Metal-free oxidative arylphosphination of activated N-substituted-N- arylacrylamide derivatives using K2S2O8

Article abstract of DOI:10.1016/j.tet.2014.01.065

A novel metal-free oxidative arylphosphination of activated N-substituted-N-arylacrylamide derivatives by phosphorylation and C-H functionalization cascade process has been developed. This methodology provides an efficient way to construct a variety of phosphorus-containing oxindole moieties.

Full text of DOI:10.1016/j.tet.2014.01.065

Tetrahedron 70 (2014) 1991e1996
Contents lists available at ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
Metal-free oxidative arylphosphination of activated N-substituted-
N-arylacrylamide derivatives using K2S2O8
,
a
a
b
Ya-Min Li a , Yuehai Shen , Kwen-Jen Chang , Shang-Dong Yang
*
a Faculty of Life Science and Technology, Kunming University of Science and Technology, 727 Jingming Nanlu, Kunming 650500, China
b State Key Laboratory of Applied Organic Chemistry, Lanzhou University, 222 Tianshui Nanlu, Lanzhou 730000, China
a r t i c l e i n f o
a b s t r a c t
Article history:
A novel metal-free oxidative arylphosphination of activated N-substituted-N-arylacrylamide derivatives
by phosphorylation and CeH functionalization cascade process has been developed. This methodology
provides an efficient way to construct a variety of phosphorus-containing oxindole moieties.
Ó 2014 Elsevier Ltd. All rights reserved.
Received 25 November 2013
Received in revised form 20 January 2014
Accepted 27 January 2014
Available online 31 January 2014
Keywords:
Arylphosphination
Oxindole
Difunctionalization
Activated alkenes
Metal-free
1. Introduction
provided a new entry to more valuable phosphorus-containing
oxindoles with high atom economy and high efficiency. We envis-
Organophosphorus compounds can be found in a wide range of
medicinal chemistry, biochemistry, photoelectric materials, catal-
ysis, and organic synthesis.1 Therefore, the development of new
and efficient CeP bond-forming method for the construction of
phosphorus compounds that are not readily available by classic
methods is urgent and very important.2 A great deal of recent effort
has focused on two general strategies: (1) transition-metal-
catalyzed coupling reactions3 and (2) alkenes or alkynes function-
alization.4 For the latter, up to now, most of the transformations
were focussed on the simple addition reactions, while less work
was reported on the phosphorus-containing difunctionalization of
alkenes,5 although the difunctionalization may offer more envi-
ronmentally benign and atom-economical processes.
aged that this transformation might be accomplished by more
simple oxidant-promoted radical cyclization. Herein we report
a metal-free K2S2O8-mediated oxidative arylphosphination of ac-
tivated alkenes to form phosphorus-containing oxindoles by using
readily available diphenylphosphine oxide as coupling partners
(Scheme 1). Over the past several years, the development of
transition-metal-free processes has become a topic of great interest
in chemical synthesis.9 Such protocols are very valuable as an at-
tractive alternative and beneficial complements for transition-
metal-catalyzed transformations. In particular, from a practical
aspect, metal-free syntheses are preferred, as the removal of metal
contamination can render a process quite expensive.
Difunctionalization of alkenes is among the most powerful
transformation in organic synthesis.6 The catalytic difunctionali-
zation of acrylamides via direct CeH bond functionalization has
attracted much attention in the past few years and has been applied
successfully for the synthesis of various functionalized oxindoles.7
In particular, metal-free oxidative coupling/cyclization reactions
were also discovered.8 Very recently, we reported a novel silver-
catalyzed oxidative arylphosphination of alkenes.5b This approach
Scheme 1. Arylphosphination of alkenes.
2. Results and discussions
We initiated our study on the reaction of N-methyl-N-phenyl-
methacrylamide (1a) with HP(O)Ph2 and an oxidant in CH3CN at
* Corresponding author. Tel.: þ86 871 65920747; fax: þ86 871 65920570; e-mail
address: liym@kmust.edu.cn (Y.-M. Li).
0040-4020/$ e see front matter Ó 2014 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.tet.2014.01.065

1992
Y.-M. Li et al. / Tetrahedron 70 (2014) 1991e1996
80 ꢀC. To our delight, the desired product 2a was obtained in 58%
yield when the reaction employed 2.0 equiv K2S2O8 (Table 1, entry
1). With regard to the optimal amount of the oxidant, the reaction
with 3.0 equiv K2S2O8 provided the best results (entries 2e3). The
concentration of substrate 1a was important. Decreasing the con-
centration of 1a from 0.1 M to 0.067 M, the yield of 2a improved to
88% (entry 2 vs entry 4). Further decreasing the substrate concen-
tration resulted in a decrease in yield (entry 5). Subsequently, dif-
ferent solvents, CH3CN, toluene, DMF, DMSO, and NMP were
screened, and among them CH3CN exhibited unmatched efficacy
for the transformation (entry 4 vs entries 6e10). Among the re-
action temperatures examined, it turned out that the reaction at
90 ꢀC gave the best results (entries 11e13). Finally, a series of oxi-
dants, such as oxone, benzoyl peroxide (BPO), tert-butyl perox-
ybenzoate (TBPB), tert-butyl hydroperoxide (TBHP, anhydrous,
about 5.5 M in decane), and di-tert-butyl peroxide (DTBP), were
examined, and K2S2O8 was found to be the best choice (entry 4
vs entries 14e18).
Table 2
Scope of arylphosphinationa,b
Table 1
Optimization of reaction conditionsa
Entry
Oxidant (equiv)
Temp (ꢀC)
Solvent
Yieldb (%)
1c
2c
3c
4
K2S2O8 (2)
K2S2O8 (3)
K2S2O8 (4)
K2S2O8 (3)
K2S2O8 (3)
K2S2O8 (3)
K2S2O8 (3)
K2S2O8 (3)
K2S2O8 (3)
K2S2O8 (3)
K2S2O8 (3)
K2S2O8 (3)
K2S2O8 (3)
Oxone (3)
BPO (3)
80
80
80
80
80
80
80
80
80
80
60
90
100
90
90
90
90
90
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
THF
Toluene
DMF
DMSO
NMP
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
58
72
63
88
86
30
70
Trace
25
Trace
75
90
78
26
83
50
73
41
5d
6
7
8
9
10
11
12
13
14
15
16
17
18
TBPB (3)
TBHP (3)
DTBP (3)
a
Reaction conditions: 1a (0.3 mmol), HP(O)Ph2 (0.9 mmol), and oxidant in dry
solvent (4.5 mL) under argon for 20 h.
b
Isolated yield.
CH3CN (3 mL) was used.
CH3CN (6 mL) was used.
c
d
a
All the reactions were carried out in the presence of 0.3 mmol of 1aev, HP(O)
R4R5 (3.0 equiv), K2S2O8 (3.0 equiv) in 4.5 mL CH3CN at 90 ꢀC.
b
Isolated yield.
With the optimized reaction conditions, the substrate scope was
then investigated as shown in Table 2. Substrates 1aec bearing
methyl, benzyl or tosyl protecting groups on the nitrogen were
good for this transformation, but unprotected NeH acrylamide
failed to give the desired product 2d. It indicated that nitrogen
protecting group was essential under the oxidative environment.
The effect of substituents at the N-aryl moiety was subsequently
examined (2eep). Screening showed that N-arylacrylamides bear-
ing electron-donating or -withdrawing substituents on aniline
moieties could be successfully converted into the desired products
in good to excellent yields (2eei). Gratifyingly, Cl, Br, and I groups
were also well tolerated, thereby facilitating possible additional
modifications at the halogenated positions (2jꢁl). N-arylacryla-
mide substrates with phenyl group at the para or ortho position
displayed high reactivity in this transformation, provided the cor-
responding oxindoles in excellent yields (2m, 2n). Substrates
having two substituents on the phenyl rings also reacted well with
HP(O)Ph2 (2o, 2p). When the benzene ring of the substrates was
changed to naphthalene, the reaction successfully provided the
product (2q). Tetrahydroisoquinoline structural motif is commonly
encountered in many biologically active compounds. Acrylamides
prepared from this amine provided the corresponding tricyclic
oxindole derivative in excellent yield under the developed reaction
conditions (2r). In addition, a series of a-substituted olefins bearing
different functional groups, such as benzyl (2s) and phenyl (2t)
could also be converted into the corresponding oxindoles in good
yields. Finally, various phosphonyl radicals were evaluated. How-
ever, under the same conditions, other phosphorus species, such as
diethyl phosphate and ethyl phenylphosphinate failed to afford the
desired products (2u, 2v).

Y.-M. Li et al. / Tetrahedron 70 (2014) 1991e1996
1993
Based on the previous mechanistic studies,5b,8 a plausible
mechanism for our methodology is depicted in Scheme 2. Initially,
potassium peroxydisulphate may be decomposed to sulfate radical
anion upon heating.10 Then HP(O)Ph2 reacts with sulfate radical
anion to form phosphoryl radical A, followed by addition to the
carbonecarbon double bond of amide 1a affording radical in-
termediate B.4b,d The resulting alkyl radical B participates in an
intramolecular radical substitution reaction. Addition of radical to
the aromatic ring generates intermediate C, followed by oxidation
of C into the corresponding carbocation, which loses Hþ to produce
the oxindole 2a.
4.2.1. Compound 2a. This compound was prepared by the general
procedures. Yield¼90%. 1H NMR (400 MHz, CDCl3):
d 7.60e7.55 (m,
2H), 7.51e7.44 (m, 2H), 7.43e7.27 (m, 6H), 7.18e7.14 (m, 2H), 6.79 (t,
J¼7.6 Hz, 1H), 6.67 (d, J¼7.6 Hz, 1H), 3.09 (dd, d, J¼10.4, 15.2 Hz, 1H),
3.01 (s, 1H), 2.86 (dd, J¼10.8, 15.2 Hz, 1H), 1.43 (d, J¼1.6 Hz, 3H). 13
C
NMR (100 MHz, CDCl3):
d
179.4 (d, JCeP¼4.1 Hz), 142.9, 133.8 (d,
JCeP¼98.5 Hz), 133.0 (d, JCeP¼97.9 Hz), 131.4 (d, JCeP¼2.5 Hz), 131.3
(d, JCeP¼2.0 Hz), 131.2 (d, JCeP¼2.6 Hz), 130.7 (d, JCeP¼9.2 Hz), 130.4
(d, JCeP¼9.1 Hz), 128.3 (d, JCeP¼11.7 Hz), 128.1 (d, JCeP¼11.6 Hz),
127.9, 127.8, 122.1, 107.8, 45.4 (d, JCeP¼3.7 Hz), 37.8 (d,
JCeP¼71.4 Hz), 26.8 (d, JCeP¼11.9 Hz). 31P NMR (162 MHz, CDCl3):
d
25.71. IR (film) nmax: 3407, 3054, 2931, 1712, 1612, 1491, 1439, 1376,
1188, 1119, 861, 748, 696, 537, 501 cmꢁ1
. HRMS calcd for
C
23H22NO2P (MþNa)þ, 398.1280; found, 398.1286.
4.2.2. Compound 2b. This compound was prepared by the General
procedures. Yield¼92%. 1H NMR (400 MHz, CDCl3):
d 7.63e7.53 (m,
4H), 7.43 (t, J¼7.2 Hz, 2H), 7.38e7.34 (m, 4H), 7.31e7.22 (m, 4H),
7.20 (d, J¼7.2 Hz, 2H), 7.03 (t, J¼7.6 Hz, 1H), 6.73 (t, J¼7.6 Hz, 1H),
6.55 (d, J¼8.0 Hz, 1H), 5.04 (d, J¼16.0 Hz, 1H), 4.40 (d, J¼16.0 Hz,
1H), 3.09 (dd, J¼10.8, 19.2 Hz, 1H), 2.93 (dd, J¼10.0, 14.6 Hz, 1H),
1.49 (s, 3H). 13C NMR (100 MHz, CDCl3):
d
179.7 (d, JCeP¼5.1 Hz),
142.1, 136.2, 133.7 (d, JCeP¼98.9 Hz), 133.3 (d, JCeP¼98.3 Hz), 131.6
(d, JCeP¼2.7 Hz), 131.5 (d, JCeP¼2.8 Hz), 131.3 (d, JCeP¼2.7 Hz), 130.7
(d, JCeP¼9.4 Hz), 130.6 (d, JCeP¼9.3 Hz), 128.7, 128.4 (d,
JCeP¼11.7 Hz), 128.3 (d, JCeP¼11.7 Hz), 127.8, 127.4, 127.1, 125.0,
122.2, 108.9, 45.7 (d, JCeP¼4.5 Hz), 44.0, 37.3 (d, JCeP¼71.1 Hz), 27.0
Scheme 2. Proposed mechanisms.
(d, JCeP¼11.4 Hz). 31P NMR (162 MHz, CDCl3):
d 26.20. IR (film) nmax:
3427, 3055, 2923, 1710, 1611, 1489, 1437, 1354, 1176, 1116, 999, 744,
696, 536 cmꢁ1. HRMS calcd for C29H26NO2P (MþNa)þ, 474.1593;
found, 474.1603.
3. Conclusion
In summary, we have developed a novel metal-free oxidative
arylphosphination of activated alkenes by phosphorylation and
CeH functionalization cascade process using K2S2O8 oxidant. This
4.2.3. Compound 2c. This compound was prepared by the General
procedures. Yield¼66%. 1H NMR (400 MHz, CDCl3):
d 8.48 (s, 1H),
reaction creates an opportunity to construct
a variety of
7.67e7.63 (m, 2H), 7.48e7.42 (m, 5H), 7.39e7.32 (m, 3H), 7.25e7.20
(m, 3H), 7.09 (d, J¼8.0 Hz, 2H), 7.04 (t, J¼7.2 Hz, 1H), 6.81 (d,
J¼8.4 Hz, 1H), 3.26 (dd, J¼12.4, 15.6 Hz, 1H), 3.10 (dd, J¼8.8, 15.6 Hz,
phosphorus-containing oxindole moieties. Further investigations
toward the reaction scope, and applications in organic synthesis are
currently ongoing in our laboratory.
1H), 2.18 (s, 3H), 1.96 (s, 3H). 13C NMR (100 MHz, CDCl3):
d 174.4 (d,
JCeP¼9.3 Hz), 138.3, 138.2, 136.9, 134.2 (d, JCeP¼100.0 Hz), 132.9 (d,
JCeP¼99.0 Hz), 131.3 (d, JCeP¼2.7 Hz), 130.7 (d, JCeP¼2.8 Hz), 130.5,
130.4, 130.3, 130.2, 128.9, 128.7, 128.4 (d, JCeP¼11.6 Hz), 128.1 (d,
JCeP¼11.7 Hz), 127.0, 123.9, 119.7, 50.5 (d, JCeP¼2.8 Hz), 39.2 (d,
JCeP¼70.8 Hz), 25.8 (d, JCeP¼4.9 Hz), 20.8 (d, JCeP¼1.5 Hz). 31P NMR
4. Experimental section
4.1. General
1H and 13C NMR spectra were recorded on a Bruker advance III
400 spectrometer in CDCl3 with TMS as internal standard. 31P NMR
spectra and 19F NMR were recorded on the same instrument. IR
spectra were recorded on a Nexus 670 FT-IR spectrometer and only
major peaks are reported in cmꢁ1. HRMS data were determined on
a Bruker Daltonics APEXII 47e FT-ICR spectrometer. The starting
materials were purchased from Aldrich, Acros Organics, J&K
Chemicals or TCI and used without further purification. Solvents
were dried and purified according to the procedure from ‘Purifi-
cation of Laboratory Chemicals book’. Column chromatography was
carried out on silica gel (particle size 200e400 mesh ASTM).
(162 MHz, CDCl3):
d 28.69. IR (film) nmax: 3441, 3285, 3051, 2932,
1662, 1599, 1533, 1436, 1315, 1246, 1184, 1114, 753, 695, 526 cmꢁ1
.
HRMS calcd for C29H26NO4PS (MþNa)þ, 538.1212; found, 538.1211.
4.2.4. Compound 2e. This compound was prepared by the General
procedures. Yield¼87%. 1H NMR (400 MHz, CDCl3):
d 7.56e7.46 (m,
4H), 7.40 (t, J¼7.2 Hz, 1H), 7.35e7.28 (m, 4H), 6.93 (d, J¼7.6 Hz, 1H),
6.78 (s, 1H), 6.59 (d, J¼8.0 Hz, 1H), 3.11e3.05 (m, 4H), 2.82 (dd,
J¼9.6, 15.2 Hz, 1H), 2.06 (s, 3H), 1.43 (s, 3H). 13C NMR (100 MHz,
CDCl3):
d
179.3 (d, JCeP¼4.1 Hz), 140.3, 133.6 (d, JCeP¼98.6 Hz), 133.3
(d, JCeP¼100.8 Hz), 131.3 (d, JCeP¼2.6 Hz), 131.2, 131.1 (d,
JCeP¼2.7 Hz), 130.9 (d, JCeP¼2.7 Hz), 130.5 (d, JCeP¼9.4 Hz), 130.4 (d,
JCeP¼9.2 Hz), 128.1 (d, JCeP¼1.9 Hz), 128.1, 128.0 (d, JCeP¼1.9 Hz),
125.4, 107.5, 45.3 (d, JCeP¼5.0 Hz), 37.5 (d, JCeP¼71.2 Hz), 26.6 (d,
4.2. General procedures for arylphosphination of alkenes
In a Schlenk tube, amide 1 (0.30 mmol), HP(O)Ph2 (182 mg,
0.90 mmol), K2S2O8 (243 mg, 0.90 mmol) were added and charged
with Ar three times. Then, anhydrous CH3CN (4.5 mL) were added.
The mixture was allowed to stir at 90 ꢀC for 20 h. The reaction
was cooled to room temperature and diluted with CH3CN,
then filtering through a bed of Celite. The filtered reaction mix-
ture was concentrated by rotary evaporation and purified by col-
umn chromatography (hexane/isopropanol¼10:1) to give the
product 2.
JCeP¼12.1 Hz), 26.3, 20.8. 31P NMR (162 MHz, CDCl3):
d 25.71. IR
(film) nmax: 3402, 3071, 2928, 1709, 1622, 1495, 1436, 1353, 1190,
1113, 751, 694, 538, 506 cmꢁ1. HRMS calcd for C24H24NO2P
(MþNa)þ, 412.1437; found, 412.1437.
4.2.5. Compound 2f. This compound was prepared by the General
procedures. Yield¼72%. 1H NMR (400 MHz, CDCl3):
d 7.57e7.50 (m,
4H), 7.44e7.39 (m, 2H), 7.37e7.31 (m, 4H), 6.75 (d, J¼2.4 Hz, 1H),
6.70 (dd, J¼2.4, 8.4 Hz, 1H), 6.59 (d, J¼8.4 Hz, 1H), 3.64 (s, 3H),

1994
Y.-M. Li et al. / Tetrahedron 70 (2014) 1991e1996
3.11e3.04 (m, 4H), 2.82 (dd, J¼10.4, 15.2 Hz, 1H), 1.43 (d, J¼1.2 Hz,
3H). 13C NMR (100 MHz, CDCl3):
179.9, 155.5, 136.6, 133.7 (d,
(162 MHz, CDCl3): d 25.51. IR (film) nmax: 3417, 3058, 2983, 1715,
d
1609, 1488, 1435, 1189, 1118, 808, 743, 695, 542 cmꢁ1. HRMS calcd
JCeP¼98.4 Hz), 133.2 (d, JCeP¼98.1 Hz), 132.6 (d, JCeP¼2.6 Hz), 131.4
(d, JCeP¼2.5 Hz), 131.2 (d, JCeP¼2.6 Hz), 130.6 (d, JCeP¼9.4 Hz), 130.5
(d, JCeP¼9.3 Hz), 128.3 (d, JCeP¼6.9 Hz), 128.2 (d, JCeP¼6.9 Hz), 113.2,
111.5, 108.2, 55.6, 46.0 (d, JCeP¼3.8 Hz), 37.5 (d, JCeP¼71.6 Hz), 26.7
for C23H21ClNO2P (MþNa)þ, 432.0891; found, 432.0883.
4.2.10. Compound 2k. This compound was prepared by the General
procedures. Yield¼89%. 1H NMR (400 MHz, CDCl3):
d 7.61e7.56 (m,
(d, JCeP¼12.3 Hz), 26.5. 31P NMR (162 MHz, CDCl3):
d
26.01. IR (film)
2H), 7.48e7.42 (m, 4H), 7.39e7.32 (m, 4H), 7.26e7.23 (m, 1H), 6.94
(d, J¼2.0 Hz, 1H), 6.61 (d, J¼8.3 Hz, 1H), 3.13e3.06 (m, 4H), 2.78 (dd,
J¼8.4, 15.2 Hz, 1H), 1.42 (d, J¼1.6 Hz, 3H). 13C NMR (100 MHz,
nmax: 3398, 3054, 2934, 1707, 1599, 1497, 1435, 1236, 1189, 1116,
1041, 750, 695, 540, 509 cmꢁ1. HRMS calcd for C24H24NO3P
(MþNa)þ, 428.1386; found, 428.1388.
CDCl3):
d
178.9 (d, JCeP¼3.5 Hz), 142.4, 133.3 (d, JCeP¼98.8 Hz),
133.12, 133.10, 132.8 (d, JCeP¼99.0 Hz), 131.6, 130.8, 130.4 (d,
JCeP¼9.3 Hz), 130.2 (d, JCeP¼9.1 Hz), 128.4 (d, JCeP¼6.1 Hz), 128.3 (d,
JCeP¼6.2 Hz), 127.7, 114.6, 109.3, 45.4 (d, JCeP¼4.0 Hz), 37.6 (d,
JCeP¼70.7 Hz), 26.54, 26.53 (d, JCeP¼12.1 Hz). 31P NMR (162 MHz,
4.2.6. Compound 2g. This compound was prepared by the General
procedures. Yield¼94%. 1H NMR (400 MHz, CDCl3):
d 7.60e7.55 (m,
2H), 7.45e7.34 (m, 7H), 7.31e7.27 (m, 2H), 7.08 (s, 1H), 6.82 (d,
J¼8.4 Hz, 1H), 3.20e3.13 (m, 4H), 2.86 (dd, J¼8.0, 15.2 Hz, 1H), 1.46
CDCl3):
d 25.42. IR (film) nmax: 3397, 3057, 2985, 2229, 1710, 1604,
(d, J¼1.6 Hz, 3H). 13C NMR (100 MHz, CDCl3)
d
179.5 (d, JCeP¼3.2 Hz),
1488, 1190, 1118, 912, 739, 540 cmꢁ1. HRMS calcd for C23H21BrNO2P
146.4, 133.5 (d, JCeP¼98.9 Hz), 132.7 (d, JCeP¼99.0 Hz), 132.2, 131.6
(d, JCeP¼2.5 Hz), 131.5 (d, JCeP¼2.7 Hz), 130.3 (d, JCeP¼9.4 Hz), 130.1
(d, JCeP¼9.3 Hz), 128.4 (d, JCeP¼6.8 Hz), 128.3 (d, JCeP¼7.0 Hz), 125.8
(d, JCeF¼3.8 Hz), 124.0 (d, JCeF¼270.0 Hz), 123.9 (d, JCeF¼32.6 Hz),
121.1 (d, JCeF¼3.8 Hz), 107.7, 45.2 (d, JCeP¼4.0 Hz), 37.7 (d,
(MþNa)þ, 476.0385; found, 476.0372.
4.2.11. Compound 2l. This compound was prepared by the General
procedures. Yield¼25%. 1H NMR (400 MHz, CDCl3):
d 7.62e7.57 (m,
2H), 7.50e7.29 (m, 9H), 7.07 (d, J¼1.2 Hz, 1H), 6.53 (d, J¼4.4 Hz, 1H),
JCeP¼71.2 Hz), 26.7, 26.6. 31P NMR (162 MHz, CDCl3):
d
25.36. 19F
3.14e3.02 (m, 4H), 2.77 (dd, J¼7.6, 14.8 Hz, 1H), 1.41 (d, J¼1.2 Hz,
NMR (376 MHz, CDCl3):
d
ꢁ61.10. IR (film) nmax: 3429, 3057, 2908,
3H). 13C NMR (100 MHz, CDCl3):
d
180.1 (d, JCeP¼3.2 Hz), 143.2,
1724, 1624, 1398, 1328, 1182, 1119, 743, 695, 533 cmꢁ1. HRMS calcd
140.6, 134.4 (d, JCeP¼2.8 Hz), 133.6 (d, JCeP¼99.0 Hz), 132.2 (d,
JCeP¼97.7 Hz),131.6 (d, JCeP¼2.5 Hz),131.4 (d, JCeP¼2.5 Hz),130.8 (d,
JCeP¼9.5 Hz), 130.5 (d, JCeP¼9.0 Hz), 128.4 (d, JCeP¼11.7 Hz), 128.2
(d, JCeP¼11.7 Hz), 124.7, 123.9, 71.3, 45.0 (d, JCeP¼3.7 Hz), 37.7 (d,
JCeP¼70.3 Hz), 30.2, 27.4 (d, JCeP¼12.1 Hz). 31P NMR (162 MHz,
for C24H21F3NO2P (MþNa)þ, 466.1154; found, 466.1146.
4.2.7. Compound 2h. This compound was prepared by the General
procedures. Yield¼79%. 1H NMR (400 MHz, CDCl3):
d 7.64e7.59 (m,
2H), 7.53e7.30 (m, 9H), 6.92 (d, J¼12.1 Hz, 1H), 6.83 (d, J¼8.0 Hz,
1H), 3.22 (s, 3H), 3.15 (dd, J¼12.4, 14.8 Hz, 1H), 2.48 (dd, J¼6.8,
14.8 Hz, 1H), 1.45 (d, J¼1.6 Hz, 3H). 13C NMR (100 MHz, CDCl3):
CDCl3): d 25.42. IR (film) nmax: 3403, 3063, 2896, 1715, 1601, 1485,
1342, 1190, 1118, 744, 696, 540 cmꢁ1. HRMS calcd for C23H21INO2P
(MþNa)þ, 524.0247; found, 524.0241.
d
179.1 (d, J¼2.9 Hz), 147.3, 133.2 (d, J¼99.2 Hz), 133.1, 132.5 (d,
J¼98.6 Hz), 131.8 (d, J¼2.7 Hz), 131.7 (d, J¼2.8 Hz), 131.7, 130.2 (d,
J¼10.1 Hz), 130.1 (d, J¼9.6 Hz), 128.4 (d, J¼9.1 Hz), 128.3 (d,
J¼9.1 Hz), 127.5, 118.8, 108.3, 104.7, 44.9 (d, J¼4.0 Hz), 37.7 (d,
J¼71.1 Hz), 26.7, 26.2 (d, J¼12.5 Hz). 31P NMR (162 MHz, CDCl3):
4.2.12. Compound 2m. This compound was prepared by the Gen-
eral procedures. Yield¼95%. 1H NMR (400 MHz, CDCl3):
d 7.54e7.47
(m, 4H), 7.42e7.35 (m, 6H), 7.33e7.26 (m, 7H), 6.75 (d, J¼8.0 Hz,
1H), 3.20 (dd, J¼10.8, 15.2 Hz, 1H), 3.09 (s, 3H), 2.93 (dd, J¼10.4,
d
25.24. IR (film) nmax: 3429, 3043, 2960, 2219, 1723, 1612, 1450,
15.2 Hz, 1H), 1.48 (s, 3H). 13C NMR (100 MHz, CDCl3):
d 179.5 (d,
1347, 1190, 1118, 827, 755, 697, 547, 494 cmꢁ1. HRMS calcd for
JCeP¼3.4 Hz), 142.6, 140.7, 135.3, 133.0 (d, JCeP¼99.2 Hz), 132.5 (d,
JCeP¼98.8 Hz), 131.7 (d, JCeP¼2.8 Hz),131.5 (d, JCeP¼2.6 Hz), 131.5 (d,
JCeP¼2.5 Hz), 130.7 (d, JCeP¼9.5 Hz), 130.4 (d, JCeP¼9.3 Hz), 120.5,
128.3 (d, JCeP¼7.5 Hz), 128.2 (d, JCeP¼7.4 Hz), 126.9, 126.8, 126.7,
123.8, 108.1, 45.5 (d, JCeP¼3.7 Hz), 37.4 (d, JCeP¼71.2 Hz), 27.1 (d,
C
24H21N2O2P (MþNa)þ, 423.1233; found, 423.1223.
4.2.8. Compound 2i. This compound was prepared by the General
procedures. Yield¼95%. 1H NMR (400 MHz, CDCl3):
d 7.59e7.51 (m,
4H), 7.46e7.4 (m, 2H), 7.39e7.32 (m, 4H), 7.10 (dd, J¼2.0, 8.4 Hz,
1H), 6.83 (d, J¼2.0 Hz,1H), 6.65 (d, J¼8.0 Hz,1H), 3.12e3.06 (m, 5H),
2.79 (dd, J¼8.4, 14.8 Hz, 1H), 1.42 (d, J¼1.6 Hz, 3H). 13C NMR
JCeP¼12.3 Hz), 26.5. 31P NMR (162 MHz, CDCl3):
d 27.40. IR (film)
nmax: 3431, 3056, 2926, 2219, 1892, 1713, 1619, 1486, 1437, 1352,
1190, 1119, 907, 721, 695, 544 cmꢁ1. HRMS calcd for C29H26NO2P
(MþH)þ, 452.1774; found, 452.1788.
(100 MHz, CDCl3):
d
179.0 (d, J¼4.3 Hz), 158.6 (d, JCeF¼238.7 Hz),
139.0 (d, JCeF¼1.8 Hz), 133.2 (d, J¼98.6 Hz), 133.1 (d, J¼98.6 Hz),
132.9 (dd, J¼2.6, 8.3 Hz), 131.4 (d, J¼2.7 Hz), 131.3 (d, J¼2.7 Hz),
130.4 (d, J¼9.4 Hz), 130.3 (d, J¼9.2 Hz), 128.3 (d, J¼6.5 Hz), 128.2 (d,
J¼6.5 Hz), 114.1 (d, JCeF¼23.5 Hz), 112.7 (d, JCeF¼25.2 Hz), 108.1 (d,
JCeF¼8.1 Hz), 45.8 (d, J¼2.2 Hz), 37.4 (d, J¼71.3 Hz), 26.4, 26.3. 31P
4.2.13. Compound 2n. This compound was prepared by the General
procedures. Yield¼91%. 1H NMR (400 MHz, CDCl3):
d 7.62e7.53 (m,
4H), 7.44e7.34 (m,11H), 7.13 (d, J¼6.8 Hz,1H), 6.97 (d, J¼8.0 Hz,1H),
6.75 (t, J¼7.6 Hz, 1H), 3.15 (dd, J¼10.8, 15.2 Hz, 1H), 2.88 (dd, J¼10.8,
15.2 Hz, 1H), 2.55 (s, 3H), 1.48 (d, J¼1.2 Hz, 3H). 13C NMR (100 MHz,
NMR (162 MHz, CDCl3):
d
25.59. 19F NMR (376 MHz, CDCl3):
d
ꢁ121.22. IR (film) nmax: 3414, 3057, 2902, 1716, 1497, 1178, 1119,
CDCl3):
d
180.3 (d, JCeP¼3.7 Hz), 139.8, 139.0, 133.7 (d,
748, 693, 542 cmꢁ1. HRMS calcd for C23H21FNO2P (MþNa)þ,
JCeP¼98.5 Hz), 133.1 (d, JCeP¼97.8 Hz), 132.2, 131.3 (d, JCeP¼2.4 Hz),
131.1 (d, JCeP¼2.7 Hz), 130.9, 130.7 (d, JCeP¼9.4 Hz), 130.4 (d,
JCeP¼9.0 Hz), 128.3 (d, JCeP¼11.7 Hz), 128.1 (d, JCeP¼11.7 Hz), 127.6,
127.4, 125.0, 123.7, 121.4, 44.7 (d, JCeP¼3.8 Hz), 38.0 (d,
JCeP¼70.8 Hz), 30.3, 27.2 (d, JCeP¼12.2 Hz). 31P NMR (162 MHz,
416.1186; found, 416.1193.
4.2.9. Compound 2j. This compound was prepared by the General
procedures. Yield¼78%. 1H NMR (400 MHz, CDCl3):
d 7.61e7.56 (m,
2H), 7.48e7.42 (m, 4H), 7.39e7.32 (m, 4H), 7.10 (dd, J¼2.0, 8.4 Hz,
1H), 8.63 (d, J¼2.0 Hz, 1H), 6.65 (d, J¼8.0 Hz, 1H), 3.12 (m, 5H), 2.79
(dd, J¼8.4, 14.8 Hz, 1H), 1.42 (d, J¼1.6 Hz, 3H). 13C NMR (100 MHz,
CDCl3): d 25.61. IR (film) nmax: 3404, 3055, 2926, 1711, 1601, 1458,
1438, 1372, 1340, 1194, 1119, 1064, 859, 741, 699, 543, 505 cmꢁ1
.
HRMS calcd for C29H26NO2P (MþH)þ, 452.1774; found, 452.1788.
CDCl3):
d
179.0 (d, JCeP¼3.7 Hz), 141.9, 133.3 (d, JCeP¼98.8 Hz), 132.9
(d, JCeP¼98.7 Hz),132.8 (d, JCeP¼2.7 Hz),131.6 (d, JCeP¼2.7 Hz),131.5
(d, JCeP¼2.8 Hz), 130.5 (d, JCeP¼9.4 Hz), 130.3 (d, JCeP¼9.3 Hz), 128.4
(d, JCeP¼6.0 Hz), 128.3 (d, JCeP¼6.0 Hz), 127.9, 127.2, 125.0, 108.8,
45.5 (d, JCeP¼4.0 Hz), 37.6 (d, JCeP¼70.8 Hz), 26.6, 26.5. 31P NMR
4.2.14. Compound 2o. This compound was prepared by the General
procedures. Yield¼91%. 1H NMR (400 MHz, CDCl3):
d 7.47e7.38 (m,
6H), 7.33e7.28 (m, 4H), 6.41 (s, 1H), 6.34 (s, 1H), 3.27 (dd, J¼10.4,
15.2 Hz, 1H), 2.93e2.87 (m, 4H), 2.32 (s, 3H), 2.08 (s, 3H), 1.47 (d,

Y.-M. Li et al. / Tetrahedron 70 (2014) 1991e1996
1995
J¼2.0 Hz, 3H). 13C NMR (100 MHz, CDCl3):
d
179.3, 143.5, 137.9,
46.2 (d, JCeP¼12.2 Hz), 36.4 (d, JCeP¼70.8 Hz), 25.8. 31P NMR
135.2, 133.4 (d, JCeP¼100.3 Hz), 132.4 (d, JCeP¼97.6 Hz), 131.3 (d,
JCeP¼2.6 Hz), 131.0 (d, JCeP¼2.6 Hz), 130.9 (d, JCeP¼9.4 Hz), 130.5 (d,
JCeP¼9.1 Hz), 128.0 (d, JCeP¼11.7 Hz), 127.9 (d, JCeP¼11.8 Hz), 125.6
(d, JCeP¼2.9 Hz), 125.3, 106.5, 45.2 (d, JCeP¼3.6 Hz), 36.8 (d,
JCeP¼70.1 Hz), 26.2, 25.3 (d, JCeP¼14.4 Hz), 21.5, 18.3. 31P NMR
(162 MHz, CDCl3): d 25.93. IR (film) nmax: 3411, 3051, 2900, 1713,
1610, 1493, 1436, 1380, 1186, 1121, 744, 697, 541, 500 cmꢁ1. HRMS
calcd for C29H26NO2P (MþNa)þ, 474.1593; found, 474.1583.
4.2.19. Compound 2t. This compound was prepared by the General
(162 MHz, CDCl3):
d
25.08. IR (film) nmax: 3398, 3080, 3015, 2962,
procedures. Yield¼85%. 1H NMR (400 MHz, CDCl3):
d 7.57e7.43 (m,
1909, 1708, 1620, 1596, 1439, 1337, 1205, 1192, 1120, 1047, 881, 828,
753, 722, 697, 549, 534, 507 cmꢁ1. HRMS calcd for C25H26NO2P
(MþH)þ, 404.1774; found, 404.1759.
4H), 7.41e7.23 (m, 8H), 7.25e7.16 (m, 4H), 7.04 (d, J¼7.2 Hz, 1H),
6.75e6.71 (m, 2H), 3.71 (dd, J¼11.2, 15.2 Hz, 1H), 3.23 (dd, J¼10.0,
14.8 Hz, 1H), 3.01 (s, 3H). 13C NMR (100 MHz, CDCl3):
d 177.5 (d,
JCeP¼2.1 Hz), 144.2, 140.6 (d, JCeP¼12.3 Hz), 133.5 (d, JCeP¼99.2 Hz),
133.2 (d, JCeP¼98.1 Hz),131.3 (d, JCeP¼2.7 Hz),131.0 (d, JCeP¼2.6 Hz),
130.7 (d, JCeP¼9.2 Hz), 130.4 (d, JCeP¼9.1 Hz), 129.0 (d, JCeP¼3.3 Hz),
128.5, 128.3 (d, JCeP¼7.9 Hz), 128.2 (d, JCeP¼5.1 Hz), 128.1, 127.4,
126.9, 126.4, 121.8, 108.1, 52.5 (d, JCeP¼2.9 Hz), 38.5 (d,
4.2.15. Compound 2p. This compound was prepared by the General
procedures. Yield¼90%. 1H NMR (400 MHz, CDCl3):
d 7.59e7.54 (m,
2H), 7.49e7.44 (m, 4H), 7.40e7.34 (m, 4H), 6.84 (s, 1H), 6.67 (d,
J¼1.6 Hz, 1H), 3.35 (s, 3H), 3.14 (dd, J¼11.6, 15.2 Hz, 1H), 2.77 (dd,
J¼8.8, 14.8 Hz, 1H), 2.47 (s, 3H), 1.39 (d, J¼1.2 Hz, 3H). 13C NMR
JCeP¼69.6 Hz), 26.6. 31P NMR (162 MHz, CDCl3):
d 24.90. IR (film)
(100 MHz, CDCl3):
d
179.7 (d, JCeP¼2.7 Hz), 139.8, 133.3 (d,
nmax: 3406, 3056, 2930, 1714, 1612, 1493, 1373, 1188, 1119, 744, 696,
542, 514 cmꢁ1. HRMS calcd for C28H24NO2P (MþNa)þ, 460.1437;
found, 460.1427.
JCeP¼2.5 Hz), 132.7 (d, JCeP¼99.0 Hz), 132.5 (d, JCeP¼99.3 Hz), 131.7,
131.6 (d, JCeP¼2.9 Hz), 131.3, 130.6 (d, JCeP¼9.5 Hz), 130.3 (d,
JCeP¼9.3 Hz), 128.4 (d, JCeP¼1.9 Hz), 128.3 (d, JCeP¼1.8 Hz), 126.9,
122.6, 121.0, 44.9 (d, JCeP¼3.9 Hz), 37.9 (d, JCeP¼71.0 Hz), 29.8, 27.1
Acknowledgements
(d, JCeP¼12.7 Hz), 18.7. 31P NMR (162 MHz, CDCl3):
d 26.77. IR (film)
nmax: 3424, 3024, 2928, 1720, 1597, 1463, 1437, 1354, 1331, 1192,
We gratefully acknowledge the National Natural Science Foun-
dation of China (Nos. 21072079 and 21272100) and Program for
New Century Excellent Talents in University (NCET-11-0215) for
their financial support.
1122, 815, 743, 694, 547, 531, 508 cmꢁ1
. HRMS calcd for
C
24H23ClNO2P (MþH)þ, 424.1228; found, 424.1210.
4.2.16. Compound 2q. This compound was prepared by the General
procedures. Yield¼65%. 1H NMR (400 MHz, CDCl3):
d 7.55 (d,
Supplementary data
J¼8.0 Hz, 1H), 7.49e7.41 (m, 3H), 7.37e7.19 (m, 9H), 7.11e7.07 (m,
2H), 6.79 (d, J¼7.6 Hz, 1H), 3.83 (dd, J¼10.0, 15.2 Hz, 1H), 3.34 (s,
3H), 2.99 (dd, J¼11.2, 15.2 Hz, 1H), 1.74 (d, J¼2.0 Hz, 3H). 13C NMR
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.tet.2014.01.065.
(100 MHz, CDCl3):
d
172.3 (d, JCeP¼2.1 Hz), 136.5, 135.3 (d,
JCeP¼2.4 Hz), 133.5 (d, JCeP¼98.1 Hz), 133.0, 132.9 (d, JCeP¼97.5 Hz),
131.0 (d, JCeP¼2.5 Hz), 131.0, 130.9, 130.8, 130.5 (d, JCeP¼9.1 Hz),
128.0 (d, JCeP¼11.7 Hz), 127.6 (d, JCeP¼11.7 Hz), 126.3 (d,
JCeP¼4.2 Hz), 126.1, 124.1, 122.2, 119.1, 108.4, 45.2 (d, JCeP¼3.3 Hz),
42.2 (d, JCeP¼69.4 Hz), 34.8 (d, JCeP¼13.5 Hz), 29.8. 31P NMR
References and notes
1. (a) Kolio, D. T. Chemistry and Application of H-Phosphonates; Elsevier Science:
Amsterdam, 2006; (b) Tang, W.; Zhang, X. Chem. Rev. 2003, 103, 3029e3070; (c)
Van der Jeught, S.; Stevens, C. V. Chem. Rev. 2009, 109, 2672e2702; (d) George,
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392e395.
(162 MHz, CDCl3):
d 27.29. IR (film) nmax: 3439, 3052, 2923, 1668,
1586, 1378, 1315, 1178, 1120, 740, 695, 544 cmꢁ1. HRMS calcd for
C
27H24NO2P (MþNa)þ, 448.1437; found, 448.1449.
4.2.17. Compound 2r. This compound was prepared by the General
2. For reviews, see: (a) Engel, R. Synthesis of CarbonePhosphorus Bonds; CRC: Boca
Raton, USA, 1988; (b) Prim, D.; Campagne, J.; Joseph, D.; Andrioletti, B. Tetra-
hedron 2002, 58, 2041e2075; (c) Baillie, C.; Xiao, J.-L. Curr. Org. Chem. 2003, 7,
477e514; (d) Schwan, A. L. Chem. Soc. Rev. 2004, 33, 218e224; (e) Baumgartner,
procedures. Yield¼82%. 1H NMR (400 MHz, CDCl3):
d 7.63e7.58 (m,
2H), 7.53e7.48 (m, 2H), 7.45e7.29 (m, 6H), 7.03 (d, J¼7.4 Hz, 1H),
6.90 (d, J¼7.7 Hz, 1H), 6.70 (t, J¼7.6 Hz, 1H), 3.65e3.59 (m, 1H),
3.38e3.32 (m, 1H), 3.08 (dd, J¼10.1, 15.2 Hz, 1H), 2.87 (dd, J¼11.1,
15.2 Hz, 1H), 2.71e2.60 (m, 2H), 1.95e1.84 (m, 2H), 1.43 (d, J¼1.4 Hz,
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T.; Reau, R. Chem. Rev. 2006, 106, 4681e4727; (f) Glueck, D. S. Synlett 2007,
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3H). 13C NMR (100 MHz, CDCl3):
d
178.3 (d, JCeP¼4.5 Hz), 138.6,
133.8 (d, JCeP¼98.7 Hz), 133.0 (d, JCeP¼97.9 Hz), 131.3 (d,
JCeP¼2.7 Hz), 131.2 (d, JCeP¼2.4 Hz), 130.8 (d, JCeP¼9.4 Hz), 130.5 (d,
JCeP¼9.2 Hz), 130.0 (d, JCeP¼2.8 Hz), 128.3 (d, JCeP¼11.6 Hz), 128.1
3. (a) Oshiki, T.; Imamoto, T. J. Am. Chem. Soc. 1992, 114, 3975e3977; (b) Mon-
tchamp, J.-L.; Dumond, Y. R. J. Am. Chem. Soc. 2001, 123, 510e511; (c) Moncarz, J.
R.; Laritcheva, N. F.; Glueck, D. S. J. Am. Chem. Soc. 2002, 124, 13356e13357; (d)
Moncarz, J. R.; Brunker, T. J.; Glueck, D. S.; Sommer, R. D.; Rheingold, A. L. J. Am.
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Lett. 2003, 5, 2315e2318; (f) Chan, V. S.; Bergman, R. G.; Toste, F. D. J. Am. Chem.
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(d, JCeP¼11.7 Hz),126.6. 31P NMR (162 MHz, CDCl3):
d 26.10. IR (film)
nmax: 3414, 3054, 2963, 2891, 1707, 1627, 1483, 1357, 1189, 1118, 745,
697, 537 cmꢁ1. HRMS calcd for C25H24NO2P (MþNa)þ, 424.1437;
found, 424.1438.
4.2.18. Compound 2s. This compound was prepared by the General
€
€
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procedures. Yield¼92%. 1H NMR (400 MHz, CDCl3):
d 7.63e7.58 (m,
2H), 7.48e7.40 (m, 3H), 7.38e7.33 (m, 3H), 7.30e7.25 (m, 2H), 7.13
(d, J¼7.2 Hz,1H), 7.08 (dd, J¼0.8, 7.6 Hz,1H), 7.05e6.96 (m, 3H), 6.79
(dd, J¼0.8, 7.6 Hz, 1H), 6.74 (m, 2H), 6.35 (d, J¼7.6 Hz, 1H),
3.26e2.95 (m, 2H), 2.68 (s, 3H). 13C NMR (100 MHz, CDCl3):
d 177.8
(d, JCeP¼3.7 Hz), 143.4, 134.6, 133.8 (d, JCeP¼98.7 Hz), 132.8 (d,
JCeP¼98.1 Hz), 131.2 (d, JCeP¼2.7 Hz), 130.8 (d, JCeP¼9.4 Hz), 130.5
(d, JCeP¼9.0 Hz), 129.9, 128.5, 128.4, 128.3, 128.0, 127.9 (d,
JCeP¼4.4 Hz), 127.3, 126.6, 125.8, 121.6, 107.4, 50.9 (d, JCeP¼93.6 Hz),
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