Nickel-catalysed P-C bond formation via P-H/C-CN cross coupling reactions

Article abstract of DOI:10.1039/c5cc01182e

Nickel-catalysed P-H/C-CN cross coupling reactions take place efficiently under mild reaction conditions affording the corresponding sp²C-P bonds. This transformation provides a convenient method for the preparation of arylphosphines and arylphosphine oxides from the readily available P-H compounds and arylnitriles. This journal is

Full text of DOI:10.1039/c5cc01182e

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ARTICLE TYPE
Nickel-Catalysed P–C Bond Formation via P–H/C–CN Cross Couplings
Ji-Shu Zhang,a Tieqiao Chen,*a Jia Yanga and Li-Biao Han*a,b
Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX
DOI: 10.1039/b000000x
5
Nickel-catalysed P–H/C–CN cross couplings take place
Table
1
Nickel-catalysed cross coupling of benzonitrile with
40 diphenylphosphine oxides.a
efficiently under mild reaction conditions affording the
corresponding sp2C–P bonds. This transformation provides a
convenient method for the preparation of arylphosphines and
arylphosphine oxides from the readily available P–H
O
P
O
P
cat
Ni
+
H
Ph
Ph
Ph
Ph
CN
1a
2a
3a
10 compounds and arylnitriles.
Entry Cat Ni
Base
Solvent
Temp Yield(%)b
Ligand
Arylphosphorus compounds have wide applications in material
chemistry, organic synthesis and catalysis, thus the studies on
their preparation have attracted much attention.1 Conventional
procedures use nucleophilic substitutions of the toxic phosphoryl
15 halides with organolithiums or Grignard reagents; however the
hazardous reaction conditions limited the application.1,2 Since the
palladium-mediated coupling reported by Hirao et al,3 transition
metal-catalysed cross couplings of aryl halides or counterparts
with P–H compounds have been well established for the
20 construction of sp2C–P bonds (Scheme 1).3,4 Arylphosphorus
compounds can also be produced by the palladium-catalysed
pyridine group-directed C–H/P(O)–H cross coupling (Scheme
1).5 However, the preparation of phosphorus compounds via C–
CN/P–H cross couplings has never been developed.6
1
2
K2CO3 dioxane
90 o
90 o
C
C
trace
18
Ni(COD)2
Ni(COD)2
dcype
dcype
LiOBu-t dioxane
3
4
5
6
7
8
NaOBu-t dioxane
90 o
90 o
90 o
90 o
90 o
90 o
C
C
C
C
C
C
40
72
66
59
70
65
Ni(COD)2
Ni(COD)2
Ni(COD)2
Ni(COD)2
Ni(COD)2
Ni(COD)2
Ni(COD)2
dcype
dcype
dppm
KOBu-
t
dioxane
KOBu-t dioxane
KOBu-t dioxane
KOBu-t
dppp
Ph3P
dioxane
TMEDA KOBu-t dioxane
9
KOBu-t dioxane
90 o
90 o
C
C
89
80
HQ
-
10
KOBu-t dioxane
Ni(COD)2
-
90 o
90 o
90 o
C
C
C
none
11
12
13
14
HQ
HQ
HQ
HQ
KOBu-t dioxane
KOBu-t toluene
75
Ni(COD)2
Ni(COD)2
Ni(COD)2
none
DMF
KOBu-t
KOBu-t dioxane
110 o
C
66
71
94
cat
M
+
Ar
X
H
Ar
[P]
etc
Hirao
[P]
coupling
15
16c
HQ
HQ
KOBu-t dioxane
KOBu-t dioxane
70 o
90 o
C
Ni(COD)2
Ni(COD)2
=
X
Br,
Cl,
OTf
I,
C
Py
Py
a
cat
Pd
Reaction conditions:
a
mixture of benzonitrile 1a (0.1 mmol),
+
Ar
H
Ar
and
works
H
Yu
Murakami's
P(O)
P(O)
diphenylphosphine oxide 2a (0.1 mmol), a nickel catalyst (0.01 mmol), a
ligand (0.01 mmol), a base (0.2 mmol) and solvent (0.5 mL) in a 25 mL
glass tube is heated at the indicated temperature for 16 h. HQ: 8-
45 hydroxyquinoline. b 31P NMR yield using methyldiphenylphosphine oxide
as an internal standard. c 1.3 equiv 2a was loaded.
cat
Ni
+
Ar
H
CN
Ar
[P]
work
[P]
this
=
and
P-H
[P]-H P(O)-H
25
This reaction was accidently found during the studies on the
synthesis of arylphosphorus compounds using phenol derivatives
and P(O)–H compounds by the nickel-catalysed P–H/C–O cross
50 coupling.8 It was found that 2-methoxynaphthalene reacted with
diphenylphosphine oxide 1a in the presence of 10 mol%
Ni(COD)2 and 2 equivs KOBu-t in benzonitrile at 90 oC for 16 h,
could produce 81% yield of triphenylphosphine oxide via C–
CN/P(O)–H cross coupling, while the expected product 2-
55 naphthyldiphenylphosphine oxide by C–O/P(O)–H cross
coupling was not detected at all. The cross coupling of
benzonitrile with 2a was further investigated and the results were
compiled in Table 1. The use of a proper base is crucial for this
reaction. The yield of the coupling product 3a increased as a
60 stronger base was employed and KOBu-t showed the best (entries
Scheme 1 Synthesis of arylphosphorus compounds via transition metal-
catalysed cross couplings.
Aryl nitriles are readily available chemicals which are widely
used in organic synthesis. However, known functionalization of
30 aryl nitriles via the cleavage of carbon–cyano bonds focused on
carbon–carbon bonding formations that usually use noble metal
catalysts and/or phosphine ligands.7 Herein, we report an efficient
synthesis of both arylphosphines and arylphosphine oxides from
the readily available P–H compounds and aryl nitriles by using
35 the P–H/C–CN direct cross coupling strategy (Scheme 1). This
transformation proceeds smoothly with a simple Ni(COD)2/8-
hydroxyquinoline catalyst, providing an alternative protocol for
the construction of sp2C–P bonds under mild reaction conditions.
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1-4). Phosphine ligands tested did not enhanced the reaction
efficiency (entries 5-8), because in the absence of such a ligand,
this cross coupling also proceeded to give 3a in 80% yield (entry
10). However, when 8-hydroxyquinoline was employed as the
under similar reaction conditions, perhaps due to the steric
hindrance of the substrate. Other substrates with electron-rich
groups like phenyl, methoxy and amino group were readily
phosphorylated to produce the expected products in high yields.
5
ligand, the yield increased to 89% (entry 9). The yield further 30 However,
when
an
electron-deficient
4-
increased to 94% when 1.3 equiv of 2a was used under similar
reaction conditions (entry 16). Nickel complex is essential for this
reaction, since no product was detected in the absence of a nickel
catalyst (entry 11). As to the solvent, this cross coupling also took
(trifluoromethyl)benzonitrile was used as the substrate, only a
trace of 3h was obtained. Though only 41% yield of 3i was
obtained from 1-napthylnitrile, 2-napthylnitriles served well in
the present catalytic system and were converted to the
10 place in toluene, but hardly proceeded in DMF (entries 12 and 35 corresponding coupling products in high yields. Worth noting is
13). In addition, this reaction was sensitive to the reaction
temperature (entries 14 and 15).
that cyanoindole was also successfully phosphorylated by using
this nickel-catalysed P–H/C–CN cross coupling strategy.
As to the hydrogen phosphoryl compounds, other secondary
phosphine oxides also acted as good coupling partners. For
40 example, di(p-tolyl)phosphine oxide coupled with benzonitrile
smoothly, furnishing the expected 3n in 82% yield. A high yield
of 3o was also obtained from (n-Bu)PhP(O)H. The bulky (t-
Bu)PhP(O)H also underwent P–H/C–CN cross coupling with 1a
to give 3p in a high yield. The cross coupling of dibutylphosphine
45 oxide with benzonitrile also took place to produce 3q in 27%
yield under similar reaction conditions.
Table 2 Synthesis of arylphosphine oxides via nickel-catalysed P(O)–
H/C–CN cross coupling.a
O
P
O
P
cat
Ni
+
Ar
Ar
H
R1
R2
R1
R2
CN
1
2
3
Me
O
O
O
PPh2
Me
PPh2
PPh2
3a 90%
3b 89%
,
3c 85%
,
,
Table 3 Synthesis of arylphosphines via nickel-catalysed P–H/C–CN
cross coupling.a
Me
O
O
O
PPh2
Ph
PPh2 Me2N
PPh2
cat
Ni
+
Ar
Ar
HPPh2
PPh2
CN
3d 13%b
3e 78%
,
3f 76%
,
,
1
4
5
O
PPh2
O
O
Me
MeO
PPh2 F3C
PPh2
PPh2
PPh2 Me
PPh2
traceb
5b 72%b
5c 85%b
,
3g 68%
,
3h
3i 41%
,
,
5a 90%
,
,
O
PPh2
O
PPh2
O
PPh2
PPh2
Ph
PPh2 Me2N
PPh2
MeO
5d 65%
,
5e 70%
,
5f 89%
,
PPh2
3j 82%
,
3k 71%
,
3l 69%
,
O
PPh2
PPh2
PPh2
O
O
N
n
PPhBu-
H Me-
p
P(C6
)
2
4
5g 81%
,
5h 90%
,
5i 40%
,
N
Me
a
3m 69%
3n 82%
,
3o 86%
,
,
Reaction conditions: nitrile 1 (0.2 mmol), diphenylphosphine 4 (0.26
50 mmol), Ni(COD)2 (0.02 mmol), 8-hydroxyquinoline (0.02 mmol), KOBu-
t (0.4 mmol), dioxane (1 mL), 25 mL glass tube, 90 oC, 16 h. Isolated
yield. b obtained as the corresponding phosphine oxides.
O
O
n
PPhBu-t
P(Bu- )2
3q 27%b
Interestingly, in addition to the above mentioned P(V)
compounds, the highly coordinative P(III) secondary phosphines
55 also served as the efficient coupling partner in this nickel-
catalysed P–H/C–CN cross coupling reaction to produce the
valuable P(III) phosphines. As shown in Table 3, benzonitrile
coupled with diphenylphosphine 4 readily to produce the
corresponding product 5a in 90% yield. Other benzonitrile
60 analogues bearing methyl or phenyl group also coupled with 4
and were converted to the expected phosphine 5 in high yields.
Worth noting is that substrate with amino group served well in
this catalytic system, yielding 5e in 70% yield. Under similar
reaction conditions, both 1-napthyl nitrile and 2-napthyl nitrile
65 coupled with diphenylphosphine efficiently to produce the
3p 80%
,
,
a
15 Reaction conditions: nitrile 1 (0.2 mmol), P(O)–H compound 2 (0.26
mmol), Ni(COD)2 (0.02 mmol), 8-hydroxyquinoline (0.02 mmol), KOBu-
t (0.4 mmol), dioxane (1 mL), 25 mL glass tube, 90 oC, 16 h. Isolated
yield. b 31P NMR yield.
This P–H/C–CN cross coupling strategy is applicable to other
20 substrates and a wide range of arylphosphine oxides are prepared
under similar reaction conditions (Table 2). Thus, 3-
methylbenzonitrile and 4-methylbenzonitrile coupled with
diphenylphosphine oxide 2a readily to yield the corresponding
product 3b and 3c in 89% and 85% yield, respectively. However,
25 with 2-methylbenzonitrile, only 13% of product was detected
2
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55
5
2
Ar Ni
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65
Ar Ni
[P]
Ar
[P]
C
3
70
Scheme 2 A simplified mechanism for the nickel-catalysed P–H/C–CN
cross coupling
A simplified catalytic cycle is outlined in Scheme 2 for this
10 nickel-catalysed P–H/C–CN cross coupling of P–H compounds
with aryl nitriles. The Ni(0) complex A oxidatively adds to the
C–CN bonds to give B, which subsequently reacts with KOPR1R2,
formed via the deprotonation of 2 by KOBu-t, to yield C.9
75
Reductive elimination of
C produces the corresponding
80
15 arylphosphorus compounds and regenerates Ni(0) complex A. 9
Conclusions
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20 coupling reaction, both arylphosphines and arylphosphine oxides
were produced from the readily available P–H compounds and
aryl nitriles under mild reaction conditions.
85
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Notes and references
a State Key Laboratory of Chemo/Biosensing and Chemometrics, College
25 of Chemistry and Chemical Engineering, Hunan University, Changsha
410082, China. E-mail: chentieqiao@hnu.edu.cn
95
b National Institute of Advanced Industrial Science and Technology
(AIST), Tsukuba, Ibaraki 305-8565, Japan. E-mail: libiao-han@aist.go.jp
† Electronic Supplementary Information (ESI) available: [General
30 information, experimental procedures, characterized data and copies of 1H,
13C and 31P NMR spectra for products]. See DOI: 10.1039/b000000x/
‡ Partial financial supports from NFSC (21403062, 21373080), HNNSF
2015JJ3039, the Fundamental Research Funds for the Central Universities
(Hunan University) are gratefully acknowledged.
100
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