).
Surprisingly, the coupling proceeded with good conversion in
the absence of the dtbbpy ligand, which suggests that the
aniline can also serve as a ligand (Table 1, entry 10).
Interestingly, unlike in our previously developed Ir-photo-
À
that the C N bond-forming step involves the reductive
elimination of a NiIII species.[8] This mechanistic viewpoint
stems from a seminal report by Koo and Hillhouse in which
they showed that NiII aryl amido complexes do not undergo
reductive elimination, even at elevated temperatures, and
that oxidation of the NiII species into a higher energy
À
redox/Ni dual-catalyzed C S cross-coupling method, aryl
NiIII species by a stoichiometric oxidant is necessary to
bromides and the Ni0 precatalyst, which is generated in situ
[8]
À
produce C N bonds. We therefore recognized that it
from [Ni(cod)2] (cod = 1,5-cyclooctadiene) and dtbbpy, are
À
should be possible to utilize Ir-photoredox/Ni dual catalysis
competent in this C N coupling (Table 1, entries 11–12). Blue
to access the NiIII amido aryl halide species that will undergo
LEDs are the optimal visible-light source for the C N
À
À
facile reductive elimination to form C N bonds (Scheme 1E).
coupling and no coupling was observed under white-light
(26 W CF lamp) irradiation (entry 13).[9] Although no cross-
coupling occurred under green-LED irradiation (entry 14),
This strategy eliminates the stoichiometric oxidant and
À
facilitates chemoselective C N coupling reactions under
mild conditions.
À
irradiation with violet LEDs delivered the C N coupled
Herein, we demonstrate that Ir-photoredox/Ni dual
catalysis can chemoselectively promote the cross-coupling
of primary aromatic amines with aryl iodides and bromides to
product (entry 15). Remarkably, the presence of molecular
À
oxygen does not affect the efficiency of the C N cross-
coupling (Table 1, entries 1 and 16).[6,9] Efficient coupling
without rigorous degassing further underscores the practical
À
afford C N bonds with broad functional group compatibility
À
under very mild conditions.
utility of this newly developed C N bond-forming method.
Our initial efforts focused on the development and
optimization of the catalysts and reaction conditions to
effect the coupling of aniline (1a) and 4-iodotoluene (2a)
(Table 1). To our delight, the desired coupled product 4-
methyl-N-phenylaniline (3a) was obtained in 80% yield in
the presence of NiCl2·dtbbpy (10 mol%), Ir[dF(CF3)ppy]2-
(dtbbpy)PF6 (2 mol%), and Et3N (200 mol%) in MeCN
(0.17m) under blue LED irradiation at room temperature for
24 h (Table 1, entry 1; dtbbpy = 4,4ꢀ-di-tert-butyl-2,2ꢀ-bipyr-
idyl, dF(CF3)ppy = 3,5-difluoro-2-[5-(trifluoromethyl)-2-pyri-
dinyl-N]phenyl-C). A series of control experiments estab-
Having identified the optimal reaction conditions, we
À
explored the substrate scope of the C N cross-coupling
procedure (Table 2). Sterically hindered aryl iodides bearing
methoxy, fluoro, and methyl groups at the ortho position
À
underwent cross-coupling to form C N bonds in good yields
(3b–3d). Impressively, electron-rich and electron-poor aryl
À
iodides delivered C N bonds with nearly identical yields (3e–
À
3h). The high efficiency of C N coupling in the presence of
synthetically useful functional groups, such as fluoride (3g),
chloride (3h), ketone (3i), carbamate (3j), ester (3k),
aldehyde (3l), trifluoromethyl (3m), cyano (3n), and thio-
Table 2: Scope of aryl halide coupling partner.[a]
Table 1: Effect of variation of the reaction parameters and conditions on
the reaction efficiency.
Entry
Variation from the standard conditions[a]
Conversion [%][b]
1
none
>95 (80%)
2
3
no light (dark)
0
0
no IrIII catalyst
4
5
no NiCl2·glyme and no dtbbpy
no Et3N
0
0
6
7
8
9
10
11
12
13
14
15
16
KOtBu instead of Et3N
KN(TMS)2 instead of Et3N
1.5 equiv KOtBu and 0.10 equiv Et3N
iPr2EtN instead of Et3N
no dtbbpy
4-bromotoluene instead of 4-iodotoluene
Ni0·dtbbpy[c] instead of NiCl2·dtbbpy
with a 26 W CF lamp
with 34 W green LEDs
with 34 W violet LEDs
degassed
0
0
<5
80
80-85
50
90
0
0
70
>95 (80%)
[a] Reactions carried out in 3 mL of 99.8% MeCN (0.17m). [b] Con-
version % was determined by 1H NMR spectroscopy with the aid of an
internal standard. The yield of the isolated product after purification by
column chromatography is given in parenthesis. [c] Generated in situ
from [Ni(cod)2] and dtbbpy. TMS=trimethylsilyl.
[a] Unless otherwise stated the aryl iodide was used. Boc=tert-
butoxycarbonyl.
2
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ether (3o) groups, demonstrates mild reaction conditions and
cross-coupling reaction. Most importantly, the remarkable
high chemoselectivity. In addition, heteroaryl iodides under-
went cross-coupling with aniline under these conditions (3j,
3p, and 3q). It is noteworthy that no subsequent coupling of
secondary aryl amine products was detected in any of the
reactions. However, the aryl iodides were fully consumed in
all reactions and the mass balance is the reduced arenes
(hydrodehalogenation reaction). Trace amounts of biaryl
products were also detected in some of the reactions. The
reduced and biaryl side-products indicate a mechanism
involving aryl radicals (see below).
chemoselectivity demonstrated under this Ir-photoredox/Ni
dual-catalysis will allow the orthogonal elaboration of the
reactive functional groups as well as the subsequent cross-
coupling of chloride, alkene, and organoboronate by means of
conventional Pd or Ni catalysis.[5,7]
The exploration of primary aryl amines other than
anilines that can efficiently cross-couple with aryl iodides
under our optimized photoredox-mediated conditions
revealed that sulfonamides (4r, 4s) and 3-aminopyridine
(4t) are competent amines.
The aryl amine scope was also explored to gain further
insight into this coupling reaction (Table 3). Ortho-, meta-,
and para-methylanilines all coupled with both electron-poor
The preference for primary over secondary amines under
our conditions was further demonstrated by conducting the
cross-coupling of 1-chloro-4-iodobenzene with both N-meth-
ylaniline and diphenylamine. In those reactions, little to no
À
and electron-rich aryl iodides to form new C N bonds in
À
C N coupling was detected (Table 3, 4u and 4v). We attribute
the poor efficiency of secondary amines in this reaction to
steric hindrance.
Table 3: Scope of aryl amine coupling partner.
That being said, we observed that the electronic proper-
ties of aryl amines influenced the reaction efficiency. Specif-
ically, para-substituted anilines and sulfonamides gave lower
À
yields of C N coupled products (4g–4j, 4s).
Although additional mechanistic studies are ongoing in
our laboratories, we propose the mechanism depicted in
Figure 1. Visible-light irradiation of the heteroleptic IrIII
photocatalyst generates a long-lived excited *IrIII species
(lifetime t = 2.35 ms).[6] Kinetic oxidation of the aniline
moderate to good yields (4a–4c). Satisfactorily, anilines
bearing synthetically versatile functional groups, such as
hydroxy, vinyl, acetylene, chloro, methoxy, and acetyl groups,
À
all engaged in chemoselective C N cross-coupling with
electronically diverse aryl iodides to deliver synthetically
useful scaffolds (4d–4k). In addition, substituted anilines
were cross-coupled with aryl iodides bearing useful functional
groups, such as organoboronate (4l) and heteroaryl iodides
(4m–4p), to give the desired products in good yields. A
À
À
Figure 1. Proposed C N coupling mechanism.
naphthylamine (4q) also competently engaged in the C N
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(E1/2ox =+ 0.80 V versus the saturated calomel electrode
methyl, methoxy, thioether, and acetylene, using this mild
procedure. Mechanistic studies and experimental evidence
suggest that the reaction proceeds through an aminyl radical
and a stepwise oxidative addition process. This synthetic
method should find use in the synthesis of nitrogen-containing
drug molecules and the mechanistic insights provided should
promote interest and further development.
(SCE))[10a] by the photoexcited *IrIII species (E1/2 [*IrIII/
red
IrII] =+ 1.21 V versus SCE)[11] produces both the aniline
radical cation 6 and IrII (see the Supporting Information for
emission quenching studies). Deprotonation of the aniline
radical cation 6 (pKa = 7.1)[10a] by Et3N (pKa = 11)[10b] then
produces the aniline radical 7. SETreduction of NiCl2·dtbbpy
(E1/2 [NiII/NiI] = À1.34 V versus SCE)[6] by IrII (E1/2 [IrIII/
IrII] = À1.37 V versus SCE)[11] will initially regenerate the
IrIII photocatalyst and deliver the NiI–halide complex 8. At
this juncture, 8 rapidly intercepts the aniline radical 7 to form
NiII species 9, which is then reduced to NiI–amido derivative
10 by IrII. Oxidative addition of the aryl halide to NiI–amido
species 10 delivers the NiIII complex 11, which undergoes
red
red
Acknowledgements
M.S.O. thanks AstraZeneca (Oncology and Innovative Med-
icine) for scientific innovation and achievement awards.
N.H.J. thanks the AstraZeneca Innovative Medicines and
Early Development Graduate Programme for funding.
À
facile reductive elimination to form the C N coupled product
with concomitant regeneration of the NiI–halide complex 8.
The observed reduction of the aryl halide is indicative of
a step-wise oxidative addition involving a SET process
Keywords: cross-coupling · nickel catalysis · photocatalysis ·
radical reactions · synthetic methods
(Figure 1B).[12] The oxidation potential of
a similar
NiI–amido complex (E1/2 [NiI/NiII] = À0.90 V versus Fc/Fc+
or À0.52 V versus SCE),[13] indicates that the reduction of
iodobenzene (E1/2red = À1.59 V versus SCE)[14] by NiI–amido
species 10 in its ground state is thermodynamically unfavor-
able (endergonic). However, visible-light excitation of
NiI–amido 10 should produce a long-lived and highly reducing
excited *NiI–amido species 12.[15] Subsequent SET reduction
of aryl iodides and bromides by *NiI–amido species 12 will
give an ionic NiII complex 13 together with an aryl radical. We
recognized here that the amineꢀs electronic properties will
have a strong influence on the efficiency of the excitation of
10, the resulting lifetime of 12, and the rate at which 13 reacts
with the aryl radical. To this end, the aryl radical can either be
trapped by 13 to give NiIII–amido aryl halide 11 or undergo
hydrogen atom abstraction from an aminium radical cation[12]
to give the reduced product. Should the hydrogen atom
abstraction reaction be favored, a single electron reduction of
the ionic NiII complex 13 by IrII will reproduce NiI–amido
species 10.
The high efficiency of the coupling conducted with the
Ni0 precatalyst (Table 1, entry 12) suggests that a rapid trap of
the Ni0 complex by the aniline radical 7 can also produce the
NiI–amido species 10 (Figure 1B).[9] Finally, we attribute the
low coupling efficiency of amines containing an a-Csp3-H
group, such as benzyl amines and alkyl amines (Table 3, 4w–
4y), to competitive deprotonation of their corresponding
aminium radical cation at the a position. NiI–amido com-
plexes generated from such amines may also be susceptible to
undesirable b-hydride elimination reactions.[16]
oxi
[1] For reviews, see: a) M. N. Hopkinson, B. Sahoo, J. Li, F. Glorius,
Chem. Eur. J. 2014, 20, 3874; b) E. Jahn, U. Jahn, Angew. Chem.
Int. Ed. 2014, 53, 13326; Angew. Chem. 2014, 126, 13542; c) C.
Vila, ChemCatChem 2015, 7, 1790; d) Y.-Y. Gui, L. Sun, Z.-P. Lu,
D.-G. Yu, Org. Chem. Front. 2016, 3, 522 and references therein;
e) K. L. Skubi, T. R. Blum, T. P. Yoon, Chem. Rev. 2016, DOI:
10.1021/acs.chemrev.6b00018.
[2] a) B. Sahoo, M. N. Hopkinson, F. Glorius, J. Am. Chem. Soc.
2013, 135, 5505; b) D. Kalyani, K. B. McMurtrey, S. R. Neufeldt,
M. S. Sanford, J. Am. Chem. Soc. 2011, 133, 18566; c) S. Z.
Tasker, T. F. Jamison, J. Am. Chem. Soc. 2015, 137, 9531; d) X.-Z.
Shu, M. Zhang, Y. He, H. Frei, F. D. Toste, J. Am. Chem. Soc.
2014, 136, 5844; e) C. LꢁvÞgue, L. Chenneberg, V. Corcꢁ, J.-P.
Goddard, C. Ollivier, L. Fensterbank, Org. Chem. Front. 2016, 3,
462; f) J. Xuan, T.-T. Zeng, J.-R. Chen, L.-Q. Lu, W.-J. Xiao,
Chem. Eur. J. 2015, 21, 4962; g) J. C. Tellis, D. N. Primer, G. A.
Molander, Science 2014, 345, 433; h) Z. Zuo, D. Ahneman, T. L.
Chu, J. A. Terrett, A. G. Doyle, D. W. C. MacMillan, Science
2014, 345, 437.
[3] J. A. Terrett, J. D. Cuthbertson, V. W. Shurtleff, D. W. C. Mac-
Millan, Nature 2015, 524, 330.
[4] a) N. J. Butcher, S. Boukouvala, E. Sim, R. F. Minchin, Pharma-
cogenomics J. 2002, 2, 30; b) G. E. Robinson, et al., Org. Process
Res. Dev. 2004, 8, 925; c) J.-P. Corbet, G. Mignani, Chem. Rev.
2006, 106, 2651.
[5] a) G. D. Vo, J. F. Hartwig, J. Am. Chem. Soc. 2009, 131, 11049;
b) C. W. Cheung, D. S. Surry, S. L. Buchwald, Org. Lett. 2013, 15,
3734; c) L. Jiang, X. Lu, H. Zhang, Y. Jiang, D. Ma, J. Org. Chem.
2009, 74, 4542; d) X. Xie, G. Ni, F. Ma, L. Ding, S. Xu, Z. Zhang,
Synlett 2011, 955; e) T. Hatakeyama, R. Imayoshi, Y. Yoshimoto,
S. K. Ghorai, M. Jin, H. Takaya, K. Norisuye, Y. Sohrin, M.
Nakamura, J. Am. Chem. Soc. 2012, 134, 20262; f) D. T. Ziegler,
J. Choi, J. M. Munoz-Molina, A. C. Bissember, J. C. Peters, G. C.
Fu, J. Am. Chem. Soc. 2013, 135, 13107; g) M. Pompeo, J. L.
Farmer, R. D. Froese, M. G. Organ, Angew. Chem. Int. Ed. 2014,
53, 3223; Angew. Chem. 2014, 126, 3287; h) A. S. Guram, R. A.
Rennels, S. L. Buchwald, Angew. Chem. Int. Ed. Engl. 1995, 34,
1348; Angew. Chem. 1995, 107, 1456; i) J. Louie, J. F. Hartwig,
Tetrahedron Lett. 1995, 36, 3609.
In conclusion, we have developed a mild, highly chemo-
selective photoinduced Ir/Ni dual-catalyzed procedure for the
cross-coupling of primary aryl amines with aryl and hetero-
aryl halides, which, to the best of our knowledge, is the first
method of its kind. In terms of practical utility, this dual-
À
catalyzed C N coupling procedure operates with high
efficiency in the presence of molecular oxygen using
a simple and readily available Ni-based catalyst. We also
demonstrate the tolerance of synthetically useful functional
groups, including alcohol, fluoride, chloride, aldehyde,
organoboronate, vinyl, ketone, carbamate, ester, cyano,
[6] M. S. Oderinde, M. A. Frenette, B. Aquila, D. W. Robbins, J. W.
Johannes, J. Am. Chem. Soc. 2016, 138, 1760.
4
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Communications
Chemie
[7] a) J. P. Wolfe, S. L. Buchwald, J. Am. Chem. Soc. 1997, 119, 6054;
[13] a) D. J. Mindiola, G. L. Hillhouse, J. Am. Chem. Soc. 2001, 123,
b) C. Chen, L.-M. Yang, J. Org. Chem. 2007, 72, 6324; c) C.
Chen, L.-M. Yang, Org. Lett. 2005, 7, 2209; d) B. H. Lipshutz, H.
Ueda, Angew. Chem. Int. Ed. 2000, 39, 4492; Angew. Chem.
2000, 112, 4666; e) C. Desmarets, R. Schneider, Y. Fort, J. Org.
Chem. 2002, 67, 3029.
4623; b) M. I. Lipschutz, T. D. Tilley, Angew. Chem. Int. Ed.
2014, 53, 7290; Angew. Chem. 2014, 126, 7418; c) For conversion
constants for redox potentials see: V. V. Pavlishchuk, A. W.
Addison, Inorg. Chim. Acta 2000, 298, 97.
[14] a) A. J. Fry, R. L. Krieger, J. Org. Chem. 1976, 41, 54; b) L.
Pause, M. Robert, J.-M. Savꢁant, J. Am. Chem. Soc. 1999, 121,
7158.
[8] a) K. Koo, G. L. Hillhouse, Organometallics 1995, 14, 4421; b) K.
Koo, G. L. Hillhouse, Organometallics 1996, 15, 2669; c) B. L.
Lin, C. R. Clough, G. L. Hillhouse, J. Am. Chem. Soc. 2002, 124,
2890.
[9] M. S. Oderinde, A. Varela-Alvarez, B. Aquila, D. W. Robbins,
J. W. Johannes, J. Org. Chem. 2015, 80, 7642.
[15] For the CuI analogue, see: a) Q. M. Kainz, C. D. Matier, A.
Bartoszewicz, S. L. Zultanski, J. C. Peters, G. C. Fu, Science 2016,
351, 681; b) W.-J. Yoo, T. Tsukamoto, S. Kobayashi, Org. Lett.
2015, 17, 3640.
[10] a) M. Jonsson, J. Lind, T. E. Eriksen, G. Merꢁnyi, J. Am. Chem.
Soc. 1994, 116, 1423; b) M. Masui, H. Sayo, Y. Tsuda, J. Chem.
Soc. B 1968, 973.
[16] It is possible that Et3N plays an additional role in the reaction.
We are currently studying the mechanism of this reaction in
more detail.
[11] M. S. Lowry, J. I. Goldsmith, J. D. Slinker, R. Rohl, J. R. A.
Pascal, G. G. Malliaras, S. Bernhard, Chem. Mater. 2005, 17,
5712.
[12] J. D. Nguyen, E. M. D’Amato, J. M. R. Narayanam, C. R. J.
Stephenson, Nat. Chem. 2012, 4, 854.
Received: May 6, 2016
Published online: && &&, &&&&
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Communications
Dual Catalysis
Lights, metal, action: A visible-light-pro-
moted dual-catalytic cross-coupling pro-
cedure combining Ir photoredox catalysis
M. S. Oderinde,* N. H. Jones, A. Juneau,
M. Frenette, B. Aquila, S. Tentarelli,
D. W. Robbins,
À
and Ni catalysis to form C N bonds has
been developed. This mild and opera-
tionally simple method proceeds at room
temperature without rigorous exclusion
of O2 and was employed for the cross-
coupling of various aryl amines with
electronically and sterically diverse aryl
iodides and bromides.
J. W. Johannes*
&&&& — &&&&
Highly Chemoselective Iridium
Photoredox and Nickel Catalysis for the
Cross-Coupling of Primary Aryl Amines
with Aryl Halides
6
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