The Chan-Evans-Lam N-arylation of phosphonic/phosphinic amides

Article abstract of DOI:10.1016/j.tet.2017.06.028

A stoichiometric copper(II)-mediated arylation protocol of phosphinamides and phosphonamides was herein demonstrated. Various unreported N-aryl phosphinamides and phosphonamides were successfully prepared through Chan-Evans-Lam reaction with high efficiency (up to 88% yields) and good functional groups tolerance (30 examples) in the absence of any ligands or co-catalysts.

Full text of DOI:10.1016/j.tet.2017.06.028

Accepted Manuscript
The Chan-Evans-Lam N-arylation of phosphonic/phosphinic amides
Yuqin Xu, Qiong Su, Wanrong Dong, Zhihong Peng, Delie An
PII:
S0040-4020(17)30647-6
10.1016/j.tet.2017.06.028
TET 28793
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 1 May 2017
Revised Date: 12 June 2017
Accepted Date: 14 June 2017
Please cite this article as: Xu Y, Su Q, Dong W, Peng Z, An D, The Chan-Evans-Lam N-arylation of
phosphonic/phosphinic amides, Tetrahedron (2017), doi: 10.1016/j.tet.2017.06.028.
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The Chan-Evans-Lam N-Arylation of
Phosphonic/Phosphinic amides
Yuqin Xu,† Qiong Su,† Wanrong Dong*, Zhihong Peng* and Delie An*
State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical
Engineering, Hunan University, Lushan South Rd. 2, Changsha, 410082, P.R. China
wanrongdong@hnu.edu.cn; pzh7251@hnu.edu.cn; deliean@hnu.edu.cn.
† Y.Q. Xu and Q. Su devoted equal contribution to the publication.
A general and efficient arylation protocol of phosphinamides and phosphonamides was herein demonstrated. And various
unreported N-aryl phosphinamides and phosphonamides were successfully prepared through the Chan-Evans-Lam reaction
with high efficiency (up to 88% yields) and good functional groups tolerance (30 examples). The stoichiometric copper(II)-
mediated transformation required for no organic ligands or co-catalysts.

1
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Tetrahedron
journal homepage: www.elsevier.com
The Chan-Evans-Lam N-Arylation of Phosphonic/Phosphinic amides
Yuqin Xu,† Qiong Su,† Wanrong Dong*, Zhihong Peng* and Delie An*
State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Lushan South Rd.2,
Changsha, 410082, P.R. China.
† Y.Q. Xu and Q. Su made equal contributions to the publication.
Emails: wanrongdong@hnu.edu.cn; pzh7251@hnu.edu.cn; deliean@hnu.edu.cn.
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
A
stoichiometric copper(II)-mediated arylation protocol of phosphinamides and
phosphonamides was herein demonstrated. Various unreported N-aryl phosphinamides and
phosphonamides were successfully prepared through Chan-Evans-Lam reaction with high
efficiency (up to 88% yields) and good functional groups tolerance (30 examples) in the absence
of any ligands or co-catalysts.
Available online
Keywords:
2009 Elsevier Ltd. All rights reserved
.
Chan-Evans-Lam Couplings
Phosphinamides
Phosphonamides
Copper diacetate
Arylboronic acids
1. Introduction
Constructions of carbon-hetero bonds have gained widespread
research interests. Despite great contributions have been made
for higher efficiency,[1] Chan-Evans-Lam reactions have been
considered as a powerful tool in the field for the advantages
including stable reagents, easy-to-workup procedure and good
compatibility.[2] Arylboronic acids have been generally coupled
in the presence of different transition metal-catalysts, such as
Cu,[3] Ni,[4] and Au,[5] for the formations of various carbon-hetero
bonds such as C-N,[3, 6] C-O,[7] C-P[8] and C-S bonds[9]. Amines,
amides, azides have been arylated successfully with arylboronic
acids for the generation of Ar-N bonds under mild conditions.
Be aware of those phosphonic amides and phosphinic amides
have attracted extensive attention in the fields of synthetic and
pharceutical chemistry[10] for not only the unique structures, but
also the versatile roles in the clinical chemistry, explorations for
the derivations of the useful compounds have been carried out
and inter or intra-molecular annulation towards heterocycles like
benzazaphosphole 1-oxides and phosphaisoquinoline 1-oxides
have been realized by kinds of synthetic tools.[11] However,
arylation of phosphonic amides and phosphinic amides reamined
unexplored except the only example from Guo,[12] wherein aryl
iodides were successfully applied as the arylation reagents of
phosphinic amides in the presence of CuI and (±)-trans-
cyclohexane-1,2-diamine (Scheme 1, A)). Thus, to enrich the
diversity of the –P(=O)-N- backboned molecules, novel
methodologies are still severely required. Within this context, we
wish to demonstrate a general arylation method towards N-aryl
phosphonic amides and N-aryl phosphinic amides with assistance
of a simple Cu(II)-salt without participation of any organic
ligands (Scheme 1, B)).
Scheme 1. Arylation of phosphonic/phosphinic amides
2. Results and discussions
Firstly, reactions between P,P-diphenyl phosphinamide (1a)
and p-tolyl boronic acid (2a) were carried out for the optimal
conditions as summarized in Table 1. With a stoichiometric 1.0
equivalent of Cu(OAc)2 and 2.0 equivalents of K2CO3,
optimization on the effect of different solvents was conducted.
Alcoholic solvents and chlorinated solvents such as methyl
alcohol (entry 1), tert-butyl alcohol (entry 2), chloroform (entry 3)
and DCE (1,2-dichloro ethane for entry 4) could not provide
satisfactory results, for no reaction or only trace product 3aa was
detected after 10 hours. Other solvents, such as DMF (N,N-
dimethyl formamide, entry 5) and DMSO (dimethyl sulfoxide,
entry 6) offered the similar effects to the transformation. To our
satisfactory, participation of toluene provided the N-(4-
methylphenyl)-P,P-diphenyl phosphinamide (3aa) in 58% yield
(entry 7). Sodium carbonate gave analogous performance with
potassium carbonate, while cesium carbonate afforded superior
effect for 62% of 3aa was smoothly isolated in toluene (entries 8
and 9). But involvement of CsOAc offered 3aa in 48% yield,

2
Tetrahedron
yields. c) Stands for no reaction. d) 4Å molecular sieves (powdered, 100wt%)
inferior to the results obtained from Cs2CO3 (entry 10).
ACCEPTED MANUSCRIPT
e)
was added. The yield in the parentheses was obtained under O2 (1 atm)
Disappointingly, organic bases, such as triethyl amine and
pyridine, failed to make the arylation protocol proceed in the
Cu(II)-catalyzed system (entry 11 and 12). Other Cu(II) or Cu(I)
catalysts, such as CuSO4, CuCl2, CuI and CuBr were proved
useless to the transformation and trace 3aa were detected after 10
hours (entries 13 – 16). Increased loading of Cu(OAc)2 (2.0
equiv.) furnished the corresponding N-arylated phosphinamide
3aa in 75% yield (entry 17), while 48% yield of 3aa was
observed with reduced loading of Cu(OAc)2 (entry 18). To our
delight, addition of powdered molecular sieves (4 Å, 100 wt%)
raised the yield of 3aa to 85% (entry 19). Inner atmosphere also
had significant impact over the arylation protocol (entry 19, note
e)), for 73% of 3aa was furnished under the dioxygen
atmosphere probably because of the homo-coupling of 2a. If the
the reaction was conducted in the presence reduced amount of 4
Å MS (50 wt%), the yield of 3aa was slightly lower, up to 83%
(entry 20), whereas increased loading of MS (200 wt%) led to the
dramatic decrease in the efficiency of the coupling reaction, for
75% 3aa was successfully isolated (entry 21). This probably
resulted from insufficient stirring of the mixture.
f)
g)
atmosphere.
molecular sieves was added.
50 wt% 4Å molecular sieves was added.
200 wt% 4Å
Beyond our expectations, substituted phosphonamides showed
good compatibility in the Cu(II)-mediated system and coupled
with p-tolyl boronic acid (2a) smoothly under the optimal
conditions, which was shown in Table 2. For instance, P-Phenyl-
P-methoxy phosphonamide (1b) reacted with p-tolyl boronic acid
(2a) successfully, offering the desired arylated product 3ba in
79% yield (entry 1). In a similar pattern, other alkoxy decorated
phosphonamides, including P-ethoxy (entry 2), P-isopropoxy
(entry 3), P-butoxy (entry 4), P-(2-methoxyethoxy) (entry 5)
underwent the arylation reaction readily, providing the
corresponding N-(p-tolyl) phosphonamides 3ca – 3fa in yields
from 75% to 83%. It was noteworthy that P-phenyl-P-
cyclohexyloxy phosphonamide (1g) produced the desired product
3ga in satisfactory 85% yield (entry 6), superior to P-isopropoxy
did despite the similar steric hindrance. Unsaturated carbon-
carbon triple bond was also well tolerated in the reaction, which
was exemplified by the formation of N-(p-tolyl)-P-diphenyl-P-
(2-butynyloxy) phosphonamide (3ha), in a ratio up to 88% (entry
7). Other substituents, such as benzyloxy groups, were also found
compatible in the system. For example, benzyloxy, 3-
fluorobenzyloxy, 4-chlorobenzyloxy, 2-bromobenzyloxy groups
gave an access to the desired N-arylated phosphonamides 3ia –
3la in yields ranging from 79% to 83% (entries 8 -11). N-(p-
tolyl)-P-(4-morpholinyl)-P-phenyl phosphinamide was favorably
generated under the Cu(II)-catalysis in 56% yield (entry 12).
Table 1. Optimization of the reaction conditions[a]
Entry
1
[Cu] (equiv.)
Cu(OAc)2 (1.0)
Cu(OAc)2 (1.0)
Cu(OAc)2 (1.0)
Cu(OAc)2 (1.0)
Cu(OAc)2 (1.0)
Cu(OAc)2 (1.0)
Cu(OAc)2 (1.0)
Cu(OAc)2 (1.0)
Cu(OAc)2 (1.0)
Cu(OAc)2 (1.0)
Cu(OAc)2 (1.0)
Cu(OAc)2 (1.0)
CuCl2 (1.0)
Base
Sol.
Yield b)
n.d.c)
n.d.
Table 2. Substrates scope of the phosphonamides[a]
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
Na2CO3
Cs2CO3
CsOAc
Et3N
CH3OH
tBuOH
CHCl3
DCE
O
O
P
Cu(OAc)2, Cs2CO3
H
+
2a
P
NH2
N
2
p-Tol
toluene, 4 Å MS
80 oC, 10 h
R
R
3
trace
trace
trace
20%
1b - 1m
Entry
3ba - 3ma
Yield b)
4
1
1b
1c
1d
1e
1f
R
3
5
DMF
1
2
CH3O-
3ba
3ca
3da
3ea
3fa
3ga
3ha
3ia
79%
83%
78%
78%
75%
85%
88%
83%
79%
81%
81%
56%
6
DMSO
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
CH3CH2O-
7
58%
3
(CH3)2CHO-
CH3(CH2)3O-
CH3O(CH2)2O-
cyclo-C6H11CH2O-
CH3C≡CCH2O-
C6H5CH2O-
8
56%
4
9
62%
5
10
11
12
13
14
15
16
17
18
19d)
20f)
21g)
48%
6
1g
1h
1i
n.d.
7
pyridine
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
n.d.
8
trace
trace
trace
trace
75%
9
1j
3-FC6H5CH2O-
4-ClC6H5CH2O-
2-BrC6H5CH2O-
4-Morpholinyl-
3ja
3ka
3la
CuSO4 (1.0)
10
11
12
1k
1l
CuI (1.0)
CuBr (1.0)
1m
3ma
Cu(OAc)2 (2.0)
Cu(OAc)2 (0.5)
Cu(OAc)2 (2.0)
Cu(OAc)2 (2.0)
Cu(OAc)2 (2.0)
a)
Reaction conditions: 1 (0.5 mmol), 2a (0.6 mmol), Cu(OAc)2 (1.0 mmol),
o
b)
48%
Cs2CO3 (1.0 mmol), 4Å MS (100 wt%), in toluene (3.5 mL) at 80 C for 10 h.
Isolated yields.
85% (73%)e)
83%
Successively, the tolerance of the functional groups of aryl
boronic acids was also checked in the system as shown in Table 3.
Phenyl boronic acid (2b) coupled with phosphinamide 1a readily,
offering N,P,P-triphenyl phosphinamide (3ab) in acceptable 76%
yield (entry 1). Tolyl boronic acids were well-tolerated in the
75%
a) Reaction conditions: 1a (0.3 mmol), 2a (0.36 mmol), [Cu], base (2.0 equiv.),
under air atmosphere or noted, in sol. (2.0 mL) at 80 oC for 10 h. b) Isolated

3
system, for N-(2-methylphenyl), N-(3-methylphenyl) and N-(2,4-
dimethylphenyl) phosphinamides 3ac – 3ae were furnished in
yields ranging from 76% to 82% (entries 2 – 4). Other alkyl
substituted phenyl groups were also compatible in the protocol,
for N-(2-ethylphenyl), N-(4-ethylphenyl), N-(4-isopropylphenyl),
N-(4-tertbutylphenyl) phosphinamides 3af – 3ai in yields from
75% - 79% (entries 5 – 8). Electron-sufficient phenyl groups also
provided good performance in the reaction, as exemplified with
3-methoxyphenyl and 4-methoxyphenyl boronic acids 1j and 1k
afforded the corresponding products 3aj – 3ak in good yields, up
to 83% (entries 9 and 10). Halogenated phenyl groups fused
boronic acids, such as 4-fluorophenyl, 4-chlorophenyl and 4-
bromophenyl boronic acids furnished the desired N-arylated
phosphinamides 3al – 3an in yields up to 80% (entries 11 – 13).
Furthermore, successive arylation of 3aa was also explored in
ACCEPTED MANUSCRIPT
the system. However, trace product 3aa was detected at either 80
oC or 100 C for 10 hours. Elevated reaction temperature at 120
o
oC gave an access towards N,N-di-(p-tolyl)-P-phenyl
phosphinamide 4aa but only 32% yield was obtained (scheme 2,
B)).
O
P
O
P
H
N
Cu(OAc)2, Cs2CO3
+ p-TolylBF3K
A
B
)
)
NH2
toluene, 4 Å MS
80 oC, 10 h
p-Tolyl
1a
3aa: 82%
O
P
O
Cu(OAc)2, Cs2CO3
H
N
p-Tolyl
p-Tolyl
+
2a
P
N
toluene, 4 Å MS
Temp., 10 h
p-Tolyl
Electron-deficient
phenyl
groups,
such
as
4-
trifluoromethylphenyl, 2-nitrophenyl substituted phosphinic
amides 3ao and 3ap were readily prepared in 81% and 65%
yields, respectively (entries 14 and 15). Pleasingly, polyaryl and
heteroaryl, like N-(1-napthylation) and N-(2-pyridinylation) were
achieved by the Cu(II)-catalysis in yields of 76% and 46%,
separately (entries 16 and 17).
: trace, 80 oC
trace, 100 o
32% 120 o
3aa
4aa
C
C
Scheme 2. Control reactions
Table 3. Substrates scope on aryl boronic acids[a]
Based on the literature explorations, possible mechanism for the
C-N coupling protocol was proposed, as shown in Scheme 3.
First, coordination of substrate 1a to Cu(OAc)2 occurred, forming
a new Cu(II)-centered intermediate A with a release of HOAc,
which was basified by Cs2CO3. Then, with assistance of Cs2CO3,
2a, affording another Cu(II)-complex B. In the presence of
Cu(OAc)2, the intermediate B was transformed into a Cu(III)-
centered complex C, and a molecular of CuOAc was afforded.
And successive reductive elimination step happed on the
intermediate C, furnishing the desired product 3aa and anther
CuOAc, which was oxidized easily in the air atmosphere to
complete the catalytic cycle.
Entry
1
2
2b
2c
2d
2e
2f
Ar
3
Yieldb)
76%
82%
79%
76%
77%
79%
75%
75%
79%
83%
80%
75%
70%
81%
65%
76%
46%
C6H5
3ab
3ac
3ad
3ae
3af
2
2-CH3C6H5
3- CH3C6H5
2,4-(CH3)2C6H4
2-C2H5C6H5
4-C2H5C6H5
4-iPrC6H5
4-tBuC6H5
3-CH3OC6H5
4-CH3OC6H5
4-FC6H5
3
4
5
6
2g
2h
2i
3ag
3ah
3ai
7
8
9
2j
3aj
10
11
12
13
14
15
16
17
2k
2l
3ak
3al
2m
2n
2o
2p
2q
2r
4-ClC6H5
3am
3an
3ao
3ap
3aq
3ar
4-BrC6H5
4-CF3C6H5
2-NO2C6H5
1-Naphthyl
2-Pyridinyl
Scheme 3. Proposed mechanism
3. Conclusion
In summary, we have successfully developed an efficient and
general Cu(II)-mediated transformation towards N-arylated
phosphonamides and phosphinamides with aryl boronic acids.
The transformation enjoyed good functional group compatibility
and high efficiency. The practical and facile methodology offered
a promising avenue towards the compounds of great significance
a)
Reaction conditions: 1 (0.5 mmol), 2a (0.6 mmol), Cu(OAc)2 (1.0 mmol),
Cs2CO3 (1.0 mmol), 4Å MS (100 wt%), in toluene (3.5 mL) at 80 oC for 10 h.
b) Isolated yields.
To take a deeper insight into the reaction, controlled reactions
were conducted as shown in Scheme 2. Under the standard
conditions, phenylation of phosphinamide 1a was also realized
by the application of potassium trifluoro p-tolyl borate, affording
the desired product 3aa in good yield, up to 82% (scheme 2, A)).
4. Experimental section
4.1 General remarks

4
Tetrahedron
ACCEPTED MANUSCRIPT
1
White solid (114.6 mg, 83% yield), m.p. 106 - 108 oC. H
All the reagents were purchased from commercial companies
and used without further purification.1H and 13C NMR spectra
were recorded on a Varian INOVA-400 spectrometer in
deuterated chloroform at 25 °C with residue solvent peaks as
internal standards (δ = 7.26 ppm for 1H-NMR and δ = 77.16 ppm
for 13C-NMR). Chemical shifts (δ) are reported in ppm, and spin-
spin coupling constants (J) are given in Hz, while multiplicities
are abbreviated by s (singlet), d (doublet), t (triplet), q (quartet)
NMR (CDCl3, 400 MHz): δ = 7.84 (dd, J = 13.4, 7.7 Hz, 2H),
7.48 (t, J = 7.4 Hz, 1H), 7.41 (dd, J = 11.3, 7.4 Hz, 2H), 6.94 (d,
J = 8.0 Hz, 2H), 6.82 (d, J = 8.0 Hz, 2H), 6.43 (d, J = 8.0 Hz,
1H), 4.31 – 4.15 (m, 2H), 2.21 (s, 3H), 1.37 (t, J = 7.0 Hz, 3H)
(ppm). 13C NMR (CDCl3, 100 MHz): δ = 137.7, 132.2 (JC-P = 3.0
Hz), 131.5 (JC-P = 10.0 Hz), 130.8, 130.4 (JC-P = 176.0 Hz), 129.8,
128.6 (JC-P = 13.0 Hz), 117.7 (JC-P = 7.0 Hz), 61.0 (JC-P = 6.0 Hz),
20.6, 16.4 (JC-P = 7.0 Hz) (ppm). 31P NMR (CDCl3, 160 MHz): δ
= 17.2 ppm. IR (KBr): ν = 3160, 3064, 3033, 2927, 2858, 1741,
1615, 1517, 1448, 1384, 1285, 1214, 1133, 1034, 955, 822, 782,
732, 694, 550, 501 (cm-1). MS (ESI): m/z (%) = 77.1 (64), 106.1
(60), 107.1 (100), 141.0 (45), 275.1 (80). HRMS (ESI): m/z calcd
for [M+H]+: 276.1148; found: 276.1150.
and
m (multiplet). Mass spectra were recorded on a
ThermoFinnigan MAT95XP microspectrometer and High
resolution mass spectra (HRMS) were recorded on an Agilent
Technologies Accurate Mass Q-TOF 6530 microspectrometer.
Infrared (IR) spectra were reported in reciprocal centimeter (cm-
1). Melting points were recorded on a national standard melting
point apparatus (Model: Taike XT-4) and were uncorrected.
4.2.6 P-Phenyl-P-isoproxy-N-(p-tolyl) phosphonamide (3da)
o
1
White solid (112.8 mg, 78% yield ). m.p. 188 - 190 C. H
NMR (CDCl3, 400 MHz): δ = 7.84 (dd, J = 12.9, 7.7 Hz, 2H),
7.47 (d, J = 6.8 Hz, 1H), 7.40 (s, 2H), 6.92 (d, J = 7.6 Hz, 2H),
6.80 (d, J = 7.3 Hz, 2H), 6.33 (d, J = 16.3 Hz, 1H), 4.89 (d, J =
5.9 Hz, 1H), 2.20 (s, 3H), 1.43 (d, J = 5.4 Hz, 3H), 1.29 (d, J =
5.5 Hz, 3H) (ppm). 13C NMR (CDCl3, 100 MHz): δ = 137.8,
132.1 (JC-P =2.0 Hz), 131.6 (JC-P = 10.0 Hz), 130.9 (JC-P = 177.0
Hz), 130.6, 129.7, 128.6 (JC-P = 15.0 Hz), 117.7 (JC-P = 6.0 Hz),
70.4 (JC-P = 6.0 Hz), 24.5 (JC-P = 3.0 Hz), 23.9 (JC-P = 5.0 Hz),
20.6 (ppm). 31P NMR (CDCl3, 160 MHz): δ = 16.1 ppm. IR
(KBr): ν = 3160, 3044, 3002, 2917, 2868, 1721, 1605, 1428,
1374, 1265, 1214, 1034, 955, 802, 762, 722, 540, 505 (cm-1). MS
(ESI): m/z (%) = 77.1 (27), 106.1 (42), 107.1 (76), 247.1 (100),
289.2 (32). HRMS (ESI): m/z calcd for [M+H]+: 290.1304;
found: 290.1310.
4.2 General Procedure
4.2.1 Procedures towards N-aryl Phosphonic/Phosphinic Amides
A Schlenk tube (35 mL) equipped with a magnetic bar was
loaded with the phosphonamides or phosphinamides 1 (0.5 mmol)
and Cu(OAc)2 (181 mg, 1.0 mmol) in dry toluene (3.5 mL), then
arylboronic acids 2 (0.6 mmol, 1.2 equiv.), Cs2CO3 (1.0 mmol,
2.0 equiv.) and 4 Å MS (100 wt%) were added in portions and
the reaction mixture was allowed to stir at 80 °C (120 oC for 4aa)
for 10 h. After cooling to room temperature, the mixture was
filtered through
a
short celite pad and washed with
dichloromethane (15 mL × 3). The filtrate was concentrated and
the oily crude product was purified by column chromatography
using silica gel (200-300 mesh) as stationary phase and a
petroleum ether and ethyl acetate (3/1) as eluent to give the N-
aryl phosphonamides or phosphinamides 3 and 4aa (in sealed
tube) in noted yields
4.2.7 P-Phenyl-P-(n-butoxy)-N-(p-tolyl) phosphonamide
(3ea)
o
1
White solid (118.2 mg, 78% yield), m.p. 107 - 109 C. H
NMR (CDCl3, 400 MHz): δ = 7.85 (dd, J = 13.3, 7.7 Hz, 2H),
7.49 (t, J = 7.1 Hz, 1H), 7.41 (d, J = 3.0 Hz, 2H), 6.94 (d, J = 7.5
Hz, 2H), 6.80 (d, J = 8.0 Hz, 2H), 6.10 (s, 1H), 4.27 – 4.02 (m,
2H), 2.21 (s, 3H), 1.74 – 1.67 (m, 2H), 1.47 – 1.38 (m, 2H), 0.91
(t, J = 7.3 Hz, 3H) (ppm). 13C NMR (CDCl3, 100 MHz): δ =
137.5, 132.2 (JC-P =3.0 Hz), 131.5 (JC-P =10.0 Hz), 130.9, 130.3
(JC-P =177.0 Hz), 129.9, 128.7 (JC-P =15.0 Hz), 117.6 (JC-P = 6.0
Hz), 64.7 (JC-P = 6.0 Hz), 32.5 (JC-P = 7.0 Hz), 20.7, 19.0, 13.8
(ppm). 31P NMR (CDCl3, 160 MHz): δ = 17.3 ppm. IR (KBr): ν
= 3180, 3033, 2964, 2925, 2861, 1616, 1522, 1474, 1446, 1384,
1361, 1262, 1219, 1119, 1067, 1025, 950, 808, 742, 670, 543,
500 (cm-1). MS (ESI): m/z (%) = 77.1 (16), 106.6 (30), 107.1
(26), 247.1 (100), 303.2 (65). HRMS (ESI): m/z calcd for
[M+H]+: 304.1461; found: 304.1464.
4.2.3 P,P-Diphenyl-N-(p-tolyl) phosphinamide (3aa)
o
1
White solid (130.9 mg, 85% yield), m.p. 229 - 230 C. H
NMR (CDCl3, 400 MHz): δ = 7.88 (dd, J = 12.3, 7.7 Hz, 4H),
7.50 (t, J = 7.3 Hz, 2H), 7.48 – 7.42 (m, 4H), 6.91 (dd, J = 15.9,
7.3 Hz, 4H), 5.39 (d, J = 9.2 Hz, 1H), 2.20 (s, 3H) (ppm). 13C
NMR (CDCl3, 100 MHz): δ = 137.8, 132.3 (JC-P = 3.0 Hz), 132.2
(JC-P = 128.0 Hz), 132.1 (JC-P = 10.0 Hz), 131.4, 129.9, 128.9 (JC-P
= 13.0 Hz), 118.8 (JC-P = 7.0 Hz), 20.7 (ppm). 31P NMR (CDCl3,
160 MHz): δ = 18.3 ppm. IR (KBr): ν = 3204, 3060, 2943, 2856,
1719, 1515, 1278, 1116, 941, 814, 692, 570, 516 (cm-1). MS
(ESI): m/z (%) = 218.1, 294.1, 308.1 (100). HRMS (ESI): m/z
calcd for [M+H]+: 308.1199; found: 308.1208.
4.2.4 P-Phenyl-P-methoxy-N-(p-tolyl) phosphonamide (3ba)
4.2.8
P-Phenyl-P-(1-methoxyethoxy)-N-(p-tolyl)
o
1
White solid (103.5mg, 79% yield). m.p. 115 - 116 C. H
NMR (CDCl3, 400 MHz): δ = 7.83 (dd, J = 13.5, 7.7 Hz, 2H),
7.49 (t, J = 7.4 Hz, 1H), 7.41 (dd, J = 11.5, 5.8 Hz, 2H), 6.95 (d,
J = 8.1 Hz, 2H), 6.82 (d, J = 8.2 Hz, 2H), 6.29 (d, J = 5.2 Hz,
1H), 3.83 (d, J = 11.3 Hz, 3H), 2.21 (s, 3H) (ppm). 13C NMR
(CDCl3, 100 MHz): δ = 137.4, 132.3 (JC-P = 3.0 Hz), 131.5 (JC-P
phosphonamide (3fa)
o
1
White solid (114.4 mg, 75% yield). m.p. 92 - 94 C. H
NMR (CDCl3, 400 MHz): δ = 7.86 (dd, J = 13.4, 7.6 Hz, 2H),
7.48 (d, J = 7.0 Hz, 1H), 7.41 (d, J = 2.9 Hz, 2H), 6.95 (d, J = 7.0
Hz, 2H), 6.84 (d, J = 8.0 Hz, 2H), 6.30 – 6.13 (m, 1H), 4.38 –
4.26 (m, 2H), 3.71 – 3.59 (m, 2H), 3.39 (d, J = 1.6 Hz, 3H), 2.21
(s, 3H) (ppm). 13C NMR (CDCl3, 100 MHz): δ = 137.5, 132.3,
131.8 (JC-P = 10.0 Hz), 131.0 (JC-P = 4.0 Hz), 130.0 (JC-P = 139.0
Hz), 129.9, 128.6 (JC-P = 15.0 Hz), 117.8 (JC-P = 6.0 Hz), 71.8 (JC-
P = 6.0 Hz), 63.8, 59.0, 20.7 (ppm). 31P NMR (CDCl3, 160 MHz):
δ = 18.0 ppm. IR (KBr): ν = 3173, 3060, 3036, 2926, 2875, 1619,
1525, 1478, 1450, 1393, 1284, 1209, 1129, 1039, 955, 803, 747,
704, 549, 502 (cm-1). MS (ESI): m/z (%) = 77.1 (14), 107.1 (50),
229.1 (26), 247.1 (100), 305.1 (32). HRMS (ESI): m/z calcd for
[M+H]+: 306.1254; found: 306.1259.
= 10.0 Hz), 131.1, 129.9, 129.8 (JC-P = 177.0 Hz), 128.7 (JC-P
=
15.0 Hz), 117.7 (JC-P =6.0 Hz), 51.3 (JC-P = 6.0 Hz), 20.6 (ppm).
31P NMR (CDCl3, 160 MHz): δ = 19.2 ppm. IR (KBr): ν = 3152,
3067, 2957, 2871, 1756, 1514, 1458, 1404, 1273, 1203, 1134,
1093, 1050, 967, 801, 760, 551, 489 (cm-1). MS (ESI): m/z (%) =
155.0, 262.1 (100). HRMS (ESI): m/z calcd for [M+H]+:
262.0991; found: 262. 0995.
4.2.5 P-Phenyl-P-ethoxy-N-(p-tolyl)-phosphonamide (3ca)

5
4.2.9
P-Phenyl-P-cyclohexylmethyl-N-(p-tolyl)
(JC-P = 6.0 Hz), 115.1 (JP-C-F= 21.0 Hz), 64.2 (JC-P = 6.0 Hz),
ACCEPTED MANUSCRIPT
phosphonamide (3ga)
19.5 (ppm). 31P NMR (CDCl3, 160 MHz): δ = 18.3 ppm. 19F
NMR (CDCl3, 370 MHz): = -112.7 ppm. IR (KBr): ν = 3175,
3065, 3035, 2925, 2895, 1599, 1517, 1450, 1380, 1273, 1254,
1214, 1128, 1044, 945, 816, 807, 747, 686, 562, 532 (cm-1). MS
(ESI): m/z (%) = 79.0, 118.1, 137.0, 157.0, 356.1 (100). HRMS
(ESI): m/z calcd for [M+H]+: 356.1210; found: 356.1220.
o
1
White solid (145.9 mg, 85% yield), m.p. 131 - 132 C. H
NMR (CDCl3, 400 MHz): δ = 7.83 (dd, J = 13.4, 7.6 Hz, 2H),
7.49 (t, J = 7.2 Hz, 1H), 7.41 (dt, J = 11.2, 5.7 Hz, 2H), 6.94 (d, J
= 8.0 Hz, 2H), 6.79 (d, J = 8.1 Hz, 2H), 6.04 (d, J = 7.4 Hz, 1H),
4.08 – 3.77 (m, 2H), 2.21 (s, 3H), 1.80 – 1.70 (m, 4H), 1.70 (s,
1H), 1.30 – 1.16 (m, 4H), 1.03 – 0.97 (m, 2H) (ppm). 13C NMR
4.2.13
P-Phenyl-P-(4-chlorobenzyloxy)-N-(p-tolyl)
(CDCl3, 100 MHz): δ = 137.5, 132.2 (JC-P =3.0 Hz), 131.5 (JC-P
10.0 Hz), 130.9, 130.4 (JC-P = 177.0 Hz), 129.8, 128.6 (JC-P
15.0 Hz), 117.6 (JC-P = 7.0 Hz), 69.7 (JC-P = 7.0 Hz), 38.5 (JC-P
=
=
=
phosphonamide (3ka)
o
1
White solid (150.7 mg, 81% yield). m.p. 118-120 C. H
NMR (CDCl3, 400 MHz): δ = 7.83 (dd, J = 13.6, 7.7 Hz, 2H),
7.50 (t, J = 7.9 Hz, 1H), 7.45 (t, J = 7.4 Hz, 2H), 7.29 (s, 4H),
6.93 (d, J = 7.8 Hz, 2H), 6.79 (d, J = 7.9 Hz, 2H), 6.23 (d, J = 5.2
Hz, 1H), 5.24 – 5.01 (m, 2H), 2.12 (s, 3H) (ppm).13C NMR
(CDCl3, 100 MHz): δ = 137.2, 134.7 (JC-P = 8.0 Hz), 134.4, 132.5
(JC-P = 3.0 Hz), 131.6 (JC-P = 10.0 Hz), 131.3, 129.9 (JC-P = 176.0
Hz), 129.8 (JC-P = 28.0 Hz), 128.9, 128.7 (JC-P = 15.0 Hz), 117.9
(JC-P = 6.0 Hz) 65.6 (JC-P = 6.0 Hz), 20.7 (ppm). 31P NMR
(CDCl3, 160 MHz): δ = 18.3 ppm. IR (KBr): ν = 3218, 3052,
2916, 2855, 1065, 1515, 1454, 1490, 1380, 1274, 1210, 1125,
1091, 1018, 938, 808, 748, 697, 546, 494 (cm-1). MS (ESI): m/z
(%) = 79.0, 118.1, 157.0, 356.1, 372.1 (100). HRMS (ESI): m/z
calcd for [M+H]+: 372.0915; found: 372.0915.
7.0 Hz), 29.5 (JC-P = 3.0 Hz), 26.5, 25.7, 20.7 (ppm). 31P NMR
(CDCl3, 160 MHz): δ = 17.2 ppm. IR (KBr): ν = 3200, 3071,
3030, 2929, 2853, 1615, 1517, 1450, 1392, 1294, 1217, 1124,
1029, 944, 846, 806, 752, 712, 694, 565, 502 (cm-1). MS (ESI):
m/z (%) = 77.1 (5), 107.1 (24), 247.1 (100), 248.1 (25), 343.2
(27). HRMS (ESI): m/z calcd for [M+H]+: 344.1774; found:
344.1780.
4.2.10
P-Phenyl-P-(2-butynyl
ester)-N-(p-tolyl)
phosphonamide (3ha)
o
1
White solid (131.6 mg, 88% yield), m.p. 198 - 200 C. H
NMR (CDCl3, 400 MHz): δ = 7.86 (dd, J = 13.6, 7.7 Hz, 2H),
7.50 (t, J = 7.3 Hz, 1H), 7.41 (dd, J = 11.4, 7.2 Hz, 2H), 6.95 (d,
J = 7.9 Hz, 2H), 6.85 (d, J = 7.9 Hz, 2H), 6.07 (d, J = 5.9 Hz,
1H), 4.76 (d, J = 9.1 Hz, 2H), 2.21 (s, 3H), 1.76 (s, 3H) (ppm).
13C NMR (CDCl3, 100 MHz): δ = 137.3, 132.4 (JC-P = 4.0 Hz),
131.7 (JC-P = 8.0 Hz), 131.2, 129.8, 129.8 (JC-P = 176.0 Hz),
128.6 (JC-P = 15.0 Hz), 118.1 (JC-P = 7.0 Hz), 84.4, 73.7 (JC-P =8.0
Hz), 53.3 (JC-P = 5.0 Hz), 20.6, 3.7 (ppm). 31P NMR (CDCl3, 160
MHz): δ = 18.6 ppm. IR (KBr): ν = 3162, 3060, 3023, 2960,
2923, 1617, 1517, 1443, 1375, 1270, 1212, 1122, 1097, 1018,
975, 948, 806, 754, 701, 659, 554, 502 (cm-1). MS (ESI): m/z (%)
= 118.1, 300.1 (100). HRMS (ESI): m/z calcd for [M+H]+:
300.1148; found: 300.1151.
4.2.14
P-Phenyl-P-(2-bromobenzyloxy)-N-(p-tolyl)
phosphonamide (3la)
o
1
White solid (168.5 mg, 81% yield), m.p. 121 - 122 C. H
NMR (400 MHz, CDCl3) δ = 7.83 (dd, J = 13.5, 7.5 Hz, 2H),
7.47 (dd, J = 17.0, 7.6 Hz, 3H), 7.41 – 7.35 (m, 2H), 7.23 (d, J =
11.4 Hz, 1H), 7.12 (t, J = 7.6 Hz, 1H), 6.88 (d, J = 7.9 Hz, 2H),
6.77 (d, J = 8.0 Hz, 2H), 5.91 (d, J = 5.4 Hz, 1H), 5.32 – 5.12 (m,
2H), 2.16 (s, 3H). 13C NMR (CDCl3, 100 MHz): δ = 137.1,
135.8, 153.7, 132.5 (JC-P = 3.0 Hz), 131.7 (JC-P = 10.0 Hz),
131.4, 129.9, 129.9 (JC-P = 176.0 Hz), 129.8 (JC-P = 7.0 Hz),
128.8 (JC-P = 15.0 Hz), 127.7, 123.1, 118.1 (JC-P = 6.0 Hz), 65.9
(JC-P = 5.0 Hz), 20.7 (ppm). 31P NMR (CDCl3, 160 MHz): δ =
18.1 ppm. IR (KBr): ν = 3142, 3058, 3022, 2923, 2858, 1607,
1517, 1474, 1384, 1277, 1208, 1126, 1064, 1030, 940, 853, 812,
747, 696, 547, 534 (cm-1). MS (ESI): m/z (%) = 79.0, 118.1,
157.0, 352.3, 416.0 (100). HRMS (ESI): m/z calcd for [M+H]+:
416.0410; found: 416.0406.
4.2.11
P-Phenyl-P-phenylmethoxy-N-(p-tolyl)
phosphonamide (3ia)
o
1
White solid (139.9 mg, 83% yield). m.p. 150-151 C. H
NMR (CDCl3, 400 MHz): δ = 7.85 (dd, J = 13.6, 7.7 Hz, 2H),
7.49 (t, J = 7.4 Hz, 1H), 7.51 – 7.33 (m, 7H), 6.94 (d, J = 8.1 Hz,
2H), 6.82 (d, J = 8.1 Hz, 2H), 6.29 (s, 1H), 5.29 – 5.06 (m, 2H),
2.21 (s, 3H) (ppm). 13C NMR (CDCl3, 100 MHz): δ = 137.3,
136.2 (JC-P = 7.0 Hz), 132.4 (JC-P = 3.0 Hz), 131.6 (JC-P = 10.0
Hz), 131.2, 130.0 (JC-P = 176.0 Hz), 129.1, 128.7 (JC-P = 14.0 Hz),
128.7,128.5, 128.3, 117.9 (JC-P = 7.0 Hz), 66.3 (JC-P = 5.0 Hz),
20.7 (ppm). 31P NMR (CDCl3, 160 MHz): δ = 18.0 ppm. IR
(KBr): ν = 3201, 3069, 3033, 2954, 2922, 2859, 1615, 1517,
1445, 1386, 1279, 1215, 1126, 998, 947, 810, 742, 701, 640, 559,
527 (cm-1). MS (ESI): m/z (%) = 99.1 (22), 195.1 (25), 196.2
(55), 197.2 (20), 337.2 (100). HRMS (ESI): m/z calcd for
[M+H]+: 338.1304; found: 338.1309.
4.2.15
P-Phenyl-P-(4-morpholinyl
ester)-N-(p-tolyl)
phosphonamide (3ma)
o
1
White solid (88.5 mg, 56% yield), m.p. 193 - 194 C. H
NMR (CDCl3, 400 MHz): δ = 7.82 (m, 2H), 7.54 (t, J = 7.3 Hz,
1H), 7.48 (dd, J = 7.0, 3.1 Hz, 2H), 7.11 – 6.86 (m, 4H), 4.93 (d,
J = 11.1 Hz, 1H), 3.61 – 3.51 (m, 4H), 3.26 – 3.14 (m, 4H), 2.27
(s, 3H) (ppm). 13C NMR (CDCl3, 100 MHz): δ = 137.3, 132.3
(JC-P = 3.0 Hz), 131.8, 131.4 (JC-P = 10.0 Hz), 131.4 (JC-P = 154.0
Hz), 129.9, 128.9 (JC-P = 14.0 Hz), 119.0 (JC-P = 6.0 Hz), 67.1 (JC-
= 6.0 Hz), 44.8, 20.8 (ppm). 31P NMR (CDCl3, 160 MHz): δ =
P
4.2.12
phosphonamide (3ja)
P-Phenyl-P-(3-fluorobenzyloxy)-N-(p-tolyl)
16.0 ppm. IR (KBr): ν = 3213, 2965, 2916, 2858, 1517, 1443,
1385, 1294, 1259, 1201, 1116, 1102, 1024, 969, 924, 808, 735,
694, 603, 552, 535, 516 (cm-1). MS (ESI): m/z (%) = 86.1 (25),
107.1 (55), 229.1 (100), 259.1 (52), 316.2 (95). HRMS (ESI):
m/z calcd for [M+H]+: 317.1413; found: 317.1417.
o
1
White solid (140.3 mg, 79% yield), m.p. 116 - 118 C. H
NMR (CDCl3, 400 MHz): δ = 7.80 (dd, J = 13.5, 7.6 Hz, 2H),
7.45 (t, J = 7.2 Hz, 1H), 7.36 (dd, J = 11.1, 7.1 Hz, 2H), 7.25 –
7.20 (m, 1H), 7.07 (d, J = 7.6 Hz, 1H), 7.02 (d, J = 9.4 Hz, 1H),
6.94 (t, J = 8.4 Hz, 1H), 6.87 (d, J = 7.9 Hz, 2H), 6.76 (d, J = 7.5
Hz, 2H), 6.55 (d, J = 11.3 Hz, 1H), 5.23 – 4.97 (m, 2H), 2.15 (s,
3H) (ppm). 13C NMR (CDCl3, 100 MHz): δ = 163.0, 160.6, 138.7
(JC-F = 8.0 Hz), 137.4 (JC-F = 5.0 Hz), 132.5 (JC-P = 3.0 Hz), 131.6
4.2.16 N,P,P-Triphenyl phosphinic amide (3ab)
o
1
White solid (111.4 mg, 76% yield). m.p. 230 - 232 C. H
NMR (CDCl3, 400 MHz): δ = 7.89 (dd, J = 12.3, 7.5 Hz, 4H),
7.53 (t, J = 7.0 Hz, 2H), 7.49 – 7.43 (m, 4H), 7.14 (t, J = 7.5 Hz,
2H), 6.98 (d, J = 7.8 Hz, 2H), 6.89 (t, J = 7.3 Hz, 1H), 5.35 (d, J
= 9.2 Hz, 1H) (ppm). 13C NMR (CDCl3, 100 MHz): δ = 140.5,
132.4 (JC-P = 3.0 Hz), 132.1 (JC-P = 10.0 Hz), 132.1 (JC-P = 129.0
(JC-P =10.0 Hz), 131.2, 130.2 (JC-F = 8.0 Hz), 129.9, 129.9 (JC-P
177.0 Hz), 128.8 (JC-F = 15.0 Hz), 123.5 (JC-F = 4.0 Hz), 117.8
=

6
Tetrahedron
Hz), 129.0 (JC-P = 13.0 Hz), 129.4, 122.0, 118.7 (JC-P = 7.0 Hz)
1591, 1501, 1435, 1245, 1115, 1035, 945, 807, 755, 696, 560,
ACCEPTED MANUSCRIPT
(ppm). 31P NMR (CDCl3, 160 MHz): δ = 18.4 ppm. IR (KBr): ν
= 3111, 3070, 2960, 2930, 2890, 1600, 1494, 1434, 1408, 1270,
1184, 1100, 1031, 930, 803, 748, 694, 525 (cm-1). MS (ESI): m/z
(%) = 218.1, 294.1 (100). HRMS (ESI): m/z calcd for [M+H]+:
294.1042; found: 294.1051.
520 (cm-1). MS (ESI): m/z (%) = 77.1 (25), 120.1 (45), 196.1
(23), 201.1 (57), 321.2 (100). HRMS (ESI): m/z calcd for
[M+H]+: 322.1355; found: 322.1358.
4.2.21 P,P-Diphenyl-N-(4-ethylphenyl) phosphinic amide
(3ag)
4.2.17 P,P-Diphenyl-N-(o-tolyl) phosphinic amide (3ac)
o
1
White solid (126.9 mg, 79% yield), m.p. 260 - 261 C. H
NMR (CDCl3, 400 MHz): δ = 7.88 (dd, J = 11.9, 7.8 Hz, 4H),
7.52 (t, J = 6.9 Hz, 2H), 7.46 (d, J = 5.9 Hz, 4H), 6.96 (d, J = 7.9
Hz, 2H), 6.90 (d, J = 8.0 Hz, 2H), 5.28 (d, J = 9.1 Hz, 1H), 2.51
(q, J = 7.5 Hz, 2H), 1.14 (t, J = 7.5 Hz, 3H) (ppm). 13C NMR
(CDCl3, 100 MHz): δ = 137.9, 132.9, 132.2 (JC-P = 129.0 Hz),
o
1
White solid (125.9 mg, 82% yield), m.p. 238-240 C. H
NMR (CDCl3, 400 MHz): δ = 7.89 (dd, J = 12.2, 7.6 Hz, 4H),
7.53 (t, J = 6.0 Hz, 2H), 7.48 – 7.44 (m, 4H), 7.20 (d, J = 8.0 Hz,
1H), 7.11 (d, J = 7.4 Hz, 1H), 6.94 (t, J = 7.6 Hz, 1H), 6.84 (t, J =
7.4 Hz, 1H), 5.04 (d, J = 8.7 Hz, 1H), 2.28 (s, 3H) (ppm). 13C
NMR (CDCl3, 100 MHz): δ = 138.7, 132.4 (JC-P = 30 Hz), 132.2
132.3 (JC-P =3.0 Hz), 132.1 (JC-P =5.0 Hz), 129.0, 128.8 (JC-P
=
(JC-P = 129.0Hz), 132.0 (JC-P = 10.0Hz), 130.6, 129.0 (JC-P
=
11.0 Hz), 118.8 (JC-P =7.0 Hz), 28.1, 15.7 (ppm). 31P NMR
(CDCl3, 160 MHz): δ = 18.4 ppm. IR (KBr): ν = 3117, 3042,
2934, 2859, 1613, 1519, 1475, 1291, 1247, 1190, 1120, 829, 735,
690, 582, 512 (cm-1).MS (ESI): m/z (%) = 218.1, 322.1
(100).HRMS (ESI): m/z calcd for [M+H]+: 322.1355; found:
322.1363.
13.0Hz), 127.2, 125.7 (JC-P = 8.0Hz), 122.2, 119.0 (JC-P = 4.0
Hz), 17.9 (ppm). 31P NMR (CDCl3, 160 MHz): δ = 18.6 ppm. IR
(KBr): ν = 3194, 3047, 2970, 2905, 1589, 1499, 1439, 1399,
1269, 1188, 1103, 1028, 917, 807, 751, 697, 536 (cm-1). MS
(ESI): m/z (%) = 77.1 (25), 106.1 (22), 182.1 (45), 201.1 (55),
307.2 (100). HRMS (ESI): m/z calcd for [M+H]+: 308.1199;
found: 308.1203.
4.2.22 P,P-Diphenyl-N-(4-isopropylphenyl) phosphinic
amide (3ah)
4.2.18 P,P-Diphenyl-N-(m-tolyl) phosphinic amide (3ad)
o
1
White solid (125.7 mg, 75% yield). m.p. 212-214 C. H
NMR (CDCl3, 400 MHz): δ = 7.88 (dd, J = 12.0, 7.6 Hz, 4H),
7.52 (t, J = 6.9 Hz, 2H), 7.46 (d, J = 7.4 Hz, 4H), 6.99 (d, J = 7.6
Hz, 2H), 6.89 (d, J = 7.7 Hz, 2H), 5.30 (d, J = 9.0 Hz, 1H), 2.80 –
2.74 (m, 1H), 1.15 (d, J = 6.8 Hz, 6H) (ppm). 13C NMR (CDCl3,
o
1
White solid (121.3 mg, 79% yield), m.p. 248 - 249 C. H
NMR (CDCl3, 400 MHz): δ = 7.88 (dd, J = 12.2, 7.8 Hz, 4H),
7.52 (t, J = 7.2 Hz, 2H), 7.46 (d, J = 6.8 Hz, 4H), 7.01 (t, J = 7.7
Hz, 1H), 6.81 (s, 1H), 6.78 (d, J = 8.2 Hz, 1H), 6.71 (d, J = 7.5
Hz, 1H), 5.31 (d, J = 8.1 Hz, 1H), 2.19 (s, 3H) (ppm). 13C NMR
(CDCl3, 100 MHz): δ = 140.4, 139.3, 132.2 (JC-P = 128.0Hz),
100 MHz): δ = 142.5, 138.0, 132.3 (JC-P =3.0 Hz), 132.3 (JC-P
=
128.0 Hz), 132.1 (JC-P = 10.0 Hz), 128.9 (JC-P = 13.0 Hz), 127.3,
118.7 (JC-P = 6.0 Hz), 33.4, 24.1 (ppm). 31P NMR (CDCl3, 160
MHz): δ = 18.5 ppm. IR (KBr): ν = 3119, 3046, 2957, 2862,
1619, 1520, 1469, 1270, 1191, 1111, 1026, 946, 807, 742, 693,
567, 518 (cm-1). MS (ESI): m/z (%) = 130.1, 336.1 (100). HRMS
(ESI): m/z calcd for [M+H]+: 336.1512; found: 336.1522.
132.2 (JC-P = 3.0Hz), 131.6 (JC-P = 10.0Hz), 129.2, 128.9 (JC-P
=
13.0Hz), 122.8, 119.3 (JC-P =6.7Hz), 115.7 (JC-P =6.4Hz), 21.5
(ppm). 31P NMR (CDCl3, 160 MHz): δ = 18.3 ppm. IR (KBr): ν
= 3128, 3082, 2966, 2863, 1608, 1484, 1434, 1401, 1285, 1187,
1115, 1024, 947, 792, 726, 693, 620, 525 (cm-1). MS (ESI): m/z
(%) = 77.1 (25), 183.1 (20), 201.1 (65), 306.1 (90), 307.2 (100).
HRMS (ESI): m/z calcd for [M+H]+: 308.1199; found: 308.1202.
4.2.23 P,P-Diphenyl-N-(4-(t-butyl) phenyl) phosphinic
amide (3ai)
4.2.19 P,P-Diphenyl-N-(2,4-dimethylphenyl) phosphinic
amide (3ae)
o
1
White solid (130.9 mg, 75% yield). m.p. 226 - 227 C. H
NMR (CDCl3, 400 MHz): δ = 7.89 (dd, J = 12.3, 7.5 Hz, 4H),
7.51 (d, J = 7.1 Hz, 2H), 7.46 (dd, J = 7.4, 3.0 Hz, 4H), 7.14 (d, J
= 8.4 Hz, 2H), 6.89 (d, J = 8.4 Hz, 2H), 5.31 (d, J = 9.1 Hz, 1H),
1.22 (s, 9H) (ppm). 13C NMR (CDCl3, 100 MHz): δ = 144.7,
o
1
White solid (122.0 mg, 76% yield). m.p. 194-196 C. H
NMR (CDCl3, 400 MHz): δ = 7.88 (dd, J = 11.1, 8.5 Hz, 4H),
7.52 (t, J = 6.9 Hz, 2H), 7.45 (d, J = 7.3 Hz, 4H), 7.10 (d, J = 8.1
Hz, 1H), 6.93 (s, 1H), 6.75 (d, J = 8.1 Hz, 1H), 4.93 (d, J = 8.4
Hz, 1H), 2.25 (s, 3H), 2.19 (s, 3H) (ppm). 13C NMR (CDCl3, 100
MHz): δ = 136.0, 132.3 (JC-P = 128.0 Hz), 132.2 (JC-P = 2.0 Hz),
132.0 (JC-P = 9.0 Hz), 131.7, 131.3, 128.9 (JC-P =13.0 Hz), 127.6,
137.7, 132.3 (JC-P = 129Hz), 132.2 (JC-P = 3.0 Hz), 132.1 (JC-P
=
10.0 Hz), 128.9 (JC-P = 13.0 Hz), 126.2, 118.3 (JC-P = 6.0 Hz),
34.2, 31.5 (ppm). 31P NMR (CDCl3, 160 MHz): δ = 18.5 ppm. IR
(KBr): ν = 3136, 3034, 2960, 2863, 1625, 1523, 1471, 1288,
1247, 1185, 1104, 1025, 945, 807, 739, 683, 567, 522 (cm-1). MS
(ESI): m/z (%) = 218.1, 339.1, 350.1 (100). HRMS (ESI): m/z
calcd for [M+H]+: 350.1668; found: 350.1676.
126.0 (JC-P = 8.0 Hz), 119.4 (JC-P = 4.0 Hz), 20.7, 17.9 (ppm). 31
P
NMR (CDCl3, 160 MHz): δ = 18.5 ppm. IR (KBr): ν = 3061,
2971, 2923, 2807, 1510, 1429, 1262, 1181, 1106, 1026, 945, 909,
817, 714, 685, 581, 530 (cm-1). MS (ESI): m/z (%) = 201.0,
322.1 (100). HRMS (ESI): m/z calcd for [M+H]+: 322.1355;
found: 322.1364.
4.2.24 P,P-Diphenyl-N-(3-methoxyphenyl) phosphinic
amide (3aj)
o
1
White solid (127.6 mg, 79% yield), m.p. 213 - 214 C. H
NMR (CDCl3, 400 MHz): δ = 7.89 (dd, J = 12.4, 7.7 Hz, 4H),
7.53 (t, J = 7.3 Hz, 2H), 7.46 (td, J = 7.1, 2.4 Hz, 4H), 7.03 (t, J =
8.1 Hz, 1H), 6.58 – 6.53 (m, 2H), 6.45 (d, J = 8.3 Hz, 1H), 5.34
(d, J = 9.4 Hz, 1H), 3.64 (s, 3H) (ppm). 13C NMR (CDCl3, 100
MHz): δ = 160.5, 141.7, 132.0 (JC-P = 129.0 Hz),132.4 (JC-P = 2.0
Hz),132.1 (JC-P = 10.0 Hz), 130.1, 128.9 (JC-P = 6.0 Hz),111.2 (JC-
4.2.20 P,P-Diphenyl-N-(2-ethylphenyl) phosphinic amide
(3af)
o
1
White solid (123.6 mg, 77% yield). m.p. 159 - 160 C. H
NMR (CDCl3, 400 MHz): δ = 7.89 (dd, J = 12.1, 7.5 Hz, 4H),
7.52 (t, J = 6.9 Hz, 2H), 7.46 (d, J = 7.3 Hz, 4H), 7.21 (d, J = 7.9
Hz, 1H), 7.13 (d, J = 7.3 Hz, 1H), 6.94 (t, J = 7.5 Hz, 1H), 6.88
(t, J = 7.3 Hz, 1H), 5.13 (d, J = 8.5 Hz, 1H), 2.61 (q, J = 7.4 Hz,
2H), 1.29 (t, J = 7.5 Hz, 3H) (ppm). 13C NMR (CDCl3, 100
MHz): δ = 137.8, 132.0 (JC-P = 3.0 Hz), 131.9 (JC-P = 129.0 Hz),
131.7 (JC-P = 9.0 Hz), 128.7 (JC-P = 8.0 Hz), 128.2, 126.7, 122.1,
118.9 (JC-P = 4.0 Hz), 24.0, 13.2 (ppm). 31P NMR (CDCl3, 160
MHz): δ = 18.5 ppm. IR (KBr): ν = 3072, 2962, 2920, 2833,
= 7.0 Hz), 107.8, 104.5 (JC-P = 7.0 Hz), 55.2 (ppm). 31P NMR
P
(CDCl3, 160 MHz): δ = 18.4 ppm. IR (KBr): ν = 3135, 3095,
2964, 2893, 1560, 1500, 1450, 1293, 1195, 1123, 1032, 947, 857,
727, 695, 610, 518 (cm-1). MS (ESI): m/z (%) = 79.0, 157.0,
259.5, 324.1 (100). HRMS (ESI): m/z calcd for [M+H]+:
324.1148; found: 324.1149.

7
4.2.25 P,P-Diphenyl-N-(4-methoxyphenyl) phosphinic
amide (3ak)
13.0 Hz), 126.6 (JC-F = 3.7 Hz), 118.1 (ppm). 31P NMR (CDCl3,
ACCEPTED MANUSCRIPT
160 MHz): δ = 19.0 ppm. 19F NMR (CDCl3, 370 MHz): δ = -61.8
ppm. IR (KBr): ν = 3122, 3000, 2928, 2855, 1615, 1455, 1400,
1235, 1088, 1000, 884, 792, 714, 675, 554, 521 (cm-1). MS (ESI):
m/z (%) = 79.0, 157.0, 324.9, 331.1, 362.1 (100). HRMS (ESI):
m/z calcd for [M+H]+: 362.0916; found: 362.0920.
o
1
White solid (134.1 mg, 83% yield). m.p. 194-195 C. H
NMR (CDCl3, 400 MHz): δ = 7.87 (dd, J = 12.1, 7.6 Hz, 4H),
7.49 (d, J = 7.0 Hz, 2H), 7.44 (d, J = 7.2 Hz, 4H), 6.96 (d, J = 8.2
Hz, 2H), 6.68 (d, J = 8.2 Hz, 2H), 5.30 (d, J = 8.8 Hz, 1H), 3.68
(s, 3H) (ppm). 13C NMR (CDCl3, 100 MHz): δ = 155.1, 133.4,
132.2, 132.2 (JC-P = 128.0 Hz), 131.1, 128.8 (JC-P = 13.0 Hz),
120.8 (JC-P = 6.0 Hz), 114.7, 55.5 (ppm). 31P NMR (CDCl3, 160
MHz): δ = 18.6 ppm. IR (KBr): ν = 3074, 2957, 2905, 2833,
1517, 1284, 1230, 1187, 1110, 1027, 927, 831, 725, 694, 582,
522 (cm-1). MS (ESI): m/z (%) = 218.1, 324.1 (100). HRMS
(ESI): m/z calcd for [M+H]+: 324.1148; found: 324.1155.
4.2.30 P,P-Diphenyl-N-(2-nitrophenyl) phenyl) phosphinic
amide (3ap)
o
1
White solid (109.9 mg, 65% yield). m.p. 160 - 162 C. H
NMR (CDCl3, 400 MHz): δ = 9.19 (d, J = 12.1 Hz, 1H), 8.20 (d,
J = 8.5 Hz, 1H), 7.89 (dd, J = 12.6, 7.7 Hz, 4H), 7.58 (t, J = 7.6
Hz, 3H), 7.51 (dd, J = 7.0, 2.7 Hz, 4H), 7.37 (t, J = 7.8 Hz, 1H),
6.96 (t, J = 7.8 Hz, 1H) (ppm). 13C NMR (CDCl3, 100 MHz): δ =
139.2, 136.1, 132.9 (JC-P =3.0 Hz), 131.7 (JC-P = 10.0 Hz), 131.2
(JC-P = 128.0 Hz), 129.3 (JC-P =13.0 Hz), 126.5, 121.1, 120.8 (JC-P
= 5.0 Hz), 100.1 (ppm). 31P NMR (CDCl3, 160 MHz): δ = 19.7
ppm. IR (KBr): ν = 3291, 2966, 2923, 2843, 1608, 1497, 1447,
1392, 1261, 1026, 931, 811, 745, 685, 519 (cm-1). MS (ESI): m/z
(%) = 218.1, 339.1 (100). HRMS (ESI): m/z calcd for [M+H]+:
339.0893; found: 339.0903.
4.2.26 P,P-Diphenyl-N-(4-fluorophenyl) phosphinic amide
(3al)
1
White solid (124.4 mg, 80% yield). m.p. 170 - 172 oC. H
NMR (CDCl3, 400 MHz): δ = 7.84 (dd, J = 11.8, 8.0 Hz, 4H),
7.51 (t, J = 7.2 Hz, 2H), 7.43 (d, J = 7.0 Hz, 4H), 6.99 – 6.94 (m,
2H), 6.80 (t, J = 8.1 Hz, 2H), 5.66 (d, J = 9.2 Hz, 1H) (ppm). 13
C
NMR (CDCl3, 100 MHz): δ = 158.3 (JC-P = 239.0 Hz), 136.5,
132.4 (JC-P = 3.0 Hz), 132.1 (JC-P =5.0 Hz), 131.8 (JC-P = 3.0 Hz),
128.9 (JC-P = 3.0 Hz), 120.3 (JF-C-P = 7.0 Hz), 115.9 (ppm). 31P
NMR (CDCl3, 160 MHz): δ = 18.9 ppm. 19F NMR (CDCl3, 370
MHz): δ = -121.9 ppm. IR (KBr): ν = 3470, 3265, 2982, 2895,
2351, 2319, 1630, 1548, 1516, 1396, 1046, 694, 644 (cm-1). MS
(ESI): m/z (%) = 79.0, 157.0, 312.0 (100). HRMS (ESI): m/z
calcd for [M+H]+: 312.1148; found: 312.0958.
4.2.31 P,P-Diphenyl-N-(1-naphthyl) phosphinic amide (3aq)
o
1
White solid (126.6 mg, 76% yield), m.p. 193 - 195 C. H
NMR (CDCl3, 400 MHz): δ = 7.96 (d, J = 8.2 Hz, 4H), 7.92 (s,
1H), 7.83 (d, J = 7.8 Hz, 1H), 7.58 – 7.51 (m, 2H), 7.49 (d, J =
8.0 Hz, 4H), 7.44 (d, J = 6.3 Hz, 4H), 7.20 (t, J = 7.8 Hz, 1H),
5.78 (d, J = 7.9 Hz, 1H) (ppm). 13C NMR (CDCl3, 100 MHz): δ =
135.5, 134.4, 132.4 (JC-P = 2.0 Hz), 132.1 (JC-P = 10.0 Hz), 132.0
(JC-P = 129.0 Hz), 129.1, 129.0 (JC-P = 13.0 Hz), 126.3 (JC-P = 8.0
Hz), 126.1, 123.2, 120.3, 117.0 (JC-P = 4.0 Hz) (ppm). 31P NMR
(CDCl3, 160 MHz): δ = 19.1 ppm. IR (KBr): ν = 3453, 3403,
3058, 2963, 2914, 1585, 1503, 1450, 1426, 1318, 1253, 1172,
1099, 928, 804, 739, 685, 656, 530 (cm-1). MS (ESI): m/z (%) =
228.2, 322.1, 338.3, 339.3, 344.1 (100). HRMS (ESI): m/z calcd
for [M+H]+: 344.1199; found: 344.1203.
4.2.27 P,P-Diphenyl-N-(4-chlorophenyl) phosphinic amide
(3am)
o
1
White solid (122.6 mg, 75% yield). m.p. 233 - 234 C. H
NMR (DMSO-d6, 400 MHz) δ = 8.43 (d, J = 11.6 Hz, 1H), 7.81
– 7.76 (m, 4H), 7.59 – 7.55 (m, 2H), 7.52 (d, J = 7.2 Hz, 4H),
7.16 (d, J = 8.2 Hz, 2H), 7.07 (d, J = 8.3 Hz, 2H) (ppm). 13C
NMR (DMSO-d6, 100 MHz) δ = 141.2, 132.5 (JC-P = 129.0 Hz),
132.1 (JC-P = 2.0 Hz), 131.8 (JC-P = 9.0 Hz), 128.9, 128.8, 124.6,
119.8 (JC-P = 7.0 Hz) (ppm). 31P NMR (DMSO-d6, 160 MHz) δ =
17.0 (ppm). IR (KBr): ν = 3131, 3029, 2923, 2846, 1587, 1450,
1440, 1290, 1193, 1103, 930, 833, 812, 716, 694, 652, 554, 520
cm-1. MS (ESI): m/z (%): 218.1, 328.0 (100). HRMS (ESI) (m/z)
[M+H] +: Calcd.328.0653, Found 328.0658.
4.2.32 P,P-Diphenyl-N-(2-pyridinyl) phosphinic amide (3ar)
o
1
White solid (67.6 mg, 46% yield), m.p. 191 - 192 C. H
NMR (CDCl3, 400 MHz): δ = 7.87 (dd, J = 12.5, 7.4 Hz, 4H),
7.66 (s, 1H), 7.51 (t, J = 7.0 Hz, 2H), 7.43 (s, 4H), 7.34 (t, J = 7.5
Hz, 1H), 6.98 (d, J = 8.3 Hz, 1H), 6.71 – 6.60 (m, 1H) (ppm). 13
NMR (CDCl3, 100 MHz): δ = 154.2, 148.0, 138.1, 132.44(JC-P
C
=
4.2.28 P,P-Diphenyl-N-(4-bromophenyl) phosphinic amide
(3an)
2.0 Hz), 132.00(JC-P = 12.0 Hz), 131.7 (JC-P =129.0 Hz), 128.9
(JC-P = 13.0 Hz), 117.2, 112.1 (ppm). 31P NMR (CDCl3, 160
MHz): δ = 18.9 ppm. IR (KBr): ν = 3514, 3440, 3157, 3065,
3040, 2965, 2848, 2791, 1593, 1450, 1401, 1301, 1263, 1183,
1041, 917, 717, 774, 731, 687, 614, 529 (cm-1). MS (ESI): m/z
(%) = 218.1, 295.1 (100). HRMS (ESI): m/z calcd for [M+H]+:
295.0995; found: 295.1005.
o
1
White solid (130.2 mg, 70% yield). m.p. 241 – 242 C. H
NMR (DMSO-d6, 400 MHz): δ = 8.42 (d, J = 11.6 Hz, 1H), 7.78
(dd, J = 12.0, 7.4 Hz, 4H), 7.62 – 7.55 (m, 2H), 7.53 (d, J = 7.3
Hz, 4H), 7.29 (d, J = 8.1 Hz, 2H), 7.01 (d, J = 8.1 Hz, 2H) (ppm).
13C NMR (DMSO-d6, 100 MHz): δ = 141.6, 132.5 (JC-P = 126.0
Hz), 132.1 (JC-P = 3.0 Hz), 131.7, 131.6, 128.8 (JC-P = 13.0 Hz),
120.3 (JC-P = 7.0 Hz), 112.3 (ppm). 31P NMR (DMSO-d6, 160
MHz): δ = 17.0 ppm. IR (KBr): ν = 3122, 3000, 2928, 2855,
1615, 1455, 1400, 1235, 1088, 1000, 884, 792, 714, 675, 554,
521 (cm-1).MS (ESI): m/z (%) = 169.1, 338.13 (42), 372.0 (100).
HRMS (ESI): m/z calcd for [M+H]+: 372.0147; found: 372.0142.
4.2.33 P,P-Diphenyl-N,N-di(p-tolyl) phosphinamide (4aa)
o
1
White solid (63.7mg, 32% yield). m.p. 160 - 162 C. H
NMR (CDCl3, 400 MHz): δ = 7.77 (dd, J = 11.9, 7.7 Hz, 4H),
7.37 (t, J = 7.2 Hz, 2H), 7.29 (t, J = 6.6 Hz, 4H), 7.14 (d, J = 7.9
Hz, 4H), 6.90 (d, J = 7.8 Hz, 4H), 2.18 (s, 6H) (ppm). 13C NMR
(CDCl3, 100 MHz): δ = 142.3, 134.9, 132.9 (JC-P = 9.0 Hz), 132.0
(JC-P = 132.00 Hz), 131.5 (JC-P = 3.0 Hz), 129.6, 128.2 (JC-P =13.0
Hz), 127.6 (JC-P = 4.0 Hz), 20.9 (ppm). 31P NMR (CDCl3, 160
MHz): δ = 24.8 ppm. IR (KBr): ν = 3230, 2963, 2920, 2859,
1603, 1507, 1439, 1257, 1195, 1106, 1025, 806, 693, 623, 558,
509 (cm-1). MS (ESI): m/z (%) = 118.1, 338.3, 338.3, 398.1
(100). HRMS (ESI): m/z calcd for [M+H]+: 398.1668; found:
398.1671.
4.2.29
P,P-Diphenyl-N-(4-(trifluoromethyl)
phenyl)
phosphinic amide (3ao)
o
1
White solid (146.2 mg, 81% yield). m.p. 160 - 162 C. H
NMR (CDCl3, 400 MHz): δ = 7.83 (dd, J = 12.5, 7.7 Hz, 4H),
7.54 (t, J = 7.4 Hz, 2H), 7.45 (td, J = 7.5, 3.2 Hz, 4H), 7.35 (d, J
= 8.4 Hz, 2H), 7.04 (d, J = 8.4 Hz, 2H), 5.98 (d, J = 9.8 Hz, 1H)
(ppm). 13C NMR (CDCl3, 100 MHz): δ = 144.0, 132.7 (JC-P = 3.0
Hz), 132.0 (JC-P = 10.0 Hz), 131.3 (JC-P = 130.0 Hz), 129.1 (JC-P
=

8
Tetrahedron
(k) Yu J.-T, Guo H, Yi Y, Fei H, Jiang Y, Adv. Synth. Catal. 2014;356:
Acknowledgments
ACCEPTED MANUSCRIPT
749;
4. Raghuvanshi D. S, Gupta A. K, Singh K. N, Org. Lett. 2012;14:4326;
5. Qiao J. X, Lam P. Y. S, Synthesis 2011:829;
6. (a) Hügel H. M, Rix C. J, Fleck K, Synlett. 2006: 2290;
(b) Kantam M. L, Venkanna G. T, Sridhar C, Sreedhar B, Choudary B. M,
J. Org. Chem. 2006; 71: 9522;
(c) Grimes K. D, Gupte A, Aldrich C. C, Synthesis. 2010: 1441;
(d) Zheng Z.-G, Wen J, Wang N, Wu B, Yu X.-Q, Beilstein, J. Org. Chem.
2008;4:40;
(e) Larrosa M, Guerrero C, Rodríguez R, Cruces J, Synlett. 2010:2101;
(f) Sueki S, Kuninobu Y, Org. Lett. 2013;15:1544;
(g) Rossi S. A, Shimkin K. W, Xu Q, Mori-Quiroz L. M, Watson D. A, Org.
Lett. 2013;15:2314;
The authors are grateful for the financial support from the
National Natural Science Foundation of China (NSFC) (grant
number 21072052), the National Basic Research Program of
China (grant number 2009CB421601), and the Hunan Provincial
Science and Technology Department Program (grant number
2011WK4007, 06FJ4115) and The Fundamental Research Funds
for the Central Universities, Hunan University (grant number
531107040840).
Supplementary Material
Supporting Information is available via Http://
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