Chelation-assisted C-N cross-coupling of phosphinamides and aryl boronic acids with copper powder at room temperature

Article abstract of DOI:10.1039/c8ob00907d

A protocol for the chelation-assisted C-N cross-coupling of phosphinamides and aryl boronic acids with copper powder under an oxygen atmosphere is reported. This reaction proceeds efficiently to afford fully substituted unsymmetrical N-arylation phosphinamides at room temperature in excellent yields. Diverse unstable functional groups on the benzene ring of aryl boronic acids such as vinyl, formyl, acetyl, sulfonyl, acetylamino, cyano, nitro, and trifluoromethyl can be accommodated.

Full text of DOI:10.1039/c8ob00907d

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Takeharu Haino et al.
Solvent-induced emission of organogels based on tris(phenylisoxazolyl)
benzene
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Chelation-Assisted C–N Cross-Coupling of Phosphinamides and
Aryl Bronic Acids with Copper Powder at Room Temperature
Received 00th January 20xx,
Accepted 00th January 20xx
,a
,a
Yao Peng,
†
Jian Lei,
†
Renhua Qiu,*a Lingteng Peng, a Chak-Tong Au,b and Shuang-Feng Yin*a
DOI: 10.1039/x0xx00000x
www.rsc.org/
A
protocol for chelation-assisted C–N cross-coupling of
phosphinamides and aryl boronic acids with copper powder under
oxygen atmosphere is reported. The reaction proceeds efficiently
to afford fully substituted unsymmetrical N-arylation
phosphinamides at room temperature in excellent yields. A
diverse of unstable functional groups on the benzene ring of aryl
boronic acid such as vinyl, formyl, acetyl, sulfonyl, acetylamino,
cyano, nitro, and trifluoromethyl can be accommodated.
O
N
O
O
P
P
P
N
N
N
N
N
precursor of tetrahydrobenzo-
organic semiconductors
inhibitors of Kv1.5
1-aza-2λ5-phospholes
Figure 1.Selected examples of functionalized compounds having fully substituted
phosphinamides motif.
The high prevalence of fully substituted tertiary
phosphinamides in pharmaceuticals, functional materials and
synthetic intermediates1 has motivated synthetic chemists to
develop convenient and mild amination processes.2 Over the
and ease of separating boron-containing by-products.11
However, this protocol is also limited because of poor product
yield.
past decades, comprehensive studies were conducted on
3
Significant achievements in this direction have been realized
through the development of innovative chelation-assisted
transition-metal catalysis.12 By using naturally more abundant
and inexpensive first-row transition metals as catalysts, the
introduction of a coordinating functional group in the form of
transition-metal assisted C–N bond formation
.
Traditional
methods such as the reaction of amines with carboxylic acid
derivatives,4 aldehydes5 or alcohols,6 hydroamination of
alkynes,7 and hydrogenation of nitriles8 are commonly limited
by poor amide scope and poor reaction efficiency. The ones
that are based on Buchwald-Hartwig reactions9 using halides
as coupling partners for direct C–N bond formation together
with the cleavage of C–X (X = halides) bonds provide
straightforward routes for direct N-substituent of amides.
However, the use of precious palladium catalysts or ligands
somewhat restricted their applications. Nonetheless, a cost-
effective strategy based on the Chan-Lam-Evans reactions,10
has been developed to obtain N-substituted amides via
copper-mediated oxidative amination of aryl boronic acids. In
contrast with the use of organic halides, the use of
organoboron reagents has the advantages of ready availability
of reagents, broad functional group tolerance, low toxicity,
amide framework to promote the formation of
a
cyclometalated intermediate could enable the generation of
unsymmetrical fully substituted amides. Unlike the well-
established intramolecular amidation strategy,13 the approach
of chelation-assisted C–N cross-coupling has been rarely
reported,14 mainly due to the competing C–H functionalization
of amides that are connected to the directing group. Therefore,
a
decisive choice to realize C(sp2)–N cross-coupling is
necessary to nullify the competing C–H functionalization of
amides. Toward this end, Nicholls et al. developed the Cu(II)-
catalyzed amidation of aryl bromides using 8-amidoquinolines
at elevated temperature (Scheme 1a).14a More recently, Baidya
et al. successfully realized Cu(II)-catalyzed picolinamide-
assisted C(sp2)–N cross-coupling with boronic acids to obtain
unsymmetrical tertiary amides at room temperature under
open-flask conditions (Scheme 1b).14b Both of these methods
rely on Cu(II) catalysts with the assistance of a base or other
additive. Relatively few papers describe the use of copper
powder for these reactions.15 More to the point, the
aState Key Laboratory of Chemo/Biosensing and Chemometrics, College of
Chemistry and Chemical Engineering, Hunan University, Changsha 410082, China;
bCollege of Chemistry and Chemical Engineering, Hunan Institute of Engineering,
Xiangtan, 411104, P. R. China
*E-mail: renhuaqiu1@hnu.edu.cn; sf_yin@hnu.edu.cn.
†
Y. P., J. L. contributed equally
generation
of
potentially
useful
N,N-disubstituted
Electronic Supplementary Information (ESI) available: General information,
experimental procedures, copies of 1H, 31P, 19F and 13C NMR spectra for products.
See DOI: 10.1039/x0xx00000x
phosphinamides are still inaccessible through the described
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Table 1. Optimization of reaction conditionsa.
B(OH)2
N
H
copper powder
N
O
N
+
O
N
P
rt, time, solvent
Ph
P
O2
Ph
Ph
Ph
3a
2a
1a
recovery of 1a b
entry
copper powder
10 mol%
20 mol%
50 mol%
1 equiv
none
time (h)
solvent
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
DMF
yield of 3a b
13%
22%
71%
95%
0
1
2
24
24
24
24
24
12
6
78%
64%
14%
0%
3
4
5
100%
0%
6
1 equiv
1 equiv
1 equiv
1 equiv
1 equiv
1 equiv
1 equiv
1 equiv
1 equiv
1 equiv
1 equiv
1 equiv
1 equiv
92%
66%
53%
44%
32%
48%
74%
60%
none
43%
none
59%
none
7
32%
40%
54%
63%
49%
22%
39%
99%
54%
99%
38%
99%
8
3
9
2
10
11c
1
12
12
12
12
12
12
12
12
12d
13
14
15
16
17
18
DMAC
MeOH
toluene
CH2Cl2
o-xylene
a
Reaction conditions: 1a (0.1 mmol), copper powder, and 2a (0.2 mmol) in
Scheme 1 Chelation-Assisted C(sp2)
–N Cross-Coupling.
solvent (1.0 mL) under oxygen atmosphere at room temperature. b Yield was
determined by 31P NMR analysis, using triphenylphosphine oxide (0.1 mmol) as
internal standard. c Under nitrogen atmosphere. dUnder air atmosphere.
Cu(II)-catalysis methods14a,b (Scheme 2c, vide infra).
Herein, we disclose a facile strategy for C(sp2)–N cross-
coupling to produce N,N-disubstituted phosphinamides in high
yields under mild conditions using copper powder (Scheme
1c). Aryl boronic acids are raw chemical materials that are
abundantly available. Oxygen, which is one of the simplest
oxidant, is the only additive in this system. To the best of our
acknowledge, the synthesis of N,N-disubstituted tertiary
amides mediated by copper powder has never been reported.
We initiated our study by using P,P-diphenyl-N-(quinolin-8-
yl) phosphinamides 1a as representative substrate for
condition optimization (Table 1). A proper amount of copper
powder is critical in this reaction. When the reaction
proceeded with catalytic amount of copper powder, only trace
amount of desired product was obtained (entries 1 and 2). If
50 mol% of copper powder was used instead, 3a was obtained
in 71% yield (Table 1, entry 3). When equivalent amount of
copper powder was used, the reaction proceeded efficiently to
obtain the coupling product 3a in 95% yield (Table 1, entry 4).
If copper powder was omitted, 3a was not formed (Table 1,
entry 5). The reaction time could be reduced from 24 h to 12 h
to afford 3a in 92% yield (Table 1, entry 6). Shortening the
reaction time to 6 h, 3 h, 2 h or 1 h are also capable of
obtaining 3a, albeit in relatively lower yields (Table 1, entries
7−10). Of significant relevance was the atmosphere. The yield
was depressed under nitrogen atmosphere (Table 1, entry 11),
indicating that oxygen has a significant effect on reaction
efficiency. Further studies showed that the use of alternate
solvents resulted in lower yields of 3a, indicating the suitability
of acetonitrile as a solvent (Table 1, entries 13−18).
substrates as shown in Table 2. It was found that both
electron-donating and electron-withdrawing groups on the
phenyl ring of aryl boronic acid are well tolerated. Aryl boronic
acid derivatives with alkyl groups at the para- or mata-
positionof phenyl ring could effectively couple with
1,
producing the desired product in up to 95% yields (3b–3g). As
a result of steric hindrance, the reaction of substituent at the
ortho-position of phenyl ring results in significantly lower
amount of desired product (3h). The reactions proceed
effectively in the presence of the C–X (X = F, Cl, Br, I) bonds
(3i–3m), albeit at elevated temperature. The results imply that
the electron-withdrawing ability of X hinders the coupling
reaction. Remarkably, various labile functional groups such as
vinyl (3o), formyl (3p
acetylamino (3u), cyano (3v), nitro (3z), and trifluoromethyl
3w 3x) can be accommodated. It is noted that the reaction
, 3q), acetyl (3r, 3s), sulfonyl (3t),
(
,
proceeds smoothly with strong electron-withdrawing (3,5-
bis(trifluoromethyl)phenyl)boronic acid to afford the
corresponding amidation product (3y) in moderate yield (24%).
The generality of this coupling reaction was further
demonstrated by using other phosphinamides as substrates.
As shown in Table 2, phosphinamides substituted with CH3
(
3ba and 3ca), F (3da and 3ea), Cl (3fa) and OCH3 (3ga) work
well to give the corresponding products in 73−91% yields,
regardless of steric hindrance.
Having extensively investigated the substrate scope and
limitation of the protocol, control experiments were
performed to gain insight into the reaction mechanism. With
the addition of radical scavengers such as TEMPO and BHT, a
significant amount of product 3a could still be obtained
With the optimal condition in hand, we explored the
applicability of the protocol and investigated the scope of
(Scheme 2a). The results confirm that the reaction does not
2 | J. Name., 2012, 00, 1-3
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Table 2. Scope of substratea.
Ar
O
P
B(OH)2
Ar
Ar
copper powder
(1.0 equiv)
O
P
+
N
N
MeCN (1.0 mL)
rt, O2, 12 h
Ar
N
H
Ar
N
Ar
2
1
3
O
O
O
O
O
P
N
P
P
P
P
N
N
N
N
N
N
N
N
N
Et
iPr
nBu
tBu
Me
3b, 92%
3c, 95%
3d, 92%
3e,
90
%
3f, 94%
O
O
O
O
O
P
N
P
N
P
P
P
N
N
F
N
N
N
N
N
N
Cl
Br
3g, 90%
3h, 22%, 31%d
3i, 61%, 93%b
3j, 58%, 96%b
3k, 75%
O
O
O
O
O
P
N
P
P
P
N
P
N
N
N
N
N
F
N
N
N
I
OMe
CHO
3l, 56%, 90%b
3m, 51%, 94%b
3n, 95%
3o, 60%, 92%b
3p, 39%
O
O
O
O
O
P
N
P
N
P
P
P
N
N
S
N
N
N
N
N
N
O
CHO
NH
O
O
O
O
3q, 37%, 82%b
3r, 48%, 57%b
3s, 45%, 70%c
3t, 25%, 55%d
3u, 27%, 89%b
O
O
O
O
O
P
N
P
N
P
P
P
N
N
N
N
N
N
N
N
CF3
F3C
CF3
CN
CF3
NO2
3v, 20%, 49%d
3w, 25%, 68%d
3x, 22%, 79%d
3y, 0%, 24%d
3z, 19%, 27%b
MeO
Me
F
Cl
O
P
N
O
P
N
O
P
N
O
N
O
O
P
N
Me
Me
P
P
F
F
N
N
N
N
N
N
N
MeO
Me
F
Cl
3ba, 78%
3ca, 73%
3da, 91%
3ea, 85%
3fa, 91%
3ga, 84%
a Reaction conditions: 1 (0.1 mmol), copper powder, and 2 (0.2 mmol) in acetonitrile (1.0 mL) under oxygen atmosphere for 12 h at 25 °C. 31P NMR yield, using
triphenylphosphine oxide (0.1 mmol) as internal standard. b Performed at 60 °C. c Performed for 24 h. d Performed at 100 °C.
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catalytically active metal species, we performed three parallel
experiments using CuO, Cu(OH)2 and Cu2O as catalysts under
the optimized conditions (Scheme 2d). We observed that
there was no reaction over CuO or Cu(OH)2. In contrast, when
Cu2O was used instead,
radical scavengers
standard conditions
O
O
B(OH)2
Ph
Ph
a)
b)
+
Q
P
P
N
N
Ph
Ph
H
Q
2.0 equiv TEMPO
2.0 equiv BHT
77%
66%
Q = 8-quinolyl group
O
O
standard conditions
B(OH)2
Ph
Ph
+
DG
P
P
Cu 2p
N
N
3/2
933.7
Ph
Ph
H
DG
F
F
F
F
931.7
F
SM recovered
SM recovered
SM recovered
N
N
N
O
N
SM recovered
N
SM recovered
SM recovered
4, 87%
Nicholls's condition
(10 mol%) X
Cu(SO3CF3)2
Cs2CO3 (3.0 equiv)
toluene (1.0 mL)
938
936
934
932
930
928
O
O
B(OH)2
Ph
Ph
Binding Energy (eV)
Figure 2 XPS Cu 2p3/2 spectrum of copper species collected after reaction under
the optimized conditions.
c)
P
+
P
Q
N
N
Ph
Ph
H
Q
Baidya's condition
X
Cu(OAc)2 H2O (20 mol%)
DMAP (20 mol%)
KI (20 mol%)
the reaction proceeded smoothly to give 3a in 91% yield. It is
hence reasonable to hypothesize that the C–N cross-coupling
reaction was enabled by Cu(I) species of low valence but
restricted by Cu(II) species.
DME, rt, air, 36h
O
O
Cu salts
(1.0 equiv)
B(OH)2
Ph
Ph
d)
e)
+
P
Q
P
acetonitrile (1.0 mL)
rt, O2, 12 h
N
N
Ph
Ph
H
Q
To test this hypothesis, we collected the copper residue by
centrifugation after the reaction. Compared to copper
powder, the recovered copper residue showed a lower yield
(only 10%) (Scheme 2e). We used X-ray photoelectron
spectroscopy (XPS) analysis technique to characterize the
copper species after the coupling reaction. As shown in
Figure 2, the peak at 933.7 eV binding energy corresponds to
Cu2+ valence state. The peak at 931.7 eV binding energy
indicates the presence of Cu0 or Cu+ species.17a,17e With peak
intensity lower than that of Cu2+ peak, the Cu0 or Cu+ species
are present in lower amount. The results suggest that Cu2+ is
the main copper species after the reaction.17
CuO
Cu(OH)2
Cu2O
0%
0%
91%
O
O
recovery copper
B(OH)2
Ph
Ph
+
P
Q
P
acetonitrile (1.0 mL)
rt, O2, 12 h
N
N
Ph
Ph
H
Q
10%
Scheme 2 Control experiments.
involve a free radical pathway. Systematic tuning of the
auxiliary groups was carried out under the optimal conditions.
Starting materials were fully recovered when phenyl,
naphthyl, perfluorophenyl, 3-pyridyl, 2-pyridyl, and 2-(1H-
pyrazol-1-yl)phenyl were used as auxiliary groups, suggesting
that the chelation with the 8-amidoquinoline is critical
(Scheme 2b). It was found that when N-(2-(4,5-
dihydrooxazol-2-yl)phenyl)-P,P-diphenylphosphinamide was
used as substrate 16, the corresponding product was also
1a
H2O
O
O
Ph
Ph
P
P
O2
N
N
CuII
LnCu(0)
Ph
Ph
Ln
CuI
N
O2
N
Ln
X
O
(B)
(A)
Ph
P
obtained in 87% 31P NMR yield (
4). With such notation, it is
N
PhB(OH)2
Ph
N
envisioned that the scope of chelating group can be further
enlarged. To further demonstrate the advantage of this
method, we attempted the C–N cross-coupling using the
Cu(II)-catalyzed amidation approach of phenyl boronic acid at
the conditions recently reported by the groups of Nicholls14a
and Baidya14b. It was found that neither of these catalytic
systems could generate the desired product 3a, and the
results demonstrate the specificity of the methodology
explored in the present study (Scheme 2c). To identify the
3a
O
O
Ph
Ph
O2
P
P
N
LnCu(II)X
N
CuIII
Ph
Ph
Ln
O2
Ln CuII
N
N
(E)
Ph
X
Ph
(C)
(D)
Scheme 3 Plausible mechanism.
4 | J. Name., 2012, 00, 1-3
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Based on the above results and those of previous reports,18
a plausible mechanism is proposed as illustrated in Scheme 3.
First, Cu(0) coordinates with the substrate to give complex 1a
(c) T.-S. Mei, X. Wang and J.-Q. Yu, J. Am. Chem. Soc., 2009,
131, 10806; (d) S. Bhunia, G. G. Pawar, S. V. Kumar, Y.-W.
Jiang and D.-W. Ma, Angew. Chem., Int. Ed., 2017, 56
16136.
,
that reacts with O2 to give bidentate chelating complex (
endowed with a Cu(I) centre, together with the generation of
H2O. After reacting with O2, is converted to Cu(II) species
A)
4
(a) K. Arnold, B. Davies, D. Hérault and A. Whiting, Angew.
Chem., Int. Ed., 2008, 47, 2673; (b) H. Charville, D. Jackson,
G. Hodges and A. Whiting, Chem. Commun., 2010, 46, 1813;
(c) C. L. Allen, A. R. Chhatwal and J. M. J. Williams, Chem.
Commun., 2012, 48, 666; (d) K. Ishihara and Y. Lu, Chem.
A
B,
which upon transmetalation with PhB(OH)2 produces complex C.
Then, undergoing disproportionation or oxidation reaction with O2,
Sci., 2016, 7, 1276; (e) J. R. Dunetz, J. Magano and G. A.
complex
C yields Cu(III) complex D that undergoes smooth
Weisenburger, Org. Process Res. Dev., 2016, 20, 140; (f) R.
M. de Figueiredo, J.-S. Suppo and J.-M. Campagne, Chem.
Rev., 2016, 116, 12029; (g) H. Lundberg, F. Tinnis, N.
Selander and H. Adolfsson, Chem. Soc. Rev., 2014, 43, 2714;
(h) T. Mohy El Dine, W. Erb, Y. Berhault, J. Rouden and J.
Blanchet, J. Org. Chem., 2015, 80, 4532.
reductive elimination to deliver product 3a with concurrent
formation of low-valence Cu(I) species. The latter can be easily
oxidized with O2 to produce Cu(II) species E, restricting the whole
reaction as a result.
5
6
(a) W.-J. Yoo and C.-J. Li, J. Am. Chem. Soc., 2006, 128,
13064; (b) G. N. Papadopoulo and C. G. Kokotos, J. Org.
Chem., 2016, 81, 7023; (c) S. C. Ghosh, J. S. Y. Ngiam, A. M.
Seayad, D. T. Tuan, C. L. L. Chai and A. Chen, J. Org. Chem.,
2012, 77, 8007; (d) P. Subramanian, S. Indu and K. P.
Kaliappan, Org. Lett., 2014, 16, 6212; (e) S. S. R. Gupta, A. V.
Nakhate, K. B. Rasal, G. P. Deshmukh and L. K. Mannepalli,
New J. Chem., 2017, 41, 15268.
Conclusions
In conclusion, we have developed an efficient method for
aminoquinoline-assisted
C–N
cross-coupling
of
phosphinamides and readily available aryl boronic acids with
copper powder under mild conditions. The reaction proceeds
(a) T. T. Nguyen and K. L. Hull, ACS Catal., 2016, 6, 8214; (b)
efficiently with
a wide array of boronic acids and
T. Higuchi, R. Tagawa, A. Iimuro, S. Akiyama, H. Nagae and K.
Mashima, Chem.-Eur. J., 2017, 23, 12795; (c) K. Yamaguchi,
H. Kobayashi, T. Oishi and N. Mizuno, Angew. Chem., Int.
Ed., 2012, 51, 544.
(a) Z.-W. Chen, H.-F. Jiang, X.-Y. Pan and Z.-J. He,
Tetrahedron, 2011, 67, 5920; (b) S. H. Cho, E. J. Yoo, I. Bae
and S Chang, J. Am. Chem. Soc., 2005, 127, 16046.
(a) P. Marce´, J. Lynch, A. J. Blackerb and J. M. J. Williams,
Chem. Commun., 2016, 52, 1436; (b) Y. Li, H. Chen, J. Liu, X.
Wan and Q. Xu, Green Chem., 2016, 18, 4865; (c) J. Li, G.
Tang, Y. Wang, Y. Wang, Z. Li and H. Li. New J. Chem., 2016,
40, 358; d) R. S. Ramon, N. Marion and S. P. Nolan, Chem.
Eur. J., 2009, 15, 8695.
phosphinamides to afford the corresponding products in up
to 96% yield. The wide substrate scopes and simple operation
demonstrates that the protocol opens a practical avenue for
C–N cross-coupling. Further investigations of the application
7
8
of
fully
substituted
unsymmetrical
N-arylation
phosphinamides are currently underway in our laboratory.
Acknowledgements
The authors thank the National Natural Science Foundation
of China (Nos. 21676076, 21725602), and Hunan Youth Talent
(2016RS3023). The authors thank Prof. Nobuaki Kambe
(Osaka University) for helpful discussion. C.T. Au thanks HNU
(Hunan University) for an adjunct professorship.
9
(a) J. F. Hartwig, Angew. Chem., Int. Ed., 1998, 37, 2046; (b)
D. S. Surry and S. L. Buchwald, Chem. Sci., 2011,
Y. Kwong and S. L. Buchwald, Org. Lett., 2003,
Giri, A. Brusoe, K. Troshin, J. Y. Wang, M. Font and J. F.
2, 27; (c) F.
5, 793; (d) R.
Hartwig, J. Am. Chem. Soc., 2018, 140, 793; (e) W. Zhou, M.
Fan, J. Yin, Y. Jiang and D.Ma, J. Am. Chem. Soc., 2015, 137
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Buchwald, Angew. Chem., Int. Ed., 2008, 47, 6338.
,
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