Cobalt-catalyzed oxidative arylmethylation of phosphorylamides

Article abstract of DOI:10.1016/j.tet.2018.07.006

A cobalt-catalyzed strategy for N-arylmethylation of phosphorylamides was herein achieved with the assistance of azodiisobutyronitrile as the radical initiator and di-tert-butyl peroxide as the oxidant. Both methylarenes and diaryl methanes were compatible under the oxidative conditions, expressing broad substrate scope (51 examples) and high efficiency (up to 87% yield).

Full text of DOI:10.1016/j.tet.2018.07.006

Tetrahedron xxx (2018) 1e11
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Cobalt-catalyzed oxidative arylmethylation of phosphorylamides
,
,
, ***
Jing Xiao a, Ping Li a, Yingjun Zhang b, Dexun Xie a c, Zhihong Peng a **, Delie An a
,
,
*
Wanrong Dong a
a State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Lushan South Rd. 2,
Changsha, 410082, PR China
b State Key Laboratory of Anti-Infective Drug Development (NO. 2015DQ780357), Sunshine Lake Pharma Co., Ltd, Dongguan, 523871, PR China
c An Chem-Tech Co., Ltd, Guangzhou, 510642, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
A cobalt-catalyzed strategy for N-arylmethylation of phosphorylamides was herein achieved with the
assistance of azodiisobutyronitrile as the radical initiator and di-tert-butyl peroxide as the oxidant. Both
methylarenes and diaryl methanes were compatible under the oxidative conditions, expressing broad
substrate scope (51 examples) and high efficiency (up to 87% yield).
Received 27 February 2018
Received in revised form
23 June 2018
Accepted 4 July 2018
Available online xxx
© 2018 Elsevier Ltd. All rights reserved.
Keywords:
Cobalt-catalysis
Oxidative
Phosphorylamides
Methyl arenes
Diaryl methanes
1. Introduction
that can function as a flame retardant (BA-DOPO, Scheme 1) [6b,6c].
Traditional means of benzylic functionalization involving pre-
Phosphorylamides [1], which possess -P(O)-N- unit, have been
appealing research topic not only because of their unique archi-
tecture, but also for the extraordinary pharmaceutical and material
properties [2]. Additionally, -P(O)-N-backboned molecules have
been elaborately designed for asymmetric syntheses [3], and some
biologically active heterocycles have been successfully prepared
from the principal intermediates [4]. However, novel methodolo-
gies are still highly demanded in the light of diversification
requirement which was driven by the nature of screening process.
Despite the rapid growth have been witnessed in the field [1e9],
the direct modifications of the NH2 group on the phosphorylamides
remained underexploited due to the facile cleavage of P-N bonds
[10] and superior stability of their N-H bonds relative to other
amides [11], which means the direct N-functionalization of the
amides has remained a great challenge. Benzylation attracted our
attention due to a recent description of a benzylated compound
activated substrates suffer from requiring harsh conditions and
tedious steps and generating halogenated waste [6,7] among other
issues. However, benzylic C-H bonds, which are highly reactive [12],
have been directly oxidized to construct different C(sp3)-N bonds
because direct functionalization is more environmentally friendly
and atom/step economical. Amines [13], amides [14], sulfonamides
[14c,15], and sulfoximines [16] can be readily benzylated by
straightforward procedures. Based on the previous successfully
established arylation [8], methylation (alkylation) [9] of phos-
phorylamides, we wish to describe our durative studies on benzy-
lation of the same substrates by (di)arylmethanes. Beyond our
expectations, simple transferring the conditions of methylation
(alkylation) for arylmethylation gave benzylated product in trace
amount. Therefore, cobalt catalysts, which were considered cheaper
and more environmentally benign, were turned to for the arrival of
the useful transformation. Additionally, the oxidative methodology
possessed the advantages including high substrate generality and P-
N bond reservation under the oxidative conditions.
* Corresponding author.
** Corresponding author.
*** Corresponding author.
2. Results and discussions
E-mail addresses: pzh7251@hnu.edu.cn (Z. Peng), deliean@hnu.edu.cn (D. An),
wanrongdong@hnu.edu.cn (W. Dong).
Firstly, the conditions for the reaction between diphenyl
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J. Xiao et al. / Tetrahedron xxx (2018) 1e11
CoBr2 offered superior effect to CoCl2 did for higher 42% of 3aa was
isolated in the CoBr2-mediated system (entries 10 and 11). Disap-
pointingly, NiCl2 and NiBr2 failed to provide positive effect to the
strategy and no reaction was checked at 120 ꢀC for 36 h (entries 12
and 13). Successive screening on the additives was also conducted.
And diamine ligands, for example, tetramethylethylenediamine
(TMEDA) and N,N0-dimethylethylenediamine (DMEDA) afforded
the similar effect to 1,10-phenanthroline did, and 35% and 32% of
3aa was isolated, respectively (entries 14 and 15). Beyond our ex-
pectations, participation of AIBN (azodiisobutyronitrile), which was
regarded as the radical initiator generally, dramatically increased
the yield of 3aa up to 68% (entry 16). And replacement of DTBP (di-
tert-butyl peroxide) with DCP led to higher efficiency of the
transformation, and 82% of 3aa was separated successfully (entry
17). However, TBHP (tert-butyl hydroperoxide) gave inferior effect
to that DTBP did (entry 18). Elevated temperature (140 ꢀC) did not
provide positive effect to the protocol and decreased yield of 3aa
was observed (entry 19). No doubt, no reaction was detected
without an addition of the cobalt catalyst to the system (entry 20).
Moreover, decreased efficiency of the transformation (42% yield of
3aa) was observed if the reaction was conducted without addition
of 4 Å MS, probably due to the absorption of the H2O, which was
generated in situ under the oxidative conditions (entry 21).
Scheme 1. Useful N-benzyl phosphorylamide.
phosphinamide (1a) and toluene (2a) were optimized, as shown in
Table 1. Under the standard methylation/alkylation conditions, the
combination of CuI/1,10-phenanthroline was capable to make the
arylmethylation reaction happen in the presence of DCP (dicumyl
peroxide) with low efficiency, and 3aa was detected in trace
amount after 36 h at 120 ꢀC (entry 1). Other copprous catalysts,
such as CuCl and CuBr did not make the reaction occur in the
presence of 1,10-phenanthroline under the oxidative conditions
(entries 2 and 3). Palladium catalysts, which were exemplified by
PdCl2 and Pd(OAc)2, failed to offer positive effect to the trans-
formation, and no reaction was detected (entries 4 and 5), either
did AgOAc (entry 6). Gratifyingly, iron catalysts in general gave
positive performance in the system. Employment of FeCl2, FeBr2,
FeBr3 rendered the benzylation of phosphorylamide 1a take place
smoothly, forming the desired product 3aa in yields from 25% to
28% (entries 7e9). The best performance of the arylmethylation
protocol was obtained with the assistance of cobalt-catalysts. And
Following the successful establishment of the optimal condi-
tions, the substrate scope and limitations of the phosphonamides
were evaluated in the CoBr2-catalyzed systems (Table 2).
Alkoxyl substituted phosphonamides, such as P-methoxy-, P-
ethoxy-, P-isopropoxy- and P-n-butoxy-P-phenyl phosphonamides
(1b e 1e) coupled efficiently with 2a in the Co-catalyzed system,
and they provided the corresponding N-benzyl amides 3ba e 3ea in
70%e76% yields. Additionally, P-cyclohexyloxy-P-phenyl phospho-
namide (1f) provided 3fa in 79% yield. In a similar fashion, P-
methoxyethoxy-P-phenyl phosphonamide (1g) and P-chlor-
opropoxy-P-phosphonamide (1h) readily coupled with 2a and
furnished 3ga and 3ha in 66% and 69% yields, respectively. (Un)
substituted benzyloxy-decorated phosphonamides were also well
tolerated in the system. For instance, P-benzyloxy-, P-(2-
Table 1
Optimization of the reaction conditions.a
fluorobenzyloxy)-,
P-(4-chlorobenzyloxy)-
and
P-(4-
bromobenzyloxy)-P-phenyl phosphonamides (1i
e
1l) were
smoothly benzylated to afford corresponding products in 3ia e 3la
in yields of 76%e80%. Similarly, the flame retardant BA-DOPO
(3ma) was also provided in 68% yield by the oxidative protocol.
Furthermore, the scope of methylarenes in the oxidative system
was also examined. To our satisfaction, 2-methyltoluene (2b), 3-
methyltoluene (2c), 4-methyltoluene (2d) and mesitylene (2e)
smoothly underwent the phosphorylamidation reaction and pro-
vided 3ab e 3ae in yields from 82% to 87%. In addition, varying the
methyl groups on the methylarenes did not affect the efficiency of
the reaction. p-tert-Butyltoluene (2f) and p-methoxytoluene (2g)
were also tolerated, and 3af and 3ag were isolated in 80% and 70%
yields, respectively. Halogenated toluenes could also serve as
benzylating agents for 4-fluoro-, 2-chloro-, 3-chloro-, 4-chloro-,
and 4-bromotoluenes (2h e 2l), which easily coupled with 1a to
give 3ah e 3al in 72%e87% yields. p-Trifluoromethyltoluene (2m)
and p-methylbenzoic methyl ester (2n) underwent amidation, and
3am and 3an were obtained in moderate yields. Polyarenes 1-
methylnaphthalene (2o) and 2-methylnaphthalene (2p) provided
3ao and 3ap in 67% and 62% yields, respectively. However, electron-
deficient methylarenes and methylheteroarenes, like 4-
nitrotoluene (2q), p-tolunitrile (2r), 2-methylfuran (2s) and 2-
methylpyridine (2t), failed to couple with 1a under the oxidative
reaction conditions. Contrary to our expectations, phosphinami-
dation occurred at the benzylic position of ethylbenzene (2u) and
afforded 3au in 62% yield.
Entry
Cat.
Additive
[O]
Yieldb
1
2
3
4
5
6
7
8
CuI
CuCl
CuBr
Phenc
Phen
Phen
Phen
Phen
Phen
Phen
Phen
Phen
Phen
Phen
Phen
Phen
TMEDA
DMEDA
AIBN
AIBN
AIBN
AIBN
AIBN
AIBN
DCP
DCP
DCP
DCP
DCP
DCP
DCP
DCP
DCP
DCP
DCP
DCP
DCP
DCP
DCP
DCP
DTBP
TBHP
DTBP
DTBP
DTBP
trace
n.d.d
n.d.
n.d.
n.d.
n.d.
20%
25%
28%
38%
42%
n.d.
n.d.
35%
32%
68%
82%
72%
78%e
n.d.
42%f
PdCl2
Pd(OAc)2
AgOAc
FeCl2
FeCl3
FeBr3
CoCl2
CoBr2
NiCl2
NiBr2
CoBr2
CoBr2
CoBr2
CoBr2
CoBr2
CoBr2
e
9
10
11
12
13
14
15
16
17
18
19
20
21
CoBr2
a
Reactions conditions: 1a (0.3 mmol), 2a (3.0 mL, ca. 30 mmol), cat. (10 mol%), 4 Å
molecular sieves (MS, powdered, 200 wt%), additive (0.2 equiv.), [O] (2.0 equiv.) at
120 ꢀC under argon (1 atm) in a sealed tube for 36 h.
b
Isolated yields.
For 1,10-phenanthroline.
For not detected.
At 140 ꢀC.
c
d
e
f
No 4 Å MS added.
Encouraged by the broad substrate scope and high efficiency of
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3
Table 2
Substrates scope of the phosphonamides.a
the method, the amidation protocol was further extended to
diphenyl methanes possessing benzylic C-H bonds (Table 3).
However, CHCl3 proved to be crucial to the oxidative protocol
while the loading of 4 was reduced (1.5 equiv.) in the presence of
CoBr2. Similar to toluene, diphenyl methane (4a) smoothly under-
went the oxidative amidation reaction with diphenyl phosphina-
reactions were conducted in the Co(II)-system, and the results are
shown in Scheme 2. The reaction of a mixture of equal amounts of
(0.25 mmol) P,P-diphenyl phosphinamide (1a) and P-phenyl-P-
methoxy phosphonamide (1b) with 2a (5.0 mL) was carried out to
evaluate the difference in reactivity of the amino groups. After 8 h,
3aa and 3ba were isolated in 18% and 16% yields, respectively, while
30% and 27% yields were obtained after 12 h, indicating that the two
amino groups exhibited almost the same reactivities under these
conditions (Eq. (1)). Notably, the reaction between 1a and a mixture
of 2a (2.5 mL) and 2u (2.5 mL) provided 65% of 3aa and trace 3au.
The result proved that the benzyl C-H bonds of toluene are more
reactive that those of ethylbenzene (Eq. (2)). Similarly, a compari-
son of the benzylic C-H bonds of 2a and 4a was conducted based on
the reaction of 1a with equal amounts of 2a and 4a (2.5 mL). After
36 h, a trace amount of 3aa was found, while 5aa was isolated in
68% yield, which was in accordance with the fact that diaryl
methane generally performed better than methylarenes under
these reaction conditions (Eq. (3)).
mide (1a) and phosphonamides 1b
e 1l and generated
corresponding derivatives 5aa e 5al in yields from 62% to 78%. The
substrate scope of diaryl methanes with various functional groups
was then explored. Symmetric diaryl methanes, such as di-(p-tolyl)
methane (4b), di-(p-methoxyphenyl) methane (4c) and di-(p-flu-
orophenyl) methane (4d), were well tolerated under the oxidative
amidation conditions, and they afforded 5ab e 5ad in 68%e72%
yields. Gratifyingly, asymmetric diaryl methanes were also well
tolerated in the system, and phosphinamino groups were suc-
cessfully installed at the benzylic positions of the substrates. (o-
Methylphenyl) phenyl methane (4e), (m-methylphenyl) phenyl
methane (4f), (p-methylphenyl) phenyl methane (4g), (4-methox-
ylphenyl) phenyl methane (4h), (4-fluorophenyl) phenyl methane
(4i), (4-chlorophenyl) phenyl methane (4j), (4-bromophenyl)
phenyl methane (4k), (4-trifluoromethylphenyl) phenyl methane
(4l) and (4-tolyl) (4-fluorophenyl) methane (4m) furnished corre-
sponding N-methyl phosphinamides 5ae e 5al in yields of 58%e
73%.
Mechanistic studies were conducted with the addition of
TEMPO (2,2,6,6-tetramethyl piperidinyl -1-oxide) in the protocol
and trace 3aa was detected. However, attempts for isolation of the
TEMPO-benzyl adduct failed probably due to the instability of the
intermediate in the system. Results that the yields of 3aa were
depressed severely indicated that the reaction likely took place
through a single-electron transfer (SET) pathway. Exemplified with
To further elucidate the newly developed protocol, competitive
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J. Xiao et al. / Tetrahedron xxx (2018) 1e11
Table 3
Substrates scope on aryl boronic acids.a
Scheme 2. Competitive reactions.
Scheme 3. Proposed mechanism.
the reaction between 1a and 2a in the presence of CuI, a plausible
radical mechanism of the phosphorylamidation of benzylic C-H
bonds was proposed as shown in Scheme 3. Initially, Co(II) was
oxidized into Cu(III) by the free-radical particle (tBuOꢁ), which was
generated easily by heating from DTBP. Then, coordination of Co(III)
and 1a led to the successful formation of the key liganded inter-
mediate A. The in situ formed intermediate A interacted with a
benzyl radical particle, which was produced from isobutyronitrile
radical by AIBN with a release of a N2 molecule under heating,
affording the desired benzylated phosphorylamide 3aa and the
Co(II), which entered the next catalytic circle. In the same manner,
cobalt-mediated transformation would occur through the Co(II)/
Co(III)-circle under the oxidative conditions.
group tolerance for methylarenes and diaryl methanes, and provide
a general and efficient avenue for the preparation of phosphina-
mide and phosphonamide derivatives. Additionally, further explo-
rations on the synthetic and clinical applications of the products are
ongoing in our laboratory.
4. Experimental section
4.1. General remarks
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 stan-
3. Conclusion
dards (
d
¼ 7.26 ppm for 1H NMR and
d
¼ 77.16 ppm for 13C NMR).
In conclusion, we have disclosed a CoBr2-catalyzed oxidative
arylmethylation of phosphorylamides, offering broad functional
Chemical shifts (d) are reported in ppm, and spin-spin coupling
constants (J) are given in Hz, while multiplicities are abbreviated by
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J. Xiao et al. / Tetrahedron xxx (2018) 1e11
5
s (singlet), d (doublet), t (triplet), q (quartet) and m (multiplet).
4.2.5. N-Benzyl-P-ethyl-P-phenylphosphonamide (3ca)
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 recip-
rocal centimeter (cmꢂ1). Melting points were recorded on a na-
tional standard melting point apparatus (Model: Taike XT-4) and
were uncorrected.
Yellowish oil (105.1 mg, 76%). 1H NMR (400 MHz, CDCl3)
d
¼ 7.74
(dd, J ¼ 12.6, 7.6 Hz, 2H), 7.47e7.40 (m, 1H), 7.40e7.32 (m, 2H),
7.25e7.11 (m, 5H), 4.09e3.91 (m, 4H), 3.30e3.15 (m, 1H), 1.23 (d,
J ¼ 6.9 Hz, 3H) (ppm). 13C NMR (100 MHz, CDCl3)
d
¼ 139.7 (JC-
¼ 6.5 Hz), 131.9 (JC-P ¼ 2.9 Hz), 131.6 (JC-P ¼ 9.7 Hz), 130.9 (JC-
¼ 172.8 Hz), 128.6, 128.5 (JC-P ¼ 14.5 Hz), 127.5, 127.4, 60.8 (JC-
¼ 5.6 Hz), 44.9, 16.4 (JC-P ¼ 6.8 Hz) (ppm). 31P NMR (100 MHz,
P
P
P
CDCl3)
d
¼ 22.4 (ppm). MS (EI): m/z ¼ 77.1 (13), 94.0 (10), 106.1
(100), 141.0 (21), 246.0 (14), 275.1 (33). IR (in KBr):
n
¼ 3664, 3210,
4.2. General procedure
2940, 1444, 1207, 1127, 1036, 754, 697, 555, 518 (cmꢂ1). HRMS (ESI)
(m/z) [C15H18NO2P þ Hþ]: Calcd. 276.1153, Found. 276.1150.
4.2.1. Procedures towards N-benzyl phosphorylamides 3 (5)
Under the argon stomosphere, a Schlenk tube (35 mL) equipped
with a magnetic bar was charged with a solution of 1 (0.5 mmol),
MS (4 Å, powdered, 200 wt%), CoBr2 (10 mol%), AIBN (0.2 equiv.) in
2 or 4 (5.0 mL, ca. 30 equiv.), then DTBP (2.0 equiv.) was added
dropwise to the system and the mixture was allowed to stir at
120 ꢀC for 36 h. After cooling to room temperature, the mixture was
filtered through a short celite pad and washed with dichloro-
methane (15 mL ꢃ 3). The filtrate was concentrated and the oily
crude product was purified by column chromatography using silica
gel (200e300 mesh) as stationary phase and ethyl acetate as eluent
to give the corresponding products 3 or 5 in noted yields.
4.2.6. N-Benzyl-P-isopropyl-P-phenylphosphonamide (3da)
Yellowish oil (101.4 mg, 70% yield). 1H NMR (400 MHz, CDCl3)
d
¼ 7.75 (dd, J ¼ 12.6, 7.5 Hz, 2H), 7.46e7.40 (m, 1H), 7.40e7.33 (m,
2H), 7.25e7.13 (m, 5H), 4.75e4.63 (m, 1H), 4.03e3.95 (m, 2H), 3.01
(bs, 1H), 1.25 (dd, J ¼ 9.6, 7.0 Hz, 6H) (ppm). 13C NMR (100 MHz,
CDCl3)
d
¼ 139.7 (JC-P ¼ 7.3 Hz), 131.9 (JC-P ¼ 2.9 Hz), 131.6 (JC-
¼ 9.7 Hz), 131.5 (JC-P ¼ 172.9 Hz), 128.6, 128.5 (JC-P ¼ 14.2 Hz),
P
127.5, 127.4, 69.7 (JC-P ¼ 5.6 Hz), 45.0, 24.3 (JC-P ¼ 4.3 Hz) (ppm). 31
P
NMR (100 MHz, CDCl3)
d
¼ 21.1 (ppm). MS (EI): m/z ¼ 77.1 (5), 91.0
(6), 106.1 (100), 141.0 (11), 246.1 (7), 289.1 (4). IR (in KBr):
n
¼ 3666,
3212, 2965, 1445, 1268, 1206, 1030, 755, 696, 555, 516 (cmꢂ1).
HRMS (ESI) (m/z) [C16H20NO2P þ Hþ]: Calcd. 290.1310, Found.
290.1315.
4.2.2. Procedures for control reactions (Scheme 2)
Under the argon stomosphere, a Schlenk tube (35 mL) equipped
with a magnetic bar was charged with a solution of 1a (0.5 mmol),
or a mixture of 1a (0.25 mmol) and 1b (0.25 mmol), MS (4 Å,
powdered, 200 wt%), CoBr2 (10 mol%), AIBN (0.2 equiv.) in a
4.2.7. N-Benzyl-P-butyl-P-phenylphosphonamide (3ea)
Yellowish oil (108.8 mg, 72%). 1H NMR (400 MHz, CDCl3)
d
¼ 7.74
(dd, J ¼ 12.7, 7.5 Hz, 2H), 7.48e7.41 (m, 1H), 7.41e7.34 (m, 2H),
7.25e7.13 (m, 5H), 4.06e3.88 (m, 4H), 3.18e3.01 (m, 1H), 1.62e1.53
(m, 2H), 1.37e1.28 (m, 2H), 0.83 (t, J ¼ 7.3 Hz, 3H) (ppm). 13C NMR
mixture of 2a and 2u (2.5 mL
þ
2.5 mL) or 2a and 4a
(2.5 mL þ 2.5 mL) or 2a (5.0 mL, ca. 30 equiv.), then DTBP (2.0
equiv.) was added dropwise to the system and the mixture was
allowed to stir at 120 ꢀC for noted time. After cooling to room
temperature, the mixture was filtered through a short celite pad
and washed with dichloromethane (15 mL ꢃ 3). The filtrate was
concentrated and the oily crude product was purified by column
chromatography using silica gel (200e300 mesh) as stationary
phase and ethyl acetate as eluent to give the corresponding results.
(101 MHz, CDCl3)
d
¼ 139.7 (JC-P ¼ 6.6 Hz),132.0 (JC-P ¼ 2.9 Hz),131.6
(JC-P ¼ 9.7 Hz), 130.9 (JC-P ¼ 173.0 Hz), 128.6, 128.5 (JC-P ¼ 14.3 Hz),
127.5, 127.4, 64.6 (JC-P ¼ 5.8 Hz), 45.0, 32.6 (JC-P ¼ 6.8 Hz), 19.0, 13.8
(ppm). 31P NMR (100 MHz, CDCl3)
d
¼ 22.2 (ppm). MS (EI): m/
z ¼ 77.0 (9), 91.0 (8), 106.1 (100), 141.0 (11), 246.0 (10), 303.1 (5). IR
(in KBr):
n
¼ 3667, 3211, 2961, 1445, 1267, 1207, 1026, 754, 698,
555,519 (cmꢂ1). HRMS (ESI) (m/z) [C17H22NO2P þ Hþ]: Calcd.
304.1466, Found. 304.1463.
4.2.3. N-Benzyl-P,P-diphenylphosphinamide (3aa)
4.2.8. N-Benzyl-P-cyclohexyl-P-phenylphosphonamide (3fa)
Colorless oil (75.4 mg, 82% yield). 1H NMR (400 MHz, CDCl3)
Yellowish oil (129.9 mg, 79% yield). 1H NMR (400 MHz, CDCl3)
d
¼ 7.99e7.89 (m, 4H), 7.54e7.40 (m, 6H), 7.40e7.30 (m, 4H),
7.29e7.23 (m, 1H), 4.13 (t, J ¼ 7.2 Hz,2H), 3.32e3.19 (m, 1H)(ppm).
13C NMR (100 MHz, CDCl3)
¼ 139.6 (JC-P ¼ 8.3 Hz), 132.3 (JC-
d
¼ 7.83 (dd, J ¼ 12.8, 7.5 Hz, 2H), 7.54e7.47 (m, 1H), 7.47e7.40 (m,
2H), 7.32e7.20 (m, 5H), 4.55e4.42 (m, 1H), 4.07 (t, J ¼ 7.7 Hz, 2H),
3.15e3.01 (m, 1H), 1.96e1.85 (m, 2H), 1.79e1.66 (m, 2H), 1.61e1.45
(m, 3H), 1.37e1.19 (m, 3H), (ppm). 13C NMR (101 MHz, CDCl3)
d
¼ 9.5 Hz), 132.2 (JC-P ¼ 129.3 Hz), 132.1 (JC-P ¼ 2.6 Hz), 128.8, 128.7
P
(JC-P ¼ 12.5 Hz), 127.8, 127.5, 44.8 (ppm). 31P NMR (100 MHz, CDCl3)
d
¼ 139.8 (JC-P ¼ 7.0 Hz), 131.8 (JC-P ¼ 3.0 Hz), 131.7 (JC-P ¼ 172.9 Hz),
d
¼ 23.7 (ppm). MS (EI): m/z ¼ 77.0 (21), 91.1 (15), 106.1 (100), 155.1
131.6 (JC-P ¼ 9.7 Hz), 128.6, 128.4 (JC-P ¼ 14.2 Hz), 127.4, 127.3, 74.5
(JC-P ¼ 5.9 Hz), 45.0, 34.0 (JC-P ¼ 7.0 Hz), 25.3, 23.8 (JC-P ¼ 7.2 Hz)
(19), 201.1 (54), 202.0 (45), 307.1 (15). IR (in KBr):
n
¼ 3748, 3170,
1437, 1182, 1115, 1067, 845, 725, 692, 554, 519 (cmꢂ1). HRMS (ESI)
(ppm). 31P NMR (100 MHz, CDCl3)
d
¼ 21.0 (ppm). MS (EI): m/
(m/z) [C19H18NOP þ Hþ]: Calcd. 308.1204, Found. 308.1208.
z ¼ 77.0 (7), 91.0 (9), 106.1 (100), 141.0 (13), 223.1 (11), 329.1 (4). IR
(in KBr):
n
¼ 3662, 3212, 2962, 1447, 1207, 1130, 1040, 754, 697, 556,
4.2.4. N-Benzyl-P-methyl-P-phenylphosphonamide (3ba)
518 (cmꢂ1). HRMS (ESI) (m/z)[C19H24NO2P þ Hþ]: Calcd. 330.1623,
White solid (95.1 mg, 73% yield). m.p.: 59e60 ꢀC. 1H NMR
Found. 330.1629.
(400 MHz, CDCl3)
1H), 7.40e7.33 (m, 2H), 7.25e7.12 (m, 5H), 4.06e3.91 (m, 2H), 3.63
(d, J ¼ 11.1 Hz, 3H), 3.36e3.18 (m, 1H) (ppm). 13C NMR (100 MHz,
d
¼ 7.73 (dd, J ¼ 12.7, 7.5 Hz, 2H), 7.48e7.41 (m,
4.2.9. N-Benzyl-P-(2-methoxyethyl)-P-phenyl phosphonamide
(3ga)
CDCl3)
d
¼ 139.6 (JC-P ¼ 6.3 Hz), 132.0 (JC-P ¼ 2.9 Hz), 131.6 (JC-
Yellowish oil (100.8 mg, 66% yield). 1H NMR (400 MHz, CDCl3)
¼ 9.8 Hz), 130.3 (JC-P ¼ 173.3 Hz), 128.6, 128.5 (JC-P ¼ 14.0 Hz),
d
¼ 7.84 (dd, J ¼ 13.1, 7.3 Hz, 2H), 7.55e7.49 (m, 1H), 7.48e7.41 (m,
P
127.5, 127.4, 51.4 (JC-P ¼ 5.8 Hz), 44.9 (ppm). 31P NMR (100 MHz,
2H), 7.35e7.19 (m, 5H), 4.28e4.08 (m, 4H), 3.62e3.58 (m, 2H), 3.35
CDCl3)
d
¼ 24.0 (ppm). MS (EI): m/z ¼ 77.1 (8), 91.0 (7), 106.1 (100),
(s, 3H), 3.33e3.24 (m, 1H) (ppm). 13C NMR (101 MHz, CDCl3)
141.0 (6), 155.0 (17), 261.0 (8). IR (in KBr):
n
¼ 3208, 2945, 1443,
d
¼ 139.7 (JC-P ¼ 6.9 Hz), 132.0 (JC-P ¼ 2.8 Hz), 131.7 (JC-P ¼ 9.8 Hz),
1207, 1128, 1034, 857, 750, 698, 552, 517 (cmꢂ1). HRMS (ESI) (m/z)
[C14H16NO2P þ Hþ]: Calcd. 262.0997, Found. 262.0990.
130.7 (JC-P ¼ 174.3 Hz), 128.6, 128.5 (JC-P ¼ 14.4 Hz), 127.5, 127.4, 71.9
(JC-P ¼ 6.2 Hz), 63.7 (JC-P ¼ 5.8 Hz), 59.0, 44.9 (ppm). 31P NMR
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6
J. Xiao et al. / Tetrahedron xxx (2018) 1e11
(100 MHz, CDCl3)
d
¼ 23.1 (ppm). MS (EI): m/z ¼ 77.0 (11), 91.1 (9),
4.2.14. N-Benzyl-P-(4-bromobenzyl)-P-phenylphosphonamide (3la)
White solid (158.2 mg, 76% yield), m.p. 75e76 ꢀC. 1H NMR
(400 MHz, CDCl3)
106.1 (100), 199.0 (15), 246.1 (21), 305.1 (15). IR (in KBr):
n
¼ 3211,
2889, 1445, 1205, 1128, 1045, 957, 849, 752, 698, 559 (cmꢂ1). HRMS
d
¼ 7.81 (dd, J ¼ 12.9, 7.5 Hz, 2H), 7.57e7.50 (m,
(ESI) (m/z) [C16H20NO3P þ Hþ]: Calcd. 306.1259, Found. 306.1263.
1H), 7.49e7.41 (m, 4H), 7.32e7.17 (m, 7H), 5.05e4.93 (m, 2H),
4.13e3.97 (m, 2H), 3.30e3.17 (m, 1H) (ppm). 13C NMR (101 MHz,
4.2.10. N-Benzyl-P-(3-chloropropyl)-P-phenyl phosphonamide
(3ha)
CDCl3)
d
¼ 139.5 (JC-P ¼ 6.4 Hz), 135.8 (JC-P ¼ 7.2 Hz), 132.3 (JC-
¼ 3.0 Hz), 131.8, 131.6 (JC-P ¼ 9.9 Hz), 130.3 (JC-P ¼ 173.2 Hz), 129.6,
P
Yellowish oil (111.2 mg, 69% yield). 1H NMR (400 MHz, CDCl3)
128.8, 128.7 (JC-P ¼ 14.3 Hz), 127.5(3), 127.5(0), 122.3, 65.5 (JC-
d
¼ 7.74 (dd, J ¼ 12.1, 8.1 Hz, 2H), 7.50e7.43 (m, 1H), 7.42e7.35 (m,
¼ 5.2 Hz), 45.0 (ppm). 31P NMR (162 MHz, CDCl3)
¼ 23.3 (ppm).
d
P
2H), 7.27e7.13 (m, 5H), 4.18e3.95 (m, 4H), 3.61e3.50 (m, 2H),
MS (EI): m/z ¼ 77.1 (7), 90.1 (4), 106.0 (100), 169.0 (12), 336.1 (5),
3.30e3.10 (m, 1H), 2.09e1.97 (m, 2H) (ppm). 13C NMR (101 MHz,
415.0 (6). IR (in KBr):
n
¼ 3664, 2982, 2890, 1263, 1199, 1047, 800,
CDCl3)
d
¼ 139.6 (JC-P ¼ 6.4 Hz), 132.2 (JC-P ¼ 2.7 Hz), 131.6 (JC-
757, 690, 555, 520 (cmꢂ1). HRMS (ESI) (m/z)[C20H19BrNO2P þ Hþ]:
¼ 9.8 Hz), 130.4 (JC-P ¼ 173.4 Hz), 128.7, 128.6 (JC-P ¼ 14.3 Hz),
Calcd. 416.0415, Found. 416.0412.
P
127.5, 61.3 (JC-P ¼ 5.5 Hz), 45.0, 41.1, 33.3 (JC-P ¼ 6.8 Hz) (ppm). 31P
NMR (100 MHz, CDCl3)
d
¼ 22.9 (ppm). MS (EI): m/z ¼ 77.0 (8), 91.1
4.2.15. 6-(Benzylamino)-6H-dibenzo[c,e][1,2]oxaphosphinine 6-
oxide (3ma)
(9), 106.1 (100), 141.0 (13), 217.0 (9), 246.1 (11), 323.1 (4). IR (in KBr):
n
¼ 3661, 3210, 2966, 1443, 1267, 1205, 1128, 1032, 754, 698, 554
White solid (108.9 mg, 68% yield), m.p. 149e150 ꢀC. 1H NMR
(cmꢂ1). HRMS (ESI) (m/z)[C16H19ClNO2P þ Hþ]: Calcd. 324.0920,
(400 MHz, CDCl3)
d
¼ 8.00e7.87 (m, 3H), 7.68 (t, J ¼ 7.7 Hz,1H),7.46
Found. 324.0915.
(t, J ¼ 6.6 Hz,1H),7.35 (t, J ¼ 7.6 Hz,1H),7.31e7.20 (m, 7H), 7.27e7.20
(m, 1H),4.14e3.99 (m, 2H), 3.72e3.60 (m, 1H) (ppm). 13C NMR
4.2.11. N,P-Dibenzyl-P-phenylphosphonamide (3ia)
(100 MHz, CDCl3)
d
¼ 150.0 (JC-P ¼ 7.2 Hz),139.0 (JC-P ¼ 6.3 Hz),137.3
White solid (135.1 mg, 80% yield). m.p.: 54e55 ꢀC. 1H NMR
(JC-P ¼ 7.3 Hz), 133.0 (JC-P ¼ 2.3 Hz), 130.4, 130.3 (JC-P ¼ 9.4 Hz), 128.7,
128.4 (JC-P ¼ 14.6 Hz),127.6, 127.5,125.0,124.4,123.8 (JC-P ¼ 11.4 Hz),
123.4, 122.2 (JC-P ¼ 11.7 Hz), 120.7 (JC-P ¼ 6.4 Hz), 45.2 (ppm). 31P
(400 MHz, CDCl3)
d
¼ 7.75 (dd, J ¼ 12.6, 7.6 Hz, 2H), 7.47e7.40 (m,
1H), 7.39e7.32 (m, 2H), 7.29e7.11 (m, 10H), 5.03e4.92 (m, 2H),
4.04e3.88 (m, 2H), 3.32e3.19 (m, 1H) (ppm). 13C NMR (101 MHz,
NMR (160 MHz, CDCl3)
d
¼ 14.8 (ppm). MS (EI): m/z ¼ 77.1 (6), 90.1
CDCl3)
d
¼ 139.6 (JC-P ¼ 6.6 Hz), 136.7 (JC-P ¼ 7.3 Hz), 132.1 (JC-
(4),106.0 (100),169.0 (17), 215.1 (10), 321.0 (3). IR (in KBr):
n
¼ 3154,
¼ 2.9 Hz), 131.6 (JC-P ¼ 9.8 Hz), 130.5 (JC-P ¼ 173.4 Hz), 128.6, 128.5
2887, 1642, 1472, 1227, 1148, 925, 899, 782, 757 (cmꢂ1). HRMS (ESI)
P
(JC-P ¼ 13.3 Hz), 128.3, 127.9, 127.5, 127.4, 66.2 (JC-P ¼ 5.3 Hz), 44.9
(m/z)[C19H16NO2P þ Hþ]: Calcd. 322.0997, Found. 322.0992.
(ppm). 31P NMR (100 MHz, CDCl3)
¼ 23.1 (ppm). MS (EI): m/
z ¼ 77.1 (5), 91.1 (26), 106.0 (100), 141.0 (10), 231,1 (7), 246.0 (8),
d
4.2.16. N-(2-Methylbenzyl)-P,P-diphenylphosphinamide (3ab)
337.1 (3). IR (in KBr):
n
¼ 3659, 3283, 2984, 2901, 1267, 1205, 1047,
White solid (131.4 mg, 82% yield). m.p. 105e106 ꢀC. 1H NMR
800, 754, 692, 590 (cmꢂ1). HRMS (ESI) (m/z) [C20H20NO2P þ Hþ]:
(400 MHz, CDCl3)
7.24e7.12 (m, 3H), 4.13 (t, J ¼ 6.6 Hz, 2H), 3.08e2.96 (m, 1H), 2.28 (s,
3H)(ppm). 13C NMR (101 MHz, CDCl3)
¼ 137.4 (JC-P ¼ 9.0 Hz), 136.1,
d
¼ 8.01e7.89 (m, 4H), 7.54e7.38 (m, 7H),
Calcd. 338.1310, Found. 338.1318.
d
4.2.12. P-Phenyl-P-(3-fluorobenzyloxy)-N-(p-tolyl) phosphonamide
(3ja)
132.2 (JC-P ¼ 129.0 Hz), 132.1 (JC-P ¼ 9.5 Hz), 132.0 (JC-P ¼ 2.7 Hz),
130.4, 128.7 (JC-P ¼ 12.6 Hz), 127.8, 127.5, 126.3, 42.2, 19.1 (ppm). 31
P
Yellowish oil (136.4 mg, 77% yield). 1H NMR (400 MHz, CDCl3)
NMR (100 MHz, CDCl3)
d
¼ 23.9 (ppm). MS (EI): m/z ¼ 77.1 (15),
d
¼ 7.83 (dd, J ¼ 12.9, 7.6 Hz, 2H), 7.55e7.49 (m, 1H), 7.47e7.38 (m,
3H), 7.34e7.19 (m, 6H), 7.11 (t, J ¼ 7.5 Hz, 1H), 7.04 (t, J ¼ 9.1 Hz, 1H),
5.22e5.06 (m, 2H), 4.13e4.00 (m, 2H), 3.39e3.21 (m, 1H) (ppm). 13
NMR (101 MHz, CDCl3)
104.1 (13), 120.1 (100), 201.0 (62), 230.0 (43), 321.1 (36). IR (in KBr):
n
¼ 3661, 3184, 2921, 1437, 1269, 1184, 1116, 1072, 754, 698, 554
C
(cmꢂ1). HRMS (ESI) (m/z)[C20H20NOP þ Hþ]: Calcd. 322.1361,
d
¼ 160.8 (JC-F ¼ 248.2 Hz), 139.5 (JC-
Found. 322.1354.
¼ 6.7 Hz), 132.2 (JC-P ¼ 2.9 Hz), 131.6 (JC-P ¼ 9.9 Hz), 130.4 (JC-
¼ 3.7 Hz), 130.3 (JC-P ¼ 173.4 Hz), 130.2 (JC-F ¼ 8.2 Hz), 128.7, 128.6
P
4.2.17. N-(3-Methylbenzyl)-P,P-diphenylphosphinamide (3ac)
F
(JC-P ¼ 13.6 Hz), 127.5, 127.4, 124.3 (JC-F ¼ 3.6 Hz), 124.0 (dd, JC-
White solid (139.1 mg, 87% yield). m.p. 59e60 ꢀC. 1H NMR
¼ 14.4 Hz, JC-F ¼ 7.5 Hz), 115.5 (JC-F ¼ 21.0 Hz), 60.3 (JC-P ¼ 4.7 Hz),
(400 MHz, CDCl3)
d
¼ 7.93 (dd, J ¼ 11.6, 7.7 Hz, 4H), 7.52e7.40 (m,
P
44.9 (ppm). 19F NMR (376 MHz, CDCl3)
d
¼ ꢂ118.2 (ppm). 31P NMR
6H), 7.24e7.19 (m, 1H), 7.18e7.12 (m, 2H), 7.09e7.04 (m, 1H), 4.08 (t,
J ¼ 7.2 Hz, 2H), 3.31e3.21 (m, 1H), 2.32 (s, 3H) (ppm). 13C NMR
(100 MHz, CDCl3)
d
¼ 23.3 (ppm). MS (EI): m/z ¼ 77.0 (6), 106.1
(100), 109.1 (21), 141.0 (5), 249.1 (8), 355.1 (5). IR (in KBr):
n
¼ 3661,
(101 MHz, CDCl3)
d
¼ 139.6 (JC-P ¼ 8.4 Hz), 138.4, 132.9, 132.3 (JC-
3221, 2985, 1445, 1267, 1194, 1039, 755, 695, 554, 512 (cmꢂ1). HRMS
¼ 129.2 Hz), 132.2 (JC-P ¼ 9.5 Hz), 132.0 (JC-P ¼ 2.7 Hz), 128.7 (JC-
P
(ESI) (m/z)[C20H19FNO2P þ Hþ]: Calcd. 356.1216, Found. 356.1222.
¼ 12.6 Hz), 128.6, 128.2, 124.8, 44.7, 21.5 (ppm). 31P NMR
P
(100 MHz, CDCl3)
d
¼ 23.8 (ppm). MS (EI): m/z ¼ 77.0 (11), 104.1 (8),
4.2.13. N-Benzyl-P-(4-chlorobenzyl)-P-phenylphosphonamide
(3ka)
120.1 (100), 155.1 (12), 201.0 (43), 321.1 (27). IR (in KBr):
n
¼ 3665,
3174, 2919, 1439, 1271, 1186, 1117, 1072, 756, 697, 554 (cmꢂ1). HRMS
White solid (146.6 mg, 79% yield). m.p.: 81e82 ꢀC. 1H NMR
(ESI) (m/z) [C20H20NOP þ Hþ]: Calcd. 322.1361, Found. 322.1365.
(400 MHz, CDCl3)
d
¼ 7.82 (dd, J ¼ 12.9, 7.6 Hz, 2H), 7.56e7.51 (m,
1H), 7.49e7.42 (m, 2H), 7.33e7.20 (m, 9H), 5.08e4.96 (m, 2H),
4.2.18. N-(4-Methylbenzyl)-P,P-diphenylphosphinamide (3ad)
4.14e3.98 (m, 2H), 3.25e3.08 (m, 1H) (ppm). 13C NMR (101 MHz,
White solid (137.8 mg, 86% yield). m.p.: 102e103 ꢀC. 1H NMR
CDCl3)
d
¼ 139.5 (JC-P ¼ 6.3 Hz), 135.2 (JC-P ¼ 7.2 Hz), 134.2, 132.2 (JC-
(400 MHz, CDCl3)
d
¼ 7.94 (dd, J ¼ 11.7, 7.6 Hz, 4H), 7.51e7.41 (m,
¼ 2.9 Hz), 131.6 (JC-P ¼ 9.9 Hz), 130.3 (JC-P ¼ 173.2 Hz), 129.3, 128.8,
6H), 7.25 (d, J ¼ 7.9 Hz, 2H), 7.13 (d, J ¼ 7.6 Hz, 2H), 4.08 (t, J ¼ 7.2 Hz,
P
128.7, 128.6 (JC-P ¼ 14.3 Hz), 127.5, 65.4 (JC-P ¼ 5.2 Hz), 45.0 (ppm).
2H), 3.23e3.11 (m, 1H), 2.33 (s, 3H) (ppm). 13C NMR (101 MHz,
31P NMR (162 MHz, CDCl3)
¼ 23.4 (ppm). MS (EI): m/z ¼ 77.0 (9),
91.1 (4), 106.1 (100), 125.0 (16), 140.0 (5), 371.0 (11). IR (in KBr):
d
CDCl3)
(JC-P ¼ 9.5 Hz), 132.0 (JC-P ¼ 2.7 Hz), 129.2, 128.7 (JC-P ¼ 12.6 Hz),
125.7, 44.7, 21.4 (ppm). 31P NMR (100 MHz, CDCl3)
¼ 23.6 (ppm).
MS (EI): m/z ¼ 77.0 (8), 105.1 (5), 120.1 (100), 155.1 (14), 201.0 (62),
321.1 (26). IR (in KBr):
¼ 3660, 3177, 2920, 1439, 1269, 1186, 1117,
d
¼ 139.5 (JC-P ¼ 8.6 Hz), 138.3, 132.4 (JC-P ¼ 129.1 Hz), 132.3
n
¼ 3659, 3278, 2984, 2904, 1266, 1204, 1060, 801, 754, 700, 591
d
(cmꢂ1). HRMS (ESI) (m/z)[C20H19ClNO2P þ Hþ]: Calcd. 372.0920,
Found. 372.0926.
n
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J. Xiao et al. / Tetrahedron xxx (2018) 1e11
7
1072, 754, 696, 555 (cmꢂ1). HRMS (ESI) (m/z)[C20H20NOP þ Hþ]:
(26), 201.0 (28), 306.0 (100), 340.1 (3). IR (in KBr):
n
¼ 3174, 2985,
Calcd. 322.1361, Found. 322.1354.
2901, 1440, 1267, 1184, 1076, 801, 755, 695, 520 (cmꢂ1). HRMS (ESI)
(m/z)[C19H17ClNOP þ Hþ]: Calcd. 342.0815, Found. 342.0814.
4.2.19. N-(3,5-Dimethylbenzyl)-P,P-diphenylphosphinamide (3ae)
White solid (137.0 mg, 82% yield). m.p. 120e121 ꢀC. 1H NMR
4.2.24. N-(3-Chlorobenzyl)-P,P-diphenylphosphinamide (3aj)
(400 MHz, CDCl3)
6H), 6.95 (s, 2H), 6.90 (s, 1H), 4.05 (t, J ¼ 7.2 Hz, 2H), 3.24e3.11 (m,
1H), 2.29 (s, 6H) (ppm). 13C NMR (101 MHz, CDCl3)
¼ 139.5 (JC-
¼ 8.6 Hz), 138.3, 132.4 (JC-P ¼ 129.1 Hz), 132.3 (JC-P ¼ 9.5 Hz), 132.0
d
¼ 7.94 (dd, J ¼ 11.8, 7.7 Hz, 4H), 7.52e7.41 (m,
Yellowish oil (136.7 mg, 80% yield). 1H NMR (400 MHz, CDCl3)
d
¼ 7.97e7.87 (m, 4H), 7.54e7.48 (m, 2H), 7.48e7.41 (m, 4H), 7.33 (s,
1H), 7.28e7.20 (m, 3H), 4.10 (t, J ¼ 7.7 Hz, 2H), 3.35e3.23 (m,
1H)(ppm). 13C NMR (101 MHz, CDCl3)
d
d
¼ 141.8 (JC-P ¼ 7.9 Hz), 134.4,
P
(JC-P ¼ 2.7 Hz), 129.2, 128.7 (JC-P ¼ 12.6 Hz), 125.7, 44.7, 21.4 (ppm).
31P NMR (100 MHz, CDCl3)
¼ 23.6 (ppm). MS (EI): m/z ¼ 77.0 (7),
91.0 (5), 134.1 (100), 155.1 (8), 201.0 (35), 335.1 (20). IR (in KBr):
132.2 (JC-P ¼ 9.6 Hz), 132.1 (JC-P ¼ 4.5 Hz), 132.0 (JC-P ¼ 129.2 Hz),
d
130.0, 128.7 (JC-P ¼ 12.6 Hz), 127.8, 127.6, 126.0, 44.2 (ppm). 31P NMR
(100 MHz, CDCl3)
d
¼ 24.1 (ppm). MS (EI): m/z ¼ 77.0 (8), 125.0 (10),
n
¼ 3661, 3180, 2980, 1444, 1267, 1190, 1072, 756, 698, 555, 518
140.0 (100), 155.1 (10), 201.0 (33), 340.1 (5). IR (in KBr):
n
¼ 3175,
(cmꢂ1). HRMS (ESI) (m/z) [C21H22NOP þ Hþ]: Calcd. 336.1517,
2984, 2901, 1433, 1267, 1185, 1077, 798, 758, 696, 524 (cmꢂ1). HRMS
Found. 336.1514.
(ESI) (m/z) [ C19H17ClNOP þ Hþ]: Calcd. 342.0815, Found. 342.0820.
4.2.20. N-(4-tert-Butylbenzyl)-P,P-diphenylphosphinamide (3af)
4.2.25. N-(4-Chlorobenzyl)-P,P-diphenylphosphinamide (3ak)
White solid (145.4 mg, 80% yield). m.p.: 150e151 ꢀC. 1H NMR
White solid (149.3 mg, 87% yield). m.p. 130e131 ꢀC. 1H NMR
(400 MHz, CDCl3)
d
¼ 7.94 (dd, J ¼ 10.5, 8.6 Hz, 4H), 7.52e7.40 (m,
(400 MHz, CDCl3)
6H), 7.34e7.26 (m, 4H), 4.10 (t, J ¼ 7.8 Hz, 2H), 3.23e3.12 (m,
1H)(ppm). 13C NMR (101 MHz, CDCl3)
d
¼ 7.92 (dd, J ¼ 10.5, 8.7 Hz, 4H), 7.54e7.41 (m,
6H), 7.35 (d, J ¼ 7.9 Hz, 2H), 7.30 (d, J ¼ 7.8 Hz, 2H), 4.10 (t, J ¼ 7.1 Hz,
2H), 3.29e3.12 (m, 1H), 1.30 (s, 9H) (ppm). 13C NMR (100 MHz,
d
¼ 138.2 (JC-P ¼ 7.7 Hz),133.3,
CDCl3)
(JC-P ¼ 9.5 Hz), 132.0 (JC-P ¼ 2.6 Hz), 128.7 (JC-P ¼ 12.6 Hz), 127.6,
125.6, 44.4, 34.6, 31.4 (ppm). 31P NMR (100 MHz, CDCl3)
¼ 23.6
(ppm). MS (EI): m/z ¼ 77.0 (7), 91.0 (6), 132.1 (8), 146.1 (15), 162.1
d
¼ 150.5, 136.6 (JC-P ¼ 8.8 Hz), 132.3 (JC-P ¼ 129.2 Hz), 132.2
132.3 (JC-P ¼ 9.4 Hz), 132.2, 132.1 (JC-P ¼ 129.4 Hz), 129.2, 128.9,
128.8 (JC-P ¼ 12.6 Hz), 44.3 (ppm). 31P NMR (100 MHz, CDCl3)
d
d
¼ 24.0 (ppm). MS (EI): m/z ¼ 77.0 (10), 125.1 (12), 140.0 (100),
155.1 (7), 201.0 (21), 340.1 (5). IR (in KBr):
n
¼ 3175, 2984, 2903,
(100), 201.0 (33), 363.1 (27). IR (in KBr):
n
¼ 3667, 3180, 2910, 1439,
1439, 1267, 1182, 1074, 800, 754, 696, 526 (cmꢂ1). HRMS (ESI) (m/z)
[C19H17ClNOP þ Hþ]: Calcd. 342.0815, Found. 342.0821.
1187, 1114, 1069, 760, 691, 550, 520 (cmꢂ1). HRMS (ESI) (m/z)
[C23H26NOP þ Hþ]: Calcd. 364.1830, Found. 364.1825.
4.2.26. N-(4-Bromobenzyl)-P,P-diphenyl phosphinamide (3al)
4.2.21. N-(4-Methoxybenzyl)-P,P-diphenylphosphinamide (3ag)
White solid (142.3 mg, 74% yield). m.p. 113e114 ꢀC. 1H NMR
Brownish oil (118.4 mg, 70% yield). 1H NMR (400 MHz, CDCl3)
(400 MHz, CDCl3)
d
¼ 7.97e7.87 (m, 4H), 7.55e7.41 (m, 8H), 7.25 (d,
d
¼ 7.93 (dd, J ¼ 11.3, 7.8 Hz, 4H), 7.53e7.40 (m, 6H), 7.28 (d,
J ¼ 8.2 Hz, 2H), 6.86 (d, J ¼ 7.9 Hz, 2H), 4.06 (t, J ¼ 7.1 Hz, 2H), 3.78 (s,
3H), 3.22e3.12 (m, 1H) (ppm). 13C NMR (101 MHz, CDCl3)
J ¼ 8.1 Hz, 2H), 4.09 (t, J ¼ 7.7 Hz, 2H), 3.28e3.16 (m, 1H)(ppm). 13
C
NMR (101 MHz, CDCl3)
d
¼ 138.8 (JC-P ¼ 7.6 Hz), 132.2 (JC-P ¼ 9.5 Hz),
d
¼ 159.1,
132.2 (JC-P ¼ 2.6 Hz), 132.1 (JC-P ¼ 129.4 Hz), 131.8, 129.6, 128.8 (JC-
132.3 (JC-P ¼ 129.4 Hz), 132.2 (JC-P ¼ 9.5 Hz), 132.0 (JC-P ¼ 2.6 Hz),
¼ 12.6 Hz), 121.4, 44.3 (ppm). 31P NMR (100 MHz, CDCl3)
¼ 24.0
d
P
131.8 (JC-P ¼ 8.5 Hz), 129.1, 128.7 (JC-P ¼ 12.5 Hz), 114.1, 55.4, 44.2
(ppm). MS (EI): m/z ¼ 77.0 (14), 125.0 (10), 155.1 (20), 183.9 (100),
(ppm). 31P NMR (100 MHz, CDCl3)
d
¼ 23.7 (ppm). MS (EI): m/
201.0 (67), 384.9 (20). IR (in KBr):
n
¼ 3667, 2984, 2903, 1439, 1269,
z ¼ 77.0 (7), 136.0 (100), 155.1 (9), 201.1 (23), 337.1 (15). IR (in KBr):
1184, 1114, 1070, 754, 698, 524 (cmꢂ1). HRMS (ESI) (m/z)
n
¼ 3667, 2985, 1512, 1439, 1269, 1180, 1115, 1068, 756, 698, 519
[C19H17BrNOP]: Calcd. 386.0309, Found. 386.0306.
(cmꢂ1). HRMS (ESI) (m/z)[C20H20NO2P þ Hþ]: Calcd. 338.1310,
Found. 338.1306.
4.2.27. P,P-Diphenyl-N-4-trifluoromethylbenzyl phosphinamide
(3am)
4.2.22. N-(4-Fluorobenzyl)-P,P-diphenylphosphinamide (3ah)
Yellowish oil (130.9 mg, 70% yield). 1H NMR (400 MHz, CDCl3)
Yellowish oil (135.5 mg, 83% yield). 1H NMR (400 MHz, CDCl3)
d
¼ 7.91 (dd, J ¼ 11.7, 7.9 Hz, 4H), 7.56 (d, J ¼ 7.8 Hz, 2H), 7.54e7.41
d
¼ 7.92e7.83 (m, 4H), 7.48e7.36 (m, 6H), 7.33e7.27 (m, 2H), 6.94 (t,
(m, 8H), 4.18 (t, J ¼ 8.1 Hz, 2H), 3.44e3.31 (m, 1H) (ppm). 13C NMR
J ¼ 8.3 Hz, 2H), 4.03 (t, J ¼ 7.6 Hz, 2H), 3.61e3.47 (m, 1H) (ppm). 13
C
(101 MHz, CDCl3)
d
¼ 143.8 (JC-P ¼ 6.3 Hz), 132.3 (JC-P ¼ 4.2 Hz),
NMR (101 MHz, CDCl3)
d
¼ 162.2 (JC-P ¼ 245.5 Hz), 135.5 (dd, JC-
132.2 (JC-P ¼ 9.5 Hz), 132.1 (JC-P ¼ 130.3 Hz), 129.8 (q, JC-F ¼ 32.2 Hz),
¼ 7.9 Hz, JC-F ¼ 3.7 Hz), 132.3 (JC-P ¼ 9.6 Hz), 132.2 (JC-P ¼ 2.8 Hz),
128.8 (JC-P ¼ 12.6 Hz), 128.1, 125.7 (q, JC-F ¼ 3.4 Hz), 124.2 (q, JC-
P
132.1 (JC-P ¼ 129.1 Hz), 129.5 (JC-F ¼ 8.1 Hz), 128.8 (JC-P ¼ 12.6 Hz),
¼ 272.0 Hz), 44.5 (ppm). 19F NMR (100 MHz, CDCl3)
d
¼ ꢂ62.5
F
115.6 (JC-F ¼ 21.4 Hz), 44.2 (ppm). 19F NMR (376 MHz, CDCl3)
(ppm). 31P NMR (100 MHz, CDCl3)
d
¼ 24.3 (ppm). MS (EI): m/
d
¼ ꢂ115.1 (ppm). 31P NMR (100 MHz, CDCl3)
d
¼ 24.0 (ppm). MS
z ¼ 77.0 (7), 125.0 (5), 155.1 (9), 174.0 (34), 202.0 (100), 356.0 (14),
(EI): m/z ¼ 77.0 (8), 95.0 (7), 124.1 (100), 155.1 (12), 201.1 (24), 325.1
375.1 (58). IR (in KBr):
n
¼ 3169, 1439, 1325, 1269, 1178, 1118, 1069,
(8). IR (in KBr):
n
¼ 3173, 2984, 1601, 1508, 1439, 1267, 1184, 1117,
856, 754, 696, 555 (cmꢂ1). HRMS (ESI) (m/z)[C20H17F3NOP þ Hþ]:
822, 754, 696 (cmꢂ1). HRMS (ESI) (m/z)[C19H17FNOP þ Hþ]: Calcd.
Calcd. 376.1078, Found. 376.1076.
326.1110, Found. 326.1116.
4.2.28. Methyl 4-(((diphenylphosphoryl)amino)methyl) benzoate
(3an)
4.2.23. N-(2-Chlorobenzyl)-P,P-diphenylphosphinamide (3ai)
White solid (143.3 mg, 84% yield). m.p.: 109e110 ꢀC. 1H NMR
Yellowish oil (124.4 mg, 68% yield). 1H NMR (400 MHz, CDCl3)
(400 MHz, CDCl3)
d
¼ 7.90 (dd, J ¼ 10.8, 8.4 Hz, 4H), 7.52e7.46 (m,
d
¼ 7.98 (d, J ¼ 8.0 Hz, 2H), 7.92 (dd, J ¼ 11.5, 7.6 Hz, 4H), 7.53e7.40
(m, 8H), 4.18 (t, J ¼ 7.9 Hz, 2H), 3.89 (s, 3H), 3.41e3.29 (m, 1H)
(ppm). 13C NMR (101 MHz, CDCl3)
2H), 7.46e7.39 (m, 4H), 7.39e7.35 (m, 1H), 7.35e7.30 (m, 1H),
7.23e7.17 (m, 2H),4.23 (t, J ¼ 8.1 Hz, 2H), 3.48e3.37 (m, 1H) (ppm).
d
¼ 167.0, 144.9 (JC-P ¼ 7.6 Hz),
13C NMR (101 MHz, CDCl3)
d
¼ 137.1 (JC-P ¼ 7.2 Hz), 133.6, 132.3 (JC-
132.3 (JC-P ¼ 9.4 Hz), 132.2 (JC-P ¼ 3.1 Hz), 132.0 (JC-P ¼ 129.6 Hz),
¼ 9.6 Hz), 132.2 (JC-P ¼ 129.3 Hz), 132.1 (JC-P ¼ 2.7 Hz), 130.0, 129.6,
130.1, 129.4, 128.8 (JC-P ¼ 12.6 Hz), 127.7, 52.2, 44.6 (ppm). 31P NMR
P
128.9, 128.7 (JC-P ¼ 12.6 Hz), 127.2, 42.7 (ppm). 31P NMR (100 MHz,
(100 MHz, CDCl3)
d
¼ 24.3 (ppm). MS (EI): m/z ¼ 77.0 (7), 146.1
CDCl3)
d
¼ 24.2 (ppm). MS (EI): m/z ¼ 77.0 (12), 125.0 (15), 140.0
(100), 201.0 (34), 350.1 (21) 365.1 (12). IR (in KBr):
n
¼ 3667, 2984,
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8
J. Xiao et al. / Tetrahedron xxx (2018) 1e11
1719, 1437, 1271, 1188, 1109, 1070, 756, 700, 527 (cmꢂ1). HRMS (ESI)
d
¼ 22.8 (ppm). MS (EI): m/z ¼ 77.1 (9), 104.0 (5), 155.0 (17), 165.1
(m/z)[C21H20NO3P þ Hþ]: Calcd. 366.1259, Found. 366.1266.
(8), 182.1 (100), 260.0 (12), 337.1 (21). IR (in KBr):
n
¼ 3184, 1594,
1450, 1209, 1124, 1028, 912, 750, 700, 554 (cmꢂ1). HRMS (ESI) (m/z)
[C20H20NO2P þ Hþ]: Calcd. 338.1310, Found. 338.1313.
4.2.29. N-(1-Naphthylmethyl)-P,P-diphenyl phosphinamide (3ao)
White solid (120.1 mg, 67% yield). m.p.: 144e145 ꢀC. 1H NMR
(400 MHz, CDCl3)
d
¼ 8.05 (d, J ¼ 7.8 Hz, 1H), 8.01e7.91 (m, 4H), 7.87
4.2.34. N-Diphenylmethyl-P-ethyl-P-phenyl phosphonamide (5ca)
(d, J ¼ 7.4 Hz, 1H), 7.80 (d, J ¼ 8.1 Hz,1H), 7.58e7.39 (m, 10H), 4.60 (t,
White solid (126.3 mg, 72% yield). m.p. 121e122 ꢀC. 1H NMR
J ¼ 6.2 Hz, 2H), 3.28e3.15 (m, 1H)(ppm). 13C NMR (101 MHz, CDCl3)
(400 MHz, CDCl3)
d
¼ 7.72 (dd, J ¼ 12.9, 7.8 Hz, 2H), 7.51e7.44 (m,
d
¼ 135.0 (JC-P ¼ 9.0 Hz), 133.9, 132.3 (JC-P ¼ 128.7 Hz), 132.2 (JC-
¼ 9.6 Hz), 132.1 (JC-P ¼ 2.7 Hz), 131.2, 128.9, 128.7 (JC-P ¼ 12.6 Hz),
1H), 7.41e7.34 (m, 2H), 7.31e7.18 (m, 8H), 7.16e7.10 (m, 2H), 5.37 (t,
J ¼ 9.9 Hz, 1H), 4.10e4.00 (m, 1H), 3.88e3.78 (m, 1H), 3.60 (t,
J ¼ 9.5 Hz, 1H), 1.18 (t, J ¼ 7.0 Hz, 3H) (ppm). 13C NMR (101 MHz,
P
128.4, 126.6, 126.0, 125.8, 125.6, 123.4, 42.2 (ppm). 31P NMR
(100 MHz, CDCl3)
d
¼ 24.0 (ppm). MS (EI): m/z ¼ 77.0 (4), 115.0 (4),
CDCl3)
d
¼ 143.4 (JC-P ¼ 3.9 Hz), 143.2 (JC-P ¼ 5.6 Hz), 131.8 (JC-
141.1 (7), 156.1 (100), 201.0 (28), 357.0 (32). IR (in KBr):
n
¼ 3666,
¼ 2.7 Hz), 131.6 (JC-P ¼ 9.8 Hz), 130.9 (JC-P ¼ 174.1 Hz), 128.6, 128.5,
P
2985, 1440, 1267, 1186, 1116, 1067, 756, 697, 556, 519 (cmꢂ1). HRMS
128.4 (JC-P ¼ 14.4 Hz), 127.3, 127.2(6), 127.2(1), 60.8 (JC-P ¼ 5.7 Hz),
(ESI) (m/z)[C23H20NOP þ Hþ]: Calcd. 358.1361, Found. 358.1356.
58.8, 16.2 (JC-P ¼ 7.0 Hz) (ppm). 31P NMR (100 MHz, CDCl3)
¼ 21.2
d
(ppm). MS (EI): m/z ¼ 77.1 (11), 104.1 (8), 141.0 (15), 165.1 (10), 182.1
4.2.30. N-(2-Naphthylmethyl)-P,P-diphenyl phosphinamide (3ap)
(100), 274.0 (7), 322.0 (10), 351.0 (23). IR (in KBr):
n
¼ 3190, 1596,
White solid (110.2 mg, 62% yield). m.p. 125e126 ꢀC. 1H NMR
1452, 1209, 1126, 1034, 958, 746, 698, 555 (cmꢂ1). HRMS (ESI) (m/z)
[C21H22NO2P þ Hþ]: Calcd. 352.1466, Found. 352.1461.
(400 MHz, CDCl3)
3H), 7.75 (s, 1H), 7.54e7.41 (m, 9H), 4.29 (t, J ¼ 7.4 Hz, 2H),
3.38e3.27 (m, 1H) (ppm). 13C NMR (101 MHz, CDCl3)
¼ 137.1 (JC-
¼ 8.2 Hz), 133.4, 132.8, 132.3 (JC-P ¼ 9.5 Hz), 132.2 (JC-P ¼ 129.2 Hz),
d
¼ 7.96 (dd, J ¼ 10.8, 8.3 Hz, 4H), 7.84e7.77 (m,
d
4.2.35. N-Diphenylmethyl-P-isopropyl-P-phenyl phosphonamide
(5da)
P
132.1 (JC-P ¼ 2.6 Hz), 128.8 (JC-P ¼ 12.6 Hz), 128.6, 127.9, 127.8, 126.4,
126.3, 126.1, 126.0, 45.0 (ppm). 31P NMR (100 MHz, CDCl3)
¼ 23.9
(ppm). MS (EI): m/z ¼ 77.0 (5), 115.1 (4), 141.1 (9), 156.1 (100), 201.0
White solid (125.7mg, 69% yield). m.p. 148e149 ꢀC. 1H NMR
d
(400 MHz, CDCl3)
d
¼ 7.61 (dd, J ¼ 12.8, 7.6 Hz, 2H), 7.39e7.33 (m,
1H), 7.29e7.22 (m, 2H), 7.20e7.07 (m, 8H), 7.06e7.01 (m, 2H), 5.32
(t, J ¼ 9.9 Hz, 1H), 4.62e4.49 (m, 1H), 3.63e3.49 (m, 1H), 1.19 (d,
J ¼ 6.0 Hz, 3H), 1.00 (d, J ¼ 6.0 Hz, 3H) (ppm). 13C NMR (101 MHz,
(23), 357.0 (28). IR (in KBr):
n
¼ 3665, 2984, 1439, 1269, 1186, 1117,
1068, 756, 698, 555, 519 (cmꢂ1). HRMS (ESI) (m/z)
[C23H20NOP þ Hþ]: Calcd. 358.1361, Found. 358.1365.
CDCl3)
d
¼ 143.5 (JC-P ¼ 4.6 Hz), 143.4 (JC-P ¼ 4.0 Hz), 131.8 (JC-
¼ 174.2 Hz), 131.7 (JC-P ¼ 2.4 Hz), 131.6 (JC-P ¼ 9.8 Hz), 128.5, 128.4,
P
4.2.31. N-(1-Phenylethyl)-P,P-diphenyl phosphinamide (3au)
128.2 (JC-P ¼ 14.3 Hz), 127.2(7), 127.2(5), 127.1(8), 127.1(4), 69.9 (JC-
White solid (99.1 mg, 62% yield). m.p.: 140e141 ꢀC. 1H NMR
¼ 5.9 Hz), 58.8, 24.3 (JC-P ¼ 3.5 Hz), 23.9 (JC-P ¼ 5.1 Hz) (ppm). 31P
P
(400 MHz, CDCl3)
d
¼ 7.83 (dd, J ¼ 11.2, 7.8 Hz, 2H), 7.74 (dd, J ¼ 11.4,
NMR (100 MHz, CDCl3)
d
¼ 19.8 (ppm). MS (EI): m/z ¼ 77.1 (13),
7.9 Hz, 2H), 7.44e7.32 (m, 4H), 7.31e7.13 (m, 7H), 4.38e4.25 (m,
104.1 (14), 106.1 (17), 165.1 (15), 167.1 (16), 182.1 (100), 246.0 (19),
1H), 3.22e3.10 (m, 1H), 1.50 (d, J ¼ 6.7 Hz, 3H) (ppm). 13C NMR
322.0 (85), 365.1 (15). IR (in KBr):
n
¼ 3738, 3208, 1464, 1200, 1124,
(101 MHz, CDCl3)
d
¼ 145.2 (JC-P ¼ 6.8 Hz), 133.4 (JC-P ¼ 106.0 Hz),
978, 934, 802, 747, 699, 552 (cmꢂ1). HRMS (ESI) (m/z)
[C22H24NO2P þ Hþ]: Calcd. 366.1623, Found. 366.1619.
132.5 (JC-P ¼ 9.6 Hz), 132.1 (JC-P ¼ 108.3 Hz), 132.0 (JC-P ¼ 9.6 Hz),
131.9 (JC-P ¼ 3.2 Hz), 131.8 (JC-P ¼ 2.7 Hz), 128.7, 128.6 (JC-P ¼ 8.9 Hz),
128.5 (JC-P ¼ 8.9 Hz), 127.2, 126.0, 51.2, 26.1 (JC-P ¼ 3.2 Hz) (ppm). 31
P
4.2.36. N-Diphenylmethyl-P-n-butyl-P-phenyl phosphonamide
(5ea)
NMR (100 MHz, CDCl3)
d
¼ 22.5 (ppm). MS (EI): m/z ¼ 77.0 (11),
105.0 (9), 120.1 (100), 201.0 (23), 321.1 (8). IR (in KBr):
n
¼ 3667,
White solid (133.4 mg, 70% yield). m.p. 120e121 ꢀC. 1H NMR
2982, 1437, 1269, 1188, 1034, 1113, 962, 754, 696, 550 (cmꢂ1). HRMS
(400 MHz, CDCl3)
d
¼ 7.63 (dd, J ¼ 12.9, 7.6 Hz, 2H), 7.42e7.36 (m,
(ESI) (m/z)[C20H20NOP þ Hþ]: Calcd. 322.1361, Found. 322.1367.
1H), 7.32e7.25 (m, 2H), 7.21e7.08 (m, 8H), 7.06e7.02 (m, 2H), 5.28
(t, J ¼ 9.9 Hz, 1H), 3.93e3.85 (m, 1H), 3.71e3.55 (m, 2H), 1.47e1.35
(m, 2H), 1.23e1.16 (m, 2H), 0.76 (t, J ¼ 7.4 Hz, 3H) (ppm). 13C NMR
4.2.32. N-Diphenylmethyl-P,P-diphenyl phosphinamide (5aa)
White solid (150.1 mg, 78% yield), m.p. 182e183 ꢀC. 1H NMR
(101 MHz, CDCl3)
d
¼ 143.5 (JC-P ¼ 4.0 Hz),143.3 (JC-P ¼ 5.4 Hz),131.8
(400 MHz, CDCl3)
2H), 7.31e7.24 (m, 4H), 7.24e7.12 (m, 10H), 5.37 (t, J ¼ 10.8 Hz, 1H),
3.68e3.55 (m, 1H) (ppm). 13C NMR (101 MHz, CDCl3)
d
¼ 7.75 (dd, J ¼ 11.1, 8.2 Hz, 4H), 7.40e7.34 (m,
(JC-P ¼ 3.0 Hz), 131.6 (JC-P ¼ 9.7 Hz), 131.0 (JC-P ¼ 172.6 Hz), 128.6,
128.5, 128.4 (JC-P ¼ 14.4 Hz), 127.3, 127.2(7), 127.2(1), 64.5 (JC-
d
¼ 143.4 (JC-
¼ 6.0 Hz), 58.9, 32.4 (JC-P ¼ 6.9 Hz), 18.9, 13,7 (ppm). 31P NMR
P
¼ 4.5 Hz), 132.4 (JC-P ¼ 9.6 Hz), 132.3 (JC-P ¼ 129.5 Hz), 132.0 (JC-
(100 MHz, CDCl3)
d
¼ 21.0 (ppm). MS (EI): m/z ¼ 104.0 (5), 141.0 (5),
P
¼ 2.6 Hz), 128.6, 128.5 (JC-P ¼ 14.2 Hz), 127.7, 127.3, 58.6 (ppm). 31
P
167.1 (10),182.1 (100), 246.0 (14), 302.1 (7), 322.0 (36), 379.1 (44). IR
P
NMR (100 MHz, CDCl3)
d
¼ 23.1 (ppm). MS (EI): m/z ¼ 77.0 (9), 104.1
(in KBr):
n
¼ 3187, 1448, 1262, 1204, 1100, 1024, 800, 745, 701, 558
(9),165.1 (10),182.1 (100), 201.0 (31), 383.1 (4). IR (in KBr):
n
¼ 3143,
(cmꢂ1). HRMS (ESI) (m/z)[C23H26NO2P þ Hþ]: Calcd. 380.1779,
2865, 1594, 1447, 1259, 1184, 1112, 935, 803, 696, 539 (cmꢂ1). HRMS
Found. 380.1781.
(ESI) (m/z)[C25H22NOP þ Hþ]: Calcd. 384.1517, Found. 384.1525.
4.2.37. N-Diphenylmethyl-P-cyclohexyl-P-phenyl phosphonamide
(5fa)
4.2.33. N-Diphenylmethyl-P-methyl-P-phenyl phosphonamide
(5ba)
White solid (126.5 mg, 62% yield). m.p. 155e156 ꢀC. 1H NMR
White solid (114.5 mg, 68% yield). m.p. 132e133 ꢀC. 1H NMR
(400 MHz, CDCl3)
d
¼ 7.64 (dd, J ¼ 12.9, 7.7 Hz, 2H), 7.41e7.36 (m,
(400 MHz, CDCl3)
d
¼ 7.71 (dd, J ¼ 12.4, 7.7 Hz, 2H), 7.51e7.45 (m,
1H), 7.32e7.25 (m, 2H), 7.22e7.09 (m, 8H), 7.07e7.01 (m, 2H), 5.35
(t, J ¼ 9.9 Hz, 1H), 4.32e4.22 (m, 1H), 3.36 (t, J ¼ 9.5 Hz, 1H),
1H), 7.41e7.34 (m, 2H), 7.31e7.18 (m, 8H), 7.16e7.10 (m, 2H), 5.37 (t,
J ¼ 9.3 Hz, 1H), 3.69e3.59 (m, 1H), 3.56 (d, J ¼ 10.9 Hz, 3H) (ppm).
1.72e1.65 (m, 1H), 1.62e1.33 (m, 5H), 1.29e1.04 (m, 5H) (ppm). 13
C
13C NMR (101 MHz, CDCl3)
d
¼ 143.4 (JC-P ¼ 4.1 Hz), 143.2 (JC-
NMR (101 MHz, CDCl3)
d
¼ 143.6 (JC-P ¼ 4.8 Hz),143.5 (JC-P ¼ 4.6 Hz),
¼ 5.5 Hz), 132.0 (JC-P ¼ 2.9 Hz), 131.6 (JC-P ¼ 9.8 Hz), 130.4 (JC-
¼ 175.8 Hz), 128.6, 128.5, 128.4 (JC-P ¼ 14.4 Hz), 127.4, 127.3, 127.2,
131.9 (JC-P ¼ 174.3 Hz), 131.7 (JC-P ¼ 3.1 Hz), 131.6 (JC-P ¼ 9.8 Hz),
128.6, 128.5, 128.3 (JC-P ¼ 14.3 Hz), 127.3, 127.2, 74.8 (JC-P ¼ 5.8 Hz),
58.8, 33.9 (JC-P ¼ 3.1 Hz), 33.7 (JC-P ¼ 4.5 Hz), 25.3, 23.7, 23.6 (ppm).
P
P
127.1, 58.8, 51.3 (JC-P ¼ 6.0 Hz) (ppm). 31P NMR (100 MHz, CDCl3)
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J. Xiao et al. / Tetrahedron xxx (2018) 1e11
9
31P NMR (100 MHz, CDCl3)
104.1 (9), 182.1 (100), 223.1 (21), 322.1 (8), 405.2 (11). IR (in KBr):
d
¼ 19.6 (ppm). MS (EI): m/z ¼ 77.0 (7),
(dd, JC-F ¼ 14.6 Hz, JC-P ¼ 7.8 Hz), 115.4 (JC-F ¼ 21.0 Hz), 60.3 (t, JC-
¼ JC-F ¼ 4.8 Hz), 58.9 (ppm). 19F NMR (100 MHz, CDCl3)
¼ ꢂ118.2
d
P
n
¼ 3177, 2931, 1453, 1262, 1207, 1097, 1022, 801, 744, 696, 563
(ppm). 31P NMR (100 MHz, CDCl3)
d
¼ 22.1 (ppm). MS (EI): m/
(cmꢂ1). HRMS (ESI) (m/z)[C25H28NO2P þ Hþ]: Calcd. 406.1936,
z ¼ 91.1 (26), 109.0 (37), 121.0 (34), 161.1 (31), 182.1 (40), 282.1 (38),
Found. 406.1930.
322.0 (100), 431.0 (2). IR (in KBr):
n
¼ 3244, 1494, 1451, 1259, 1200,
1116, 995, 804, 749, 703, 549 (cmꢂ1). HRMS (ESI) (m/z)
[C26H23FNO2P þ Hþ]: Calcd. 432.1529, Found.432.1534.
4.2.38. N-Diphenylmethyl-P-(2-methoxyethyl)-P-phenyl
phosphonamide (5ga)
White solid (133.1 mg, 70% yield). m.p. 112e113 ꢀC. 1H NMR
4.2.42. N-Diphenylmethyl-P-(4-chlorobenzyl)-P-phenyl
phosphonamide (5ka)
(400 MHz, CDCl3)
d
¼ 7.71 (dd, J ¼ 13.1, 7.7 Hz, 2H), 7.48e7.42 (m,
1H), 7.37e7.31 (m, 2H), 7.27e7.16 (m, 10H), 5.45 (t, J ¼ 9.9 Hz, 1H),
White solid (157.4 mg, 70% yield). m.p. 143e144 ꢀC. 1H NMR
4.12e3.98 (m, 2H), 3.96e3.86 (m, 1H), 3.53e3.41 (m, 2H), 3.29 (s,
(400 MHz, CDCl3)
d
¼ 7.72 (dd, J ¼ 13.0, 7.7 Hz, 2H), 7.51e7.45 (m,
3H) (ppm). 13C NMR (101 MHz, CDCl3)
d
¼ 143.4 (JC-P ¼ 3.7 Hz),
1H), 7.40e7.33 (m, 2H), 7.29e7.16 (m, 10H), 7.15e7.09 (m, 2H),
7.08e7.02 (m, 2H), 5.37 (t, J ¼ 10.0 Hz, 1H), 4.98e4.89 (m, 1H),
4.72e4.63 (m, 1H), 4.06e3.93 (m, 1H) (ppm). 13C NMR (101 MHz,
143.3 (JC-P ¼ 4.9 Hz), 131.9 (JC-P ¼ 3.1 Hz), 131.7 (JC-P ¼ 9.9 Hz), 130.8
(JC-P ¼ 176.6 Hz), 128.6, 128.5, 128.3 (JC-P ¼ 14.6 Hz), 127.3, 127.2(6),
127.2(3), 127.2(0), 71.8 (JC-P ¼ 6.2 Hz), 63.5 (JC-P ¼ 6.0 Hz), 58.9, 58.7
CDCl3)
d
¼ 143.3 (JC-P ¼ 3.9 Hz), 143.1 (JC-P ¼ 5.7 Hz), 135.2 (JC-
(ppm). 31P NMR (100 MHz, CDCl3)
d
¼ 22.0 (ppm). MS (EI): m/
¼ 7.7 Hz), 134.0, 132.1 (JC-P ¼ 2.9 Hz), 131.6 (JC-P ¼ 9.9 Hz), 130.3 (JC-
¼ 174.8 Hz), 129.1, 128.7, 128.6, 128.5 (JC-P ¼ 14.6 Hz), 127.4, 127.3,
P
z ¼ 77.1 (5), 104.0 (7), 167.1 (12), 182.1 (100), 199.0 (7), 322.0 (11),
P
381.0 (19). IR (in KBr):
n
¼ 3700, 3227, 1448, 1260, 1202, 1100, 1034,
127.2, 65.2 (JC-P ¼ 5.3 Hz), 58.9 (ppm). 31P NMR (100 MHz, CDCl3)
799, 748, 702, 534 (cmꢂ1). HRMS (ESI) (m/z)[C22H24NO3P þ Hþ]:
d
¼ 22.2 (ppm). MS (EI): m/z ¼ 77.1 (6), 104.1 (9), 125.0 (27), 165.1
Calcd. 382.1572, Found. 382.1576.
(7), 182.1 (32), 322.1 (100), 447.0 (2). IR (in KBr):
n
¼ 3214, 1453,
1199, 1121, 995, 869, 803, 748, 703, 543 (cmꢂ1). HRMS (ESI) (m/z)
[C26H23ClNO2P þ Hþ]: Calcd. 448.1233, Found. 448.1238.
4.2.39. N-Diphenylmethyl-P-(3-chloropropyl)-P-phenyl
phosphonamide (5ha)
White solid (136.7 mg, 68% yield). m.p. 100e101 ꢀC. 1H NMR
4.2.43. N-Diphenylmethyl-P-(4-bromobenzyl)-P-phenyl
phosphonamide (5la)
(400 MHz, CDCl3)
d
¼ 7.64 (dd, J ¼ 12.9, 7.4 Hz, 2H), 7.44e7.39 (m,
1H), 7.35e7.28 (m, 2H), 7.24e7.11 (m, 8H), 7.09e7.04 (m, 2H), 5.31
(t, J ¼ 9.7 Hz, 1H), 4.07e3.96 (m, 1H), 3.87e3.78 (m, 1H), 3.69e3.59
(m, 1H), 3.40 (t, J ¼ 6.4 Hz, 2H), 1.94e1.83 (m, 2H) (ppm). 13C NMR
White solid (171.6 mg, 70% yield). m.p. 156e157 ꢀC. 1H NMR
(400 MHz, CDCl3)
d
¼ 7.72 (dd, J ¼ 13.0, 7.5 Hz, 2H), 7.51e7.46 (m,
1H), 7.41e7.34 (m, 4H), 7.30e7.17 (m, 8H), 7.14e7.08 (m, 2H),
7.02e6.96 (m, 2H), 5.38 (t, J ¼ 9.9 Hz, 1H), 4.97e4.89 (m, 1H),
4.71e4.63 (m, 1H), 3.91e3.79 (m, 1H) (ppm). 13C NMR (101 MHz,
(101 MHz, CDCl3)
d
¼ 143.3 (JC-P ¼ 4.1 Hz), 143.1 (JC-P ¼ 5.6 Hz), 132.1
(JC-P ¼ 3.1 Hz), 131.6 (JC-P ¼ 9.8 Hz), 130.5 (JC-P ¼ 174.2 Hz), 128.7,
128.6, 128.5 (JC-P ¼ 15.3 Hz), 127.4, 127.3(6), 127.3(4), 127.2, 61.4 (JC-
CDCl3)
d
¼ 143.3 (JC-P ¼ 4.2 Hz), 143.1 (JC-P ¼ 5.6 Hz), 135.7 (JC-
¼ 5.6 Hz), 58.9, 41.1, 33.3 (JC-P ¼ 6.7 Hz) (ppm). 31P NMR (100 MHz,
¼ 7.7 Hz), 132.2 (JC-P ¼ 3.1 Hz), 131.7, 131.6 (JC-P ¼ 9.9 Hz), 130.3 (JC-
P
P
CDCl3)
d
¼ 21.7 (ppm). MS (EI): m/z ¼ 77.1 (5), 104.0 (6), 141.0 (8),
¼ 174.8 Hz), 129.4, 128.7, 128.6, 128.5 (JC-P ¼ 14.5 Hz), 127.4,
P
165.1 (9), 182.1 (100), 322.0 (27), 399.0 (26). IR (in KBr):
n
¼ 3180,
127.3(7), 127.3(3), 127.2, 122.2, 65.3 (JC-P ¼ 5.4 Hz), 58.9 (ppm). 31P
2963, 1446, 1262, 1207, 1093, 1024, 804, 694, 562, 528 (cmꢂ1).
HRMS (ESI) (m/z)[C22H23ClNO2P þ Hþ]: Calcd. 400.1233, Found.
400.1230.
NMR (100 MHz, CDCl3)
d
¼ 22.2 (ppm). MS (EI): m/z ¼ 77.1 (5), 104.0
(7), 169.0 (14), 182.1 (27), 322.0 (100), 492.0 (2). IR (in KBr):
n
¼ 3176, 1449, 1262, 1198, 1120, 1006, 805, 749, 697, 555 (cmꢂ1).
HRMS (ESI) (m/z)[C26H23BrNO2P þ Hþ]: Calcd. 492.0728, Found.
4.2.40. N-Diphenylmethyl-P-benzyl-P-phenyl phosphonamide (5ia)
492.0731.
White solid (148.6 mg, 72% yield). m.p. 140e141 ꢀC. 1H NMR
(400 MHz, CDCl3)
1H), 7.37e7.30 (m, 2H), 7.29e7.10 (m, 15H), 5.40 (t, J ¼ 10.0 Hz, 1H),
5.05e4.96 (m, 1H), 4.79e4.69 (m, 1H), 4.06e3.87 (m, 1H) (ppm). 13
NMR (101 MHz, CDCl3)
d
¼ 7.72 (dd, J ¼ 13.0, 7.5 Hz, 2H), 7.48e7.42 (m,
4.2.44. N-(Di-p-tolylmethyl)-P,P-diphenyl phosphinamide (5ab)
White solid (148.5 mg, 72% yield). m.p. 187e188 ꢀC. 1H NMR
C
(400 MHz, CDCl3)
d
¼ 7.84 (dd, J ¼ 11.5, 8.0 Hz, 4H), 7.48e7.42 (m,
d
¼ 143.4 (JC-P ¼ 5.1 Hz), 143.2 (JC-P ¼ 5.6 Hz),
2H), 7.40e7.32 (m, 4H), 7.15 (d, J ¼ 7.5 Hz, 4H), 7.09 (d, J ¼ 7.6 Hz,
136.7 (JC-P ¼ 8.2 Hz), 132.0 (JC-P ¼ 2.9 Hz), 131.7 (JC-P ¼ 9.9 Hz), 130.6
(JC-P ¼ 174.2 Hz), 128.6, 128.5(4), 128.5(0), 128.4 (JC-P ¼ 14.6 Hz),
128.1, 127.8, 127.3(4), 127.2(9), 127.2(2), 66.0 (JC-P ¼ 5.5 Hz), 58.9
4H), 5.38 (t, J ¼ 10.7 Hz, 1H), 3.70e3.57 (m, 1H), 2.32 (s, 6H) (ppm).
13C NMR (101 MHz, CDCl3)
d
¼ 140.7 (JC-P ¼ 4.5 Hz), 136.8, 132.5 (JC-
¼ 129.4 Hz), 132.4 (JC-P ¼ 9.6 Hz), 131.9 (JC-P ¼ 2.6 Hz), 129.2, 128.5
P
(ppm). 31P NMR (100 MHz, CDCl3)
d
¼ 22.0 (ppm). MS (EI): m/
(JC-P ¼ 12.7 Hz), 127.5, 58.2, 21.2 (ppm). 31P NMR (100 MHz, CDCl3)
z ¼ 77.1 (4), 91.1 (23), 104.1 (6), 165.1 (7), 182.1 (30), 322.1 (100),
d
¼ 22.9 (ppm). MS (EI): m/z ¼ 77.1 (4), 91.1 (3), 118.1 (7), 165.1 (4),
413.0 (2). IR (in KBr):
n
¼ 3184, 1454, 1203, 1124,1008, 987, 805, 752,
201.0 (16), 210.1 (100), 320.1 (2), 411.1 (3). IR (in KBr):
n
¼ 3152,
700, 547 (cmꢂ1). HRMS (ESI) (m/z)[C26H24NO2P þ Hþ]: Calcd.
2870, 1445, 1181, 1112, 1070, 941, 747, 701, 553 (cmꢂ1). HRMS (ESI)
414.1623, Found. 414.1621.
(m/z)[C27H26NOP þ Hþ]: Calcd. 412.1830, Found. 412.1834.
4.2.41. N-Diphenylmethyl-P-(2-fluorobenzyl)-P-phenyl
phosphonamide (5ja)
4.2.45. N-(Di-4-methoxyphenylmethyl)-P,P-diphenyl
phosphinamide (5ac)
White solid (161.3 mg, 75% yield). m.p. 138e139 ꢀC. 1H NMR
White solid (151.6 mg, 68% yield). m.p.: 224e225 ꢀC. 1H NMR
(400 MHz, CDCl3)
d
¼ 7.66 (dd, J ¼ 13.0, 7.5 Hz, 2H), 7.44e7.38 (m,
(400 MHz, CDCl3)
d
¼ 7.83 (dd, J ¼ 11.8, 7.7 Hz, 4H), 7.48e7.42 (m,
1H), 7.34e7.26 (m, 2H), 7.24e7.11 (m, 10H), 7.10e7.05 (m, 2H),
7.01e6.91 (m, 2H), 5.39 (t, J ¼ 9.8 Hz,1H), 5.04e4.96 (m, 1H),
4.87e4.79 (m, 1H), 3.55e3.46 (m, 1H)(ppm). 13C NMR (101 MHz,
2H), 7.40e7.33 (m, 4H), 7.17 (d, J ¼ 8.2 Hz, 4H), 6.82 (d, J ¼ 8.2 Hz,
4H), 5.37 (t, J ¼ 10.6 Hz, 1H), 3.78 (s, 6H), 3.62e3.53 (m, 1H) (ppm).
13C NMR (101 MHz, CDCl3)
d
¼ 158.7, 136.0 (JC-P ¼ 4.6 Hz), 132.5 (JC-
CDCl3)
d
¼ 160.7 (JC-F ¼ 248.2 Hz), 143.3 (JC-P ¼ 4.4 Hz), 143.1 (JC-
¼ 129.0 Hz), 132.4 (JC-P ¼ 9.6 Hz), 132.0 (JC-P ¼ 2.6 Hz), 128.8, 128.5
P
¼ 5.5 Hz), 132.1 (JC-P ¼ 2.9 Hz), 131.6 (JC-P ¼ 10.0 Hz), 130.4 (JC-
¼ 175.0 Hz), 130.1 (JC-F ¼ 3.9 Hz), 130.0 (JC-F ¼ 8.2 Hz), 128.7, 128.6,
(JC-P ¼ 12.6 Hz), 113.9, 57.6, 55.4 (ppm). 31P NMR (100 MHz, CDCl3)
P
d
¼ 23.0 (ppm). MS (EI): m/z ¼ 77.1 (3), 134.1 (4), 201.0 (10), 242.0
P
128.5 (JC-P ¼ 14.5 Hz), 127.4, 127.3, 127.2, 124.2 (JC-F ¼ 3.7 Hz), 124.0
(100), 443.1 (3). IR (in KBr):
n
¼ 3697, 3143, 1772, 1506, 1447, 1247,
Please cite this article in press as: J. Xiao, et al., Cobalt-catalyzed oxidative arylmethylation of phosphorylamides, Tetrahedron (2018), https://
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10
J. Xiao et al. / Tetrahedron xxx (2018) 1e11
1187, 1118, 1024, 699, 554 (cmꢂ1). HRMS (ESI) (m/z)
[C27H26NO3P þ Hþ]: Calcd. 444.1729, Found. 444.1727.
(17), 320.1 (2), 397.1 (4). IR (in KBr):
n
¼ 3147, 2870, 1447, 1184, 1115,
1068, 930, 740, 701, 554 (cmꢂ1). HRMS (ESI) (m/z)
[C26H24NOP þ Hþ]: Calcd. 398.1674, Found. 398.1669.
4.2.46. N-(Di-(4-fluorophenyl)methyl)-P,P-diphenyl
phosphinamide (5ad)
4.2.50. N-((4-Methoxyphenyl)(phenyl)methyl)-P,P-diphenyl
phosphinamide (5ah)
White solid (136.0 mg, 65% yield). m.p. 183e184 ꢀC. 1H NMR
(400 MHz, CDCl3)
d
¼ 7.87e7.76 (m, 4H), 7.51e7.45 (m,
White solid (133.7 mg, 65% yield). m.p. 163e164 ꢀC. 1H NMR
2H),7.43e7.34 (m, 4H), 7.25e7.18 (m, 4H), 6.98 (t, J ¼ 8.0 Hz, 4H),
(400 MHz, CDCl3)
d
¼ 7.88e7.78 (m, 4H), 7.49e7.42 (m, 2H),
5.44 (t, J ¼ 10.7 Hz, 1H), 3.60e3.51 (m, 1H) (ppm). 13C NMR
7.40e7.33 (m, 4H), 7.31e7.22 (m, 5H), 7.17 (d, J ¼ 8.5 Hz, 2H), 6.82 (d,
J ¼ 10.7 Hz, 2H), 5.42 (t, J ¼ 10.7 Hz, 1H), 3.78 (s, 3H), 3.58 (dd,
(101 MHz, CDCl3)
d
¼ 162.0 (JC-F ¼ 246.3 Hz), 139.0 (t, JC-P ¼ JC-
¼ 3.5 Hz), 132.3 (JC-P ¼ 9.7 Hz), 132.1(4) (JC-P ¼ 129.2 Hz), 132.1(2)
J ¼ 9.7, 6.6 Hz, 1H) (ppm). 13C NMR (101 MHz, CDCl3)
d
¼ 158.8,
F
(JC-P ¼ 2.5 Hz), 129.4 (JC-F ¼ 8.1 Hz), 128.6 (JC-P ¼ 12.7 Hz), 115.5 (JC-
143.7 (JC-P ¼ 4.6 Hz), 135.8 (JC-P ¼ 4.5 Hz), 132.6 (JC-P ¼ 129.3 Hz),
132.4(4) (JC-P ¼ 9.7 Hz), 132.4(3) (JC-P ¼ 129.7 Hz), 132.3(9) (JC-
¼ 21.4 Hz), 57.4 (ppm). 19F NMR (100 MHz, CDCl3)
d
¼ ꢂ115.2
F
(ppm). 31P NMR (100 MHz, CDCl3)
d
¼ 23.3 (ppm). MS (EI): m/
¼ 9.6 Hz), 132.0 (JC-P ¼ 2.8 Hz), 128.9, 128.6, 128.5 (JC-P ¼ 12.1 Hz),
P
z ¼ 77.1 (4), 95.0 (3), 122.0 (6), 155.1 (4), 183.0 (7), 201.0 (24), 218.1
127.6, 127.3, 114.0, 58.1, 55.4 (ppm). 31P NMR (100 MHz, CDCl3)
(100), 419.1 (4). IR (in KBr):
n
¼ 3143, 1498, 1445, 1184, 1119, 1075,
d
¼ 23.0 (ppm). MS (EI): m/z ¼ 77.1 (6), 104.0 (5), 134.1 (3), 201.0
1023, 918, 697, 553 (cmꢂ1). HRMS (ESI) (m/z)[C25H20F2NOP þ Hþ]:
(19), 212.1 (100), 413.1 (4). IR (in KBr):
n
¼ 3142, 1775, 1600, 1449,
Calcd. 420.1329, Found. 420.1323.
1260, 1190, 1118, 1022, 701, 555 (cmꢂ1). HRMS (ESI) (m/z)
[C26H24NO2P þ Hþ]: Calcd. 414.1623, Found. 414.1618.
4.2.47. N-(Phenyl(o-tolyl)methyl)-P,P-diphenyl phosphinamide
(5ae)
4.2.51. N-((4-Fluorophenyl)(phenyl)methyl)-P,P-diphenyl
phosphinamide (5ai)
White solid (138.9 mg, 70% yield). m.p. 200e201 ꢀC. 1H NMR
(400 MHz, CDCl3)
d
¼ 7.96e7.88 (m, 2H), 7.85e7.77 (m, 2H),
White solid (126.8 mg, 63% yield). m.p. 189e190 ꢀC. 1H NMR
7.53e7.40 (m, 5H), 7.36e7.25 (m, 7H), 7.25e7.18 (m, 2H), 7.11e7.06
(m, 1H), 5.62 (t, J ¼ 11.0 Hz,1H), 3.71e3.61 (m, 1H), 1.91 (s, 3H)
(400 MHz, CDCl3)
d
¼ 7.82 (dd, J ¼ 11.8, 7.7 Hz, 4H), 7.50e7.44 (m,
2H), 7.41e7.34 (m, 4H), 7.33e7.28 (m, 2H), 7.28e7.21 (m, 5H), 6.96
(t, J ¼ 8.0 Hz, 2H), 5.44 (t, J ¼ 10.7 Hz, 1H), 3.67e3.57 (m, 1H) (ppm).
(ppm). 13C NMR (101 MHz, CDCl3)
d
¼ 143.0 (JC-P ¼ 4.0 Hz), 141.2 (JC-
¼ 4.5 Hz), 135.4, 132.7 (JC-P ¼ 129.2 Hz), 132.6 (JC-P ¼ 9.7 Hz), 132.1
13C NMR (101 MHz, CDCl3)
d
¼ 162.0 (JC-F ¼ 245.9 Hz), 143.2 (JC-
P
(JC-P ¼ 9.4 Hz), 132.0 (JC-P ¼ 2.5 Hz), 131.9 (JC-P ¼ 2.7 Hz), 131.8 (JC-
¼ 4.7 Hz), 139.3 (t, JC-P ¼ JC-F ¼ 3.3 Hz), 132.3(8) (JC-P ¼ 13.3 Hz),
P
¼ 131.4 Hz), 130.6, 128.7, 128.6 (JC-P ¼ 12.6 Hz), 128.4 (JC-
132.3(5) (JC-P ¼ 128.8 Hz), 132.2(9) (JC-P ¼ 13.3 Hz), 132.1(2) (JC-
P
¼ 12.7 Hz), 127.9, 127.3, 127.0, 126.4, 55.2, 19.3 (ppm). 31P NMR
¼ 128.9 Hz), 132.0(6), 129.4 (JC-F ¼ 8.1 Hz), 128.7, 128.6 (JC-
P
P
(100 MHz, CDCl3)
d
¼ 23.1 (ppm). MS (EI): m/z ¼ 77.1 (8), 104.0 (6),
¼ 12.7 Hz), 127.6, 127.5, 115.3 (JC-F ¼ 21.4 Hz), 58.0 (ppm). 19F NMR
P
165.1 (11), 179.1 (18), 196.1 (100), 201.0 (38), 218.0 (18), 306.1 (6),
(100 MHz, CDCl3)
d
¼ ꢂ115.5 (ppm). 31P NMR (100 MHz, CDCl3)
397.0 (8). IR (in KBr):
n
¼ 3148, 2874, 1445, 1189, 1117, 1067, 936, 741,
d
¼ 23.2 (ppm). MS (EI): m/z ¼ 77.1 (4), 122.0 (3), 165.1 (3), 183.0 (7),
696, 550 (cmꢂ1). HRMS (ESI) (m/z)[C26H24NOP þ Hþ]: Calcd.
200.1 (100), 201.0 (31), 401.1 (4). IR (in KBr):
n
¼ 3148, 1500, 1444,
398.1674, Found. 398.1669.
1184, 1120, 1071, 1024, 818, 700, 556 (cmꢂ1). HRMS (ESI) (m/z)
[C25H21FNOP þ Hþ]: Calcd. 402.1423, Found. 402.1427.
4.2.48. N-(Phenyl(m-tolyl)methyl)-P,P-diphenyl phosphinamide
(5af)
4.2.52. N-((4-Chlorophenyl)(phenyl)methyl)-P,P-diphenyl
phosphinamide (5aj)
White solid (140.3 mg, 71% yield). m.p. 158e159 ꢀC. 1H NMR
(400 MHz, CDCl3)
d
¼ 7.88e7.78 (m, 4H), 7.49e7.43 (m, 2H),
White solid (139.4 mg, 67% yield). m.p. 170e171 ꢀC. 1H NMR
7.40e7.34 (m, 4H), 7.31e7.26 (m, 4H), 7.24e7.16 (m, 2H), 7.10e6.99
(m, 3H), 5.42 (t, J ¼ 10.7 Hz, 1H), 3.70e3.58 (m, 1H), 2.28 (s, 3H)
(400 MHz, CDCl3)
7.39e7.32 (m, 4H), 7.32e7.18 (m, 9H), 5.41 (t, J ¼ 10.7 Hz, 1H),
3.86e3.73 (m, 1H) (ppm). 13C NMR (101 MHz, CDCl3)
¼ 143.0 (JC-
d
¼ 7.86e7.75 (m, 4H), 7.48e7.42 (m, 2H),
(ppm). 13C NMR (101 MHz, CDCl3)
d
¼ 143.5 (JC-P ¼ 4.5 Hz), 143.4 (JC-
d
¼ 4.6 Hz), 138.2, 132.4(4) (JC-P ¼ 129.2 Hz), 132.4(3) (JC-P ¼ 9.5 Hz),
¼ 5.1 Hz), 142.0 (JC-P ¼ 4.0 Hz), 133.1, 132.3(6) (JC-P ¼ 13.5 Hz),
P
P
132.3(8) (JC-P ¼ 129.5 Hz), 132.3(5) (JC-P ¼ 9.5 Hz), 132.0 (JC-
132.2(9) (JC-P ¼ 129.1 Hz), 132.2(6) (JC-P ¼ 13.4 Hz), 132.0(7) (JC-
¼ 2.7 Hz), 128.6, 128.5(0) (JC-P ¼ 12.3 Hz), 128.4(6) (JC-P ¼ 11.2 Hz),
¼ 129.3 Hz), 132.05, 129.2, 128.7, 128.6, 128.5 (JC-P ¼ 12.8 Hz),
P
P
128.4(3), 128.1, 127.6, 127.2, 124.7, 58.7, 21.6 (ppm). 31P NMR
127.6, 127.5, 58.1 (ppm). 31P NMR (100 MHz, CDCl3)
d
¼ 23.3 (ppm).
(100 MHz, CDCl3)
165.1 (9), 196.1 (100), 201.0 (28), 306.1(3), 320.1 (3), 397.0 (5). IR (in
d
¼ 23.2 (ppm). MS (EI): m/z ¼ 77.1 (6), 104.0 (6),
MS (EI): m/z ¼ 77.1 (6), 104.1 (3), 138.1 (3), 165.1 (10), 201.0 (27),
216.0 (100), 417.1 (6). IR (in KBr):
n
¼ 3152, 1452, 1200, 1123, 939,
KBr):
n
¼ 3150, 2870, 1445, 1192, 1116, 1069, 934, 748, 700, 555
872, 801, 742, 697, 555 (cmꢂ1). HRMS (ESI) (m/z)
[C25H21ClNOP þ Hþ]: Calcd. 418.1128, Found. 418.1134.
(cmꢂ1). HRMS (ESI) (m/z)[C26H24NOP þ Hþ]: Calcd. 398.1674,
Found. 398.1677.
4.2.53. N-((4-Bromophenyl)(phenyl)methyl)-P,P-diphenyl
phosphinamide (5ak)
4.2.49. N-(Phenyl(p-tolyl)methyl)-P,P-diphenyl phosphinamide
(5ag)
White solid (149.3 mg, 65% yield). m.p. 192e193 ꢀC. 1H NMR
White solid (145.5 mg, 73% yield). m.p. 177e178 ꢀC. 1H NMR
(400 MHz, CDCl3)
d
¼ 7.87e7.76 (m, 4H), 7.50e7.44 (m, 2H),
(400 MHz, CDCl3)
d
¼ 7.88e7.78 (m, 4H), 7.48e7.42 (m, 2H),
7.43e7.34 (m, 6H), 7.33e7.28 (m, 2H), 7.27e7.21 (m, 3H), 7.15 (d,
7.40e7.32 (m, 4H), 7.30e7.20 (m, 5H), 7.17e7.12 (m, 2H), 7.12e7.06
(m, 2H), 5.42 (t, J ¼ 10.8 Hz, 1H), 3.61 (dd, J ¼ 10.0, 6.7 Hz, 1H), 2.31
J ¼ 7.7 Hz, 2H), 5.41 (t, J ¼ 10.7 Hz,1H), 3.70e3.58 (m, 1H) (ppm). 13
C
NMR (101 MHz, CDCl3)
d
¼ 142.9 (JC-P ¼ 4.9 Hz),142.5 (JC-P ¼ 3.9 Hz),
(s, 3H) (ppm). 13C NMR (101 MHz, CDCl3)
d
¼ 143.6 (JC-P ¼ 4.6 Hz),
132.4 (JC-P ¼ 13.4 Hz), 132.3(0) (JC-P ¼ 13.4 Hz), 132.2(9) (JC-
140.6 (JC-P ¼ 4.6 Hz), 137.0, 132.5(2) (JC-P ¼ 129.4 Hz), 132.5(0) (JC-
¼ 127.7 Hz), 132.1(4), 132.0(8) (JC-P ¼ 129.6 Hz), 131.7, 129.5, 128.8,
P
¼ 129.5 Hz), 132.4 (JC-P ¼ 9.7 Hz), 132.0 (JC-P ¼ 2.6 Hz), 129.3,
128.6 (JC-P ¼ 12.7 Hz), 127.6, 121.3, 58.2 (ppm). 31P NMR (100 MHz,
P
128.5(6), 128.5(2) (JC-P ¼ 12.5 Hz), 128.5(0) (JC-P ¼ 11.6 Hz), 127.7,
CDCl3)
d
¼ 23.2 (ppm). MS (EI): m/z ¼ 77.1 (3), 165.1 (11), 201.0 (29),
127.6, 127.2, 58.4, 21.2 (ppm). 31P NMR (100 MHz, CDCl3)
d
¼ 23.0
260.0 (100), 308.0 (8), 461.0 (5). IR (in KBr):
n
¼ 3150, 1453, 1205,
(ppm). MS (EI): m/z ¼ 77.1 (4), 104.1 (3), 165.1 (6), 196.1 (100), 201.0
1102, 998, 937, 807, 746, 692, 554 (cmꢂ1). HRMS (ESI) (m/z)
Please cite this article in press as: J. Xiao, et al., Cobalt-catalyzed oxidative arylmethylation of phosphorylamides, Tetrahedron (2018), https://
doi.org/10.1016/j.tet.2018.07.006

J. Xiao et al. / Tetrahedron xxx (2018) 1e11
11
[C25H21BrNOP þ Hþ]: Calcd. 462.0622, Found. 462.0615.
(e) A. Mucha, A. Kunert, J. Grembecka, M. Pawełczak, P. Kafarski, Eur. J. Med.
Chem. 41 (2006) 768e772;
(f) B. Li, B. Zhou, H. Lu, L. Ma, A.-Y. Peng, Eur. J. Med. Chem. 45 (2010)
1955e1963;
(g) G.F. Ruda, P.E. Wong, V.P. Alibu, S. Norval, K.D. Read, M.P. Barrett,
I.H. Gilbert, J. Med. Chem. 53 (2010) 6071e6078.
4.2.54. N-((Phenyl)(4-trifluoromethylphenyl)methyl)-P,P-diphenyl
phosphinamide (5al)
White solid (131.1 mg, 58% yield). m.p. 199e200 ꢀC. 1H NMR
[3] (a) L. Liu, A.-A. Zhang, Y. Wang, F. Zhang, Z. Zuo, W.-X. Zhao, C.-L. Feng, W. Ma,
Org. Lett. 17 (2015) 2046e2049;
(400 MHz, CDCl3)
7.50e7.44 (m, 2H), 7.43e7.20 (m, 11H), 5.50 (t, J ¼ 10.6 Hz, 1H),
3.76e3.67 (m, 1H) (ppm). 13C NMR (101 MHz, CDCl3)
¼ 147.3 (JC-
d
¼ 7.88e7.75 (m, 4H), 7.56e7.51 (m, 2H),
(b) Z.S. Han, L. Zhang, Y. Xu, J.D. Sieber, M.A. Marsini, Z. Li, J.T. Reeves,
K.R. Fandrick, N.D. Patel, J.-N. Desrosiers, B. Qu, A. Chen, D.M. Rudzinski,
L.P. Samankumara, S. Ma, N. Grinberg, F. Roschangar, N.K. Yee, G. Wang,
J.J. Song, C.H. Senanayake, Angew. Chem. Int. Ed. 54 (2015) 5474e5477;
d
¼ 3.3 Hz), 142.6 (JC-P ¼ 4.9 Hz), 132.4 (JC-P ¼ 9.7 Hz), 132.2(6),
P
ꢀ
132.2(4) (JC-P ¼ 9.8 Hz), 132.2(0) (JC-P ¼ 128.6 Hz), 132.0 (JC-
(c) L. Copey, L. Jean-Gerard, E. Framery, G. Pilet, V. Robert, B. Andrioletti, Chem.
Eur. J. 21 (2015) 9057e9061;
¼ 129.5 Hz), 128.9, 128.7 (JC-P ¼ 12.7 Hz), 128.6 (JC-P ¼ 12.7 Hz),
P
(d) L. Wang, Z. Du, Q. Wu, R. Jin, Z. Bian, C. Kang, H. Guo, X. Ma, L. Gao, Eur. J.
Org. Chem. 2016 (2016) 2024 and the citations therein.
[4] (a) W. Tang, Y.-X. Ding, J. Org. Chem. 71 (2006) 8489e8492;
(b) S. Park, B. Seo, S. Shin, J.-Y. Son, P.H. Lee, Chem. Commun. 49 (2013)
8671e8673;
(c) Y.R. Kim, S. Cho, P.H. Lee, Org. Lett. 16 (2014) 3098e3101;
(d) T.T. Nguyen, L. Grigorjeva, O. Daugulis, ACS Catal. 6 (2015) 551e554.
[5] J. Li, S.L. Zhang, C.Z. Tao, Y. Fu, Q.X. Guo, Chin. Chem. Lett. 18 (2007)
1033e1036.
128.1, 127.8, 127.6, 125.6 (q, JC-F ¼ 3.7 Hz), 58.4 (ppm). 19F NMR
(100 MHz, CDCl3)
d
¼ ꢂ62.5 (ppm). 31P NMR (100 MHz, CDCl3)
d
¼ 23.4 (ppm). MS (EI): m/z ¼ 77.1 (4), 165.1 (4), 201.0 (20), 250.0
(100), 451.0 (5). IR (in KBr):
n
¼ 3149, 2890, 1447, 1302, 1192, 1026,
920, 801, 745, 698, 556 (cmꢂ1). HRMS (ESI) (m/z)
[C26H21F3NOP þ Hþ]: Calcd. 452.1391, Found. 452.1396.
[6] (a) I. Wilkening, G.D. Signore, C.P.R. Hackenberger, Chem. Commun. 47 (2011)
349e351;
4.2.55. N-((4-Fluorophenyl)(p-tolyl)methyl)-P,P-diphenyl
phosphinamide (5am)
(b) N.M. Neisius, M. Lutz, D. Rentsch, P. Hemberger, S. Gaan, Ind. Eng. Chem.
Res. 53 (2014) 2889e2896;
(c) S. Gaan, S. Liang, H. Mispreuve, H. Perler, R. Naescher, M. Neisius, Polym.
Degrad. Stabil. 113 (2015) 180e188.
White solid (146.2 mg, 70% yield). m.p. 180e181 ꢀC. 1H NMR
(400 MHz, CDCl3)
d
¼ 7.88e7.78 (m, 4H),7.51e7.43 (m,
€
€
[7] R.I. Olsson, I. Jacobson, J. Bostrom, T. Fex, A. Bjore, C. Olsson, J. Sundell, U. Gran,
2H),7.42e7.34 (m, 4H), 7.26e7.21 (m, 2H), 7.12 (bs, 4H), 6.96 (t,
J ¼ 8.0 Hz, 2H), 5.41 (t, J ¼ 10.6 Hz, 1H), 3.59e3.51 (m, 1H), 2.33 (s,
€
A. Ohrn, A. Nordin, J. Gyll, M. Thorstensson, A. Hayen, K. Aplander, O. Hidestål,
F. Jiang, G. Linhardt, E. Forsstrom, T. Collins, M. Sundqvist, E. Lindhardt,
A. Åstrand, B. Lofberg, Bioorg. Med. Chem. Lett. 23 (2013) 706e710.
€
3H) (ppm). 13C NMR (101 MHz, CDCl3)
d
¼ 162.0 (JC-F ¼ 245.7 Hz),
€
140.4 (JC-P ¼ 5.2 Hz), 139.4 (t, JC-P ¼ JC-F ¼ 3.6 Hz), 137.2, 132.4(3) (JC-
[8] L. Zhong, Q. Su, J. Xiao, Z. Peng, W. Dong, Y. Zhang, D. An, Asian J. Org. Chem. 6
(2017) 1072e1079.
[9] J. Xiao, Q. Su, W. Dong, Z. Peng, Y. Zhang, D. An, J. Org. Chem. 82 (2017)
9497e9504.
¼ 129.5 Hz), 132.3(9) (JC-P ¼ 14.0 Hz), 132.3(0) (JC-P ¼ 13.9 Hz),
P
132.2(1) (JC-P ¼ 129.3 Hz), 132.0(3) (JC-P ¼ 2.4 Hz), 132.0(1) (JC-
¼ 2.4 Hz), 129.3(8), 129.3(6) (JC-F ¼ 7.9 Hz), 128.6 (JC-P ¼ 12.7 Hz),
[10] (a) C. Shen, G. Yang, W. Zhang, Org. Lett. 15 (2013) 5722e5725;
P
ꢀ
ꢀ
ꢀ
(b) M.A. del Aguila-Sanchez, Y. Navarro, J. García-Lopez, G.P. Guedes, F.L. Ortiz,
Dalton Trans. 45 (2016) 2008e2022.
128.5 (JC-P ¼ 12.6 Hz), 127.5, 115.3 (JC-F ¼ 21.4 Hz), 57.8, 21.2 (ppm).
19F NMR (100 MHz, CDCl3)
d
¼ ꢂ115.7 (ppm). 31P NMR (100 MHz,
[11] (a) W.C. Smith, L.F. Audrieth, J. Org. Chem. 22 (1957) 265e267;
(b) M.F. Hersman, L.F. Audrieth, J. Org. Chem. 23 (1958) 1889e1893;
(c) G. Oliva, E.E. Castellano, L.R.F. de Carvalho, Acta Crystallogr. Sect. B Struct.
Crystallogr. Cryst. Chem. 37 (1981) 474e475.
[12] J.D. Weaver, A. Recio, A.J. Grenning, J.A. Tunge, Chem. Rev. 111 (2011)
1846e1913.
[13] (a) A.M. Voutchkova, R.H. Crabtree, J. Mol. Catal. A Chem. 312 (2009) 1e6;
(b) R. Vanjari, T. Guntreddi, K.N. Singh, Org. Lett. 15 (2013) 4908e4911;
(c) K. Azizi, M. Karimi, A. Heydari, RSC Adv. 4 (2014) 31817e31820;
(d) S.S. Kotha, S. Badigenchala, G. Sekar, Adv. Synth. Catal. 357 (2015)
1437e1445;
CDCl3)
d
¼ 23.1 (ppm). MS (EI): m/z ¼ 77.1 (4), 122.0 (5), 155.1 (3),
183.0 (7), 201.0 (17), 214.1 (100), 415.1 (3). IR (in KBr):
n
¼ 3149,
1506, 1445, 1181, 1117, 1071, 1021, 724, 694, 554 (cmꢂ1). HRMS (ESI)
(m/z) [C26H23FNOP þ Hþ]: Calcd. 416.1580, Found. 416.1577.
Acknowledgments
The authors are grateful for the financial support from the the
Natural Science Foundation of Hunan Province (No. 2017JJ3027),
the Fundamental Research Funds for Hunan University (No.
531107040840).
(e) M. Karimi, D. Saberi, K. Azizi, E. Ghonchepour, A. Heydari, Tetrahedron Lett.
56 (2015) 2674e2677;
(f) E. Eidi, M.Z. Kassaee, RSC Adv. 6 (2016) 106873e106879;
(g) N.C. Thacker, P. Ji, Z. Lin, A. Urban, W. Lin, Faraday Discuss 201 (2017)
303e315;
(h) Y. Yang, J. Gu, Z. Fang, Z. Yang, P. Wei, K. Guo, RSC Adv. 7 (2017)
22797e22801.
Appendix A. Supplementary data
[14] (a) Z. Wang, Y. Zhang, H. Fu, Y. Jiang, Y. Zhao, Org. Lett. 10 (2008) 1863e1866;
(b) X. Liu, Y. Zhang, L. Wang, H. Fu, Y. Jiang, Y. Zhao, J. Org. Chem. 73 (2008)
6207e6212;
Supplementary data related to this article can be found at
https://doi.org/10.1016/j.tet.2018.07.006.
(c) Y.-H. Ye, J. Zhang, G. Wang, S.-Y. Chen, X.-Q. Yu, Tetrahedron 67 (2011)
4649e4654;
(d) Y. Zhang, B. Feng, C. Zhu, Org. Biomol. Chem. 10 (2012) 9137e9141;
(e) H.-T. Zeng, J.-M. Huang, Org. Lett. 17 (2015) 4276e4279;
(f) Y. Zhang, J. Dong, L. Liu, L. Liu, Y. Zhou, S.-F. Yin, Org. Biomol. Chem. 15
(2017) 2897e2901.
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Please cite this article in press as: J. Xiao, et al., Cobalt-catalyzed oxidative arylmethylation of phosphorylamides, Tetrahedron (2018), https://
doi.org/10.1016/j.tet.2018.07.006