Combined C-H functionalization/O-H insertion reaction to form tertiary β-alkoxy substituted β-aminophosphonates catalyzed by [Cu(MeCN) 4]PF6

Article abstract of DOI:10.1039/c3ob40941d

The copper-catalyzed C-H functionalization/O-H insertion reaction of α-diazophosphonates with alcohols has been developed with iodine as an additive. In order to understand this reaction, we present here a possible mechanism for the combined reaction. This process provides straightforward access to tertiary β-alkoxy substituted β-aminophosphonate derivatives with moderate to good yields. The Royal Society of Chemistry.

Full text of DOI:10.1039/c3ob40941d

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ARTICLE TYPE
Combined C-H Functionalization/O-H Insertion Reaction to Form
Tertiary β-Alkoxy Substituted β-Aminophosphonates Catalyzed by
[Cu(MeCN)4]PF6
Yan Cai,a Yuchen Lu,a Chengbin Yu,a Hairong Lva and Zhiwei Miaoa,b*
5
Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX
DOI: 10.1039/b000000x
The copper-catalyzed C-H functionalization/O-H insertion reaction of α-diazophosphonates with alcohols
has been developed with iodine as additive. In order to understand this reaction, we present here a
possible mechanism for the combined reaction. This process provides straightforward access to tertiary β-
10 alkoxy substituted β-aminophosphonate derivatives with moderate to good yields.
aminophosphorus derivatives,8 here we report the combined C-H
functionalization and O-H insertion to form a tertiary β-alkoxy
substituted β-Aminophosphonates.
Introduction
The catalytic activation of a C-H or O-H bond to form a new C-C
or C-O bond provides a potent strategic approach for the
introduction of functional diversity and structural complexity into
15 compounds, and attracts considerable interest.1 Despite the
substantial progress that has been made in this field, the catalytic
insertion reaction of α-diazocarbonyl compounds into C-H bond
has attracted much attention.1h,2 In contrast to the extensive and
fruitful studies on C-H insertion, the investigation of insertion of
20 α-diazocarbonyl compounds into oxygen-hydrogen bond (O-H) is
still limited being of the presence of the highly reactive polar O-
H bond.3 The O-H insertion was an efficient method for
preparing α-alkoxy or α-aryloxy ketones and esters, and oxygen-
containing heterocyclic compounds.4 However, the catalytic
25 insertion reaction of α-diazocarbonyl compounds with saturated
alcohols remains a challenge. Carbenes are among the most
active and useful intermediates in organic reactions. Transition
metals can stabilize carbenes by forming a metal-carbene
complex.5 The decomposition of diazo compounds in the
30 presence of hydroxylic compounds results in the formation of a
new C-O bond by a formal insertion of the carbene into the O-H
bond.
Results and discussion
50 The ready availability, relative stability and facile decomposition,
under
transition-metal
catalyzed
condition
of
α-
diazophosphonates
make them useful intermediates for
synthesis.9 In an attempt to extend the utility of α-
diazophosphonic acid derivatives in synthesis, we have prepared
55 the first examples of α-diazophosphonyl compounds derived
from natural amino acids and briefly investigated their O-H
insertion reactions. The synthesis of (S)-diethyl(1-diazo-2-(1,3-
dioxoisoindolin-2-yl)propyl) phosphonate 6a started with the
condensation of L-alanine 1 and phathalic anhydride. The
60 formation of the corresponding (S)-2-(1,3-dioxoisoindolin-2-
yl)propanoic acid 2 proceeded smoothly in acetic acid under
reflux conditions. Upon success chlorination with SOCl2 in
toluene, 2 afforded acyl chloride 3. After Arbuzov reaction of 3,
α-ketophosphonate
4
was converted to tosylhydrazone
65 phosphonate 5 by a reaction with p-toluene sulfonohydrazide in
THF at room temperature. Finally, the desired α-
diazophosphonate 6a could be readily obtained by the elimination
from 5 with Et3N in CH2Cl2 and the overall yield upon to 42%
for this five-step sequence reaction (Scheme 1).10
O
β-Aminophosphonates are the phosphorus analogues of β-
amino acids, and therefore have biological and biochemical
35 properties in their role as enzyme inhibitors, agrochemicals, or
pharmaceuticals.6 The development of efficient methods for
preparation of β-aminophosphonic (or phosphinic) acids is of
high value and currently attracting increasing attention. A lot of
general and asymmetric synthetic methods exist for the
40 preparation of α-aminophosphonic acid derivatives,7 however β-
aminophosphonic acid derivatives have been scarcely
O
O
O
O
O
P(OEt)3
O
P
SOCl2
toluene
reflux
N
N
N
H2N
COOH CH3COOH
reflux
CH2Cl2, rt
COOH
OEt
COCl
O
O
O
O
OEt
1
2
3
4
O
O
TsNHNH2
O
P
Et3N
OEt CH2Cl2, rt
O
P
N
N
HCl, THF
rt
OEt
O
N
OEt
NH
O
N2
OEt
5
6a
Ts
70
described.6a Particularly, the presence of
a
quaternary
Scheme 1. Synthesis of α-diazophosphonate 6a.
stereocenter in a high substituted β-alkoxy-β-aminophosphate
unit, will interact with certain proteases and resist proteolytic
45 degradation. Continuing with our interest in the chemistry of
We began our investigations by studying the reaction of (S)-
diethyl(1-diazo-2-(1,3-dioxoisoindolin-2-yl)propyl) phosphonate
6a with benzyl alcohol 7a, catalyzed by [Cu(MeCN)4]PF6 (5
This journal is © The Royal Society of Chemistry [year]
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Organic & Biomolecular Chemistry
Page 2 of 8
mol%) in dichloromethane at 25 °C (Table 1). Normally alcohols
CuBr, and CuI) were able to promote the reaction (Table 1,
react with carbenoids should form O-H insertion product.4 To our
surprise, the reaction did not afford the desired O-H insertion
product 8a’. The corresponding reaction of α-diazo phosphonate
entries 4-7). Since [Cu(MeCN)4]PF6 gave the higher yield (51%)
compared with other catalysts, it waDsOI:u1s0e.1d03V9iien/wC3AOfrtuBicr4lteh0O9enr4l1inDe
investigations. A screening of solvents showed that toluene, 1,2-
5
6a and benzyl alcohol 7a did however lead to the formation of 35 dichloroethane, THF and DME were providing 8a in lower yields
diethyl
(2-(benzyloxy)-2-(1,3-dioxoisoindolin-2-yl)propyl)
(Table 1, entries 8-10). Therefore, the tentatively optimized
reaction conditions were determined to use CH2Cl2 as the solvent.
With further optimization of the reaction conditions, the
influence of additives on the reaction was examined. We tested
phosphonate 8a by combined C-H functionalization/O-H
insertion reaction in 40% yield. In the meantime, one 1,2-
hydrogen
migration
byproduct
(Z)-diethyl
(2-(1,3-
10 dioxoisoindolin-2-yl)prop-1-en-1-yl)phosphonate
9a
was 40 different kinds of additives, including Brønsted acid, Lewis acid,
obtained in 11% yield. The molecular structure of 8a was
Lewis base, and achiral ligand. However, the yield of 8a could
not be elevated obviously (Table 2, entries 1-15). Only iodine as
additive was proceed the reaction to afford the desired product 8a
combined with byproduct 9a in moderate yield (Table 2, entry
45 16). Moreover, in the absence of iodine, we observed the
significant formation of side product 9a and catalyst deactivation.
Thus, the optimal reaction conditions for this transformation were
determined to be 0.28 mmol α-diazophosphonate 6a, 5.0
equivalents of benzyl alcohol 7a, 5 mol% of [Cu(MeCN)4]PF6 as
50 catalyst and 20 mol% of I2 as additive in 6 mL CH2Cl2 as solvent
at 25°C for 4.5 hours.
1
determined by H-, 31P-, 13C-NMR, and 2D NMR spectra and by
mass spectrometry.10
Table 1. Optimization of the reaction conditionsa
O
O
O
O
P
O
N
OH
O
P
5 mol% catalyst
solvent, 25 °C, 4.5h
N
N
OEt
+
+
OEt
O
N2
OEt
OEt
OEt
O
O
O
P
OEt
O
6a
7a
8a
9a
O
N
P
OEt
O
O
OEt
Table 2. Screening of the additivea
8a'
O
15
O
O
5 mol% [Cu(MeCN)4]PF6
5 mol% additive
O
P
O
N
OH
Entry
Catalysts
Solvent
8a/9ab
Yield
(%)c
51
OEt +
O
P
N
N
+
CH2Cl2, 25 °C, 4.5h
OEt
O
N2
OEt
OEt
OEt
O
O
OEt
P
O
6a
7a
8a
9a
1
2
[Cu(MeCN)4]PF6
Rh2(OAc)4
Pd(PPh3)2Cl2
Cu(OTf)2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
PhCH3
78:22
—
Entry
Additive
8a/9ab
Yield (%)c
d
—
1
2
3
4
5
6
NaBArF
69:31
63:37
50:50
76:24
—
43
<10
<10
49
—
—
Ph3P
AlCl3
3
—
—
4
66:34
75:25
65:35
66:34
57:43
76:24
65:35
62:38
42
L-tartaric acid
Et3N
5
CuOTf
50
TMEDAe
—
6
CuBr
40
7f
62:38
—
83:17
80:20
PhPCl2
2,2'-bipyridine
hydroquinone
2,4-di-tert-
butylphenol
DMF
49
—
49
56
7
CuI
42
8f
9f
8
[Cu(MeCN)4]PF6
49
10f
9
[Cu(MeCN)4]PF6 ClCH2CH2Cl
32
11f
12f
13f
14f
15g
16g
72:28
75:25
77:23
76:24
66:34
80:20
10
11
[Cu(MeCN)4]PF6
[Cu(MeCN)4]PF6
THF
DMEd
<10
<10
56
45
28
48
48
67
resorcin
4-tert-butylphenol
catechol
a
Unless otherwise noted, all reactions were carried out using α-
diazophosphonate 6a (0.28 mmol, 1 equiv) and benzyl alcohol 7a (1.4
Br2
I2
mmol, 5 equiv) in 6 mL solvent with 5 mol% of catalyst at 25 °C for 4.5h
b
(of addition 1.5h, after addition 3h).
Determined by 31P NMR
c
a Reactions were carried out on a 0.28 mmol scale with 5 equiv of benzyl
20 spectroscopy of the crude reaction mixture. Combined yield of 8a and
9a after silica gel chromatography. d DME = 1,2-dimethoxyethane.
55 alcohol 7a in 6 mL of CH2Cl2. b Determined by 31P NMR spectroscopy of
the crude reaction mixture. c Combined yield of 8a and 9a after silica gel
d
Encouraged by this result, we set out to further optimize the
reaction conditions. Various catalysts were tested in the reaction
of α-diazophosphonate 6a with benzyl alcohol 7a in
25 dichloromethane at 25°C. The results revealed that Rh2(OAc)4 (5
mol%) caused decomposition of α-diazophosphonate 6a, and no
product of 8a was observed (Table 1, entry 2). When
Pd(PPh3)2Cl2 (5 mol%) was employed in this reaction, there was
no reaction occurred and the starting material 6a was recycled
30 (Table 1, entry 3). Other catalysts tested (e.g., Cu(OTf)2, CuOTf,
chromatography.
NaBArF = sodium tetrakis[3,5-bis(trifluoromethyl)
phenyl]borate. e TMEDA = N,N,N’,N’-tetra-methylethylenediamine. f 10
g
mmol% of additive was employed.
60 employed.
20 mmol% of additive was
Based on the above optimization efforts, a broad range of
alcohols was then investigated in this reaction with α-
diazophosphonate 6 under standard reaction conditions (Table 3).
A variety of substituted benzyl alcohols 7 were examined in the
2
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Journal Name, [year], [vol], 00–00
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Page 3 of 8
Organic & Biomolecular Chemistry
combined C-H functionalization/O-H insertion reaction. The 15 good yields and chemoselectivities (8/9 from 80:20 to 93:7)
substrates with an electron-withdraw group in benzyl alcohol 7b-
d, such as fluoro, nitro and trifluoromethyl group, at 4-position
showed good yields and chemoselectivities (8/9 from 84:16 to
90:10) (Table 3, entries 2-4). The substrates 7e-g, containing an
(Table 3, entries 8-15). The alcohols with a electron-withdraw
group 7j-k gave higher yields, and the DyOieIl:d1s0.1o0f3V89iel/-wCo3AOwrtBiec4lre0eO9nn4l1oinDte
influenced by the extension of the aliphatic chain.
5
Secondary aliphatic alcohol 7p-q could also processed
electron-donation group in benzyl alcohol, were also examined in 20 smoothly in the reaction with moderate yields (Table 3, entry 16-
this reaction, the desired insertion products 8e-g were isolated in
lower yields (Table 3, entry 5-7). Surprisingly the substrate with
methoxy group in benzyl alcohol at 4-position 7g only gave 32%
17). Being the exist of steric effect the tertiary aliphatic alcohol
tert-butanol 7r was unreative and could not obtain the desired
product (Table 3, entry 18). When the stereohindance of R1 group
was decreased from ethyl to methyl, similar yields turned out in
10 yield. In this reaction, lower products yield was obtained owing
to the unstable of the final product 8g. Besides benzyl alcohol, all 25 this reaction. The results showed that the size of R1 group on the
the tested saturated primary alcohols 7h-o, also exhibited the O-H
insertion reaction smoothly to afford the corresponding tertiary β-
alkoxy substituted β-Aminophosphonates 8h-o with moderate to
α-diazophosphonate 6 has almost no influence on the reactivity in
the O-H insertion reaction (Table 3, entries 19-21).
Table 3. Scope of the reactiona
R3
O
O
O
O
R2
5 mol% [Cu(MeCN)4]PF6
20 mol% I2
R2
P
R2
O
P
O
P
3
N
+
N
N
R
OH
+
OR1
CH2Cl2, 25 °C, 4.5h
OR1
OR1
OR1
N2
O
O
O
OR1
OR1
O
6
7
8
9
Entry
R1
R2
R3
C6H5CH2 (7a)
p-FC6H4CH2 (7b)
p-NO2C6H4CH2 (7c)
p-CF3C6H4CH2 (7d)
p-MeC6H4CH2 (7e)
2,4,6-tri-MeC6H4CH2 (7f)
p-MeOC6H4CH2 (7g)
CH3 (7h)
8/9b
Yield (%)c
8
8a
8b
8c
8d
8e
8f
8g
8h
8i
8j
8k
8l
8m
8n
8o
8p
8q
8r
8s
1
2
3
4
5
6
7
8
C2H5
C2H5
C2H5
C2H5
C2H5
C2H5
C2H5
C2H5
C2H5
C2H5
C2H5
C2H5
C2H5
C2H5
C2H5
C2H5
C2H5
C2H5
CH3
CH3 (6a)
CH3 (6a)
CH3 (6a)
CH3 (6a)
CH3 (6a)
CH3 (6a)
CH3 (6a)
CH3 (6a)
CH3 (6a)
CH3 (6a)
CH3 (6a)
CH3 (6a)
CH3 (6a)
CH3 (6a)
CH3 (6a)
CH3 (6a)
CH3 (6a)
CH3 (6a)
CH3 (6b)
CH3 (6b)
CH3 (6b)
80:20
84:16
90:10
86:14
75:25
80:20
60:40
83:17
84:16
80:20
93:7
84:16
80:20
85:15
82:18
85:15
82:18
—
67
73
75
77
69
59
32
72
54
89
85
65
63
73
66
59
72
—
62
74
60
62
62
68
trace
9
CH3CH2 (7i)
ClCH2CH2(7j)
CF3CH2 (7k)
CH3(CH2)3 (7l)
i-Bu (7m)
CH3 (CH2)5 (7n)
CH3 (CH2)9 (7o)
i-Pr (7p)
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
Cy (7q)
t-Bu (7r)
CH3 (7h)
83:17
72:28
75:25
75:25
70:30
80:20
—
8t
CH3
CH3
C2H5
C2H5
C2H5
C2H5
C6H5CH2 (7a)
p-FC6H5CH2 (7b)
CH3 (7h)
8u
8v
8w
8x
8y
C6H5CH2 (6c)
i-Pr (6d)
(CH3)2CHCH2 (6e)
H (6f)
CH3 (7h)
CH3 (7h)
CH3 (7h)
a
30 Reaction conditions: α-diazophosphonate 6 (0.28 mmol), alcohol 7 (1.4 mmol), I2 (20 mol%) in 6 mL of CH2Cl2 at 25°C in the presence of 5 mol% of
[Cu(MeCN)4]PF6 for 4.5h (of addition 1.5h, after addition 3h). b Determined by 31P NMR spectroscopy of the crude reaction mixture. c Combined yield of
8 and 9 after silica gel chromatography.
1,2-H-Migration represents the fundamental reactions for
insertion reactions, and hard to eliminate.13 As shown in Table 3,
both free carbenes and transition-metal-associated carbenes.1h,11 40 the 1,2-hydrogen migration product diethyl (2-(1,3-
35 The inherent migratory aptitude is in the order of H > Ar > alkyl.
This migratory preference has also been known to be affected by
steric and conformational factors.12 The β-H-migration always
occurred as a side reaction in the carbenoid C-H and O-H
dioxoisoindolin-2-yl)prop-1-en-1-yl)phosphonate 9a (R1 = C2H5,
R2 = CH3) occurred as a by-product in the O-H insertion reaction.
The configuration of the double bond in 9a was always assigned
as Z which confirmed by X-ray crystallography14 and 2D
This journal is © The Royal Society of Chemistry [year]
Journal Name, [year], [vol], 00–00 | 3

Organic & Biomolecular Chemistry
Page 4 of 8
NOESY10 measurement.
hydroxyl group migrated to the carbon attached to phosphate and
In addition to exploring the scope of α-diazophosphonate
substrates 6 in the O-H insertion with benzyl alcohol, the impact
followed by the extrusion of Cu(I) catalyst to give the O-H
insertion product 8. This transformation iDsOcI:o1n0s.i1s0te3n9t/Cw3OitBh40th9e41D
View Article Online
of substituent groups on β-position of diethyl α-diazo 30 combined C-H functionalization/O-H insertion process. The
5
phosphonates 6 was evaluated. All the tested diazo phosphonates
6c-e with different substituents on β-position, such as benzyl,
isopropyl and isobutyl groups, afforded moderate level yields of
O-H insertion products and the 1,2-migration products (Table 3,
iodine may play a role of stabilizing the carbocation
intermediates B and C. In order to explore the mechanism of this
reaction, deuterated methanol was used for the deuterium labeling
experiment to investigate the proton-transfer process (Figure 1).
entries 22-24). When R2 was changed to H, only a trace amount 35 The results clearly indicate that one of the methyene proton of
10 of 8y was obtained (Table 3, entry 25).
compound 8 derived from CH3OH by 1,3-H migration. The
intermediate C may also be transformed to by-product 9 through
loss of [Cu(MeCN)4]PF6 and iodine before the attack of alcohol.
The carbocation formed in intermediate C resembled sp2
40 hybridization with a trigonal planar molecular geometry. The
alcohol could attack the carbocation from both sides and obtained
the products almost in racemic. It seems reasonable that the
reactivity of such an intermediate C may be influenced by the
steric effect of R2 group on β-position of α-diazophosphonates 6.
45 The large R2 group caused steric block and caused the low yield
of desired O-H insertion product. When R2 becoming hydrogen,
the carbocation could not be stabilized well enough and only
obtained trace amount of O-H insertion product (Table 3, entries
22-25).
Figure 1. Deuterium labeling experiments processed with
CH3OH and CD3OD repesctively determined by 1H NMR.
R3
O
O
O
R2
50 Conclusions
R2
O
P
O
P
N
N
[Cu(MeCN)4]PF6
(CuLn)
OR1
OR1
In conclusion, we have developed a novel copper-catalyzed
combined C-H functionalization/O-H insertion reaction of α-
diazophosphonates with alcohols. The catalyst [Cu(MeCN)4]PF6
combined with iodine was proved to be efficient, producing
55 tertiary β-alkoxy substituted β-aminophosphonates in moderate to
good yields with wide substrate scope. A plausible reaction
mechanism has been proposed to explain the combined C-H
functionalization/O-H insertion reaction. Further researches for
asymmetric synthesis of this reaction are currently underway in
60 our laboratory.
OR1
O
OR1
N2
O
I2
[Cu(MeCN)4]PF6
I2
8
6
O
R2
R3
O
I2
CuLn
O
N
R2
H
I
I
OR1
OR1
N
O
A
P
CuLn
O
OR1
O
P
OR1
O
D
O
O
R2
P
R2
P
I
I
I
I
N
N
Experimental
CuLn
CuLn
H
OR1
OR1
O
O
R3 OH
OR1
OR1
O
General remarks
O
O
B
C
All reactions and manipulations were performed using standard
Schlenk techniques. All solvents were purified and dried
65 according to standard procedures before use. Unless otherwise
indicated, all materials were obtained from commercial sources,
and used as purchased without dehydration. Flash column
chromatography was performed on silica gel (particle size 10-40
μm, Ocean Chemical Factory of Qingdao, China). Nitrogen gas
70 (99.999%) was purchased from Boc Gas Inc. Preparative high
performance liquid chromatography (HPLC) for separations were
R2
P
N
OR1
O
OR1
O
9
15 Scheme 2. Plausible reaction mechanism.
The possible mechanism for the reaction is shown in Scheme
2. The α-diazophosphate 6 initially formed a metal carbene
complex A with [Cu(MeCN)4]PF6 and iodine. The metal carbene
is a resonance hybrid of a formal metal carbene A and a metal-
20 stabilized carbocation B, which together describe the reactivity of
the intermediate. It has been suggested that in this metal carbene
intermediate, the carbon attached to the metal has a partial
positive charge.15 Then the β-hydrogen on the phosphonate
migrated to the carbene center through a resonance complex B to
25 form a tertiary carbocation intermediate C. Following the attack
of relative alcohol to give the intermediate D, the proton of
performed using Agilent 1260 Infinity machines. H NMR, 13C
1
NMR and 31P NMR spectra were recorded on Brucker-400 (400
MHz for 1H, 101MHz for 13C) spectrometers. Chemical shifts
75 were reported in ppm downfield from internal Si(CH3)4. H3PO4
served as internal standard (δ = 0 ppm) for 31P NMR. The crystal
structure was determined on a Bruker SMART 1000 CCD
diffractometer. Mass spectra were recorded on a LCQ advantage
spectrometer with ESI resource. HR-MS were recorded on
80 APEXII and ZAB-HS spectrometer. Melting points were
determined on a T-4 melting point apparatus (uncorrected).
4
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Page 5 of 8
Organic & Biomolecular Chemistry
Optical rotations were recorded on a Perkin Elemer 241
Polarimeter.
CH3); 13C NMR (101 MHz, CDCl3): δ 168.64 (C=O), 147.26,
60 145.03, 134.32, 131.56, 127.89, 123.54, 123.26 (Ph), 89.17 (s, O-
C-N), 63.57 (d, J = 2.3 Hz, OCH2Ar),D6O1I:.9103.1(0d3V,9ie/JwC3=AOrt6Bic4.le60O9Hn4l1iznD,e
OCH2), 61.68 (d, J = 6.6 Hz, OCH2), 36.41 (d, J = 140.5 Hz, C-
P), 24.11 (CH3), 16.23 (d, J = 6.3 Hz, CH3), 16.12 (d, J = 6.3 Hz,
CH3); 31P NMR (162 MHz, CDCl3): δ 23.87 (s); ESI-HRMS
General procedure for the preparation of 8: The
[Cu(MeCN)4]PF6 (0.014 mmol) and I2 (0.056 mmol) in an oven-
dried Schlenk tube was dissolved in 4 mL of freshly distilled
CH2Cl2 under nitrogen, alcohol 7 (1.4 mmol) was added and the
5
solution was stirred for 30 min at 25 °C. α-Diazophosphonates 6 65 calcd for [C22H25N2O8P, M+Na]+: 499.1241; Found: 499.1242.
(0.28 mmol) was diluted with 2 mL of CH2Cl2 and was drawn
into a gastight syringe. It was then added to the reaction mixture
10 dropwise over a period of 1.5h with the help of a syringe pump.
After the addition was complete, the reaction mixture was stirred
Diethyl(2-(1,3-dioxoisoindolin-2-yl)-2-((4-
(trifluoromethyl)benzyl)oxy)propyl)phosphonate
(8d).
1
Colorless oil; H NMR (400 MHz, CDCl3): δ 7.80-7.88 (m, 2H,
Ph), 7.70-7.77 (m, 2H, Ph), 7.54 (d, J = 7.9 Hz, 2H, Ph), 7.47 (d,
for another 3 hour at 25 °C. The solvent was then removed under 70 J = 7.9 Hz, 2H, Ph), 4.69 (d, J = 11.9 Hz, 1H, OCH2Ar), 4.53 (d,
reduced pressure and the crude residue was purified by silica gel
chromatography with the eluent (CH2Cl2/EtOAc = 15:1) or
15 purified by preparative HPLC [HPLC condition: YMC-Pack
ODS-A column, MeOH/H2O (v/v) with the gradient from 20% to
J = 11.9 Hz, 1H, OCH2Ar), 3.93-4.11 (m, 4H, 2OCH2), 3.59-3.73
(m, 1H, CH2-P), 2.45-2.58 (m, 1H, CH2-P), 2.29 (s, 3H, CH3),
1.21 (t, J = 7.0 Hz, 3H, CH3), 1.13 (t, J = 7.0 Hz, 3H, CH3); 13C
NMR (101 MHz, CDCl3): δ 168.66 (C=O), 141.55, 134.21,
100% in 20min, flow rate = 2 mL/min, wavelength = 254 nm] to 75 131.62 (Ph), 129.71 (d, J = 32.6 Hz, Ph), 127.69 (Ph), 125.23 (q,
give the corresponding products 8 and by-products 9.
Diethyl (2-(benzyloxy)-2-(1,3-dioxoisoindolin-2-
20 yl)propyl)phosphonate (8a). Colorless oil; H NMR (400 MHz,
CDCl3): δ 7.81-7.86 (m, 2H, Ph), 7.70-7.75 (m, 2H, Ph), 7.34 (d,
J = 3.7 Hz, CF3), 123.19 (Ph), 89.08 (O-C-N), 64.03 (d, J = 2.7
Hz, OCH2Ar), 61.90 (d, J = 6.4 Hz, OCH2), 61.64 (d, J = 6.4 Hz,
OCH2), 36.51 (d, J = 140.3 Hz, C-P), 24.11 (CH3), 16.21 (d, J =
6.2 Hz, CH3), 16.10 (d, J = 6.2 Hz, CH3); 31P NMR (162 MHz,
1
J = 7.2 Hz, 2H, Ph), 7.16-7.31 (m, 3H, Ph), 4.62 (d, J = 11.2 Hz, 80 CDCl3): δ 24.06 (s); ESI-HRMS calcd for [C23H25F3NO6P,
1H, OCH2Ph), 4.46 (d, J = 11.2 Hz, 1H, OCH2Ph), 3.92-4.08 (m,
4H, 2OCH2), 3.66 (dd, J = 18.9, 15.7 Hz, 1H, CH2-P), 2.49 (dd, J
25 = 18.9, 15.7 Hz, 1H, CH2-P), 2.29 (s, 1H, CH3), 1.19 (t, J = 7.1
Hz, 3H, CH3), 1.11 (t, J = 7.1 Hz, 3H, CH3); 13C NMR (101
M+Na]+: 522.1264; Found: 522.1266.
Diethyl
(2-(1,3-dioxoisoindolin-2-yl)-2-((4-
methylbenzyl)oxy)propyl)phosphonate (8e). Colorless oil; 1H
NMR (400 MHz, CDCl3): δ 7.78-7.83 (m, 2H, Ph), 7.68-7.73 (m,
MHz, CDCl3): δ 168.70 (C=O), 137.39, 134.14, 131.70, 128.33, 85 2H, Ph), 7.19 (d, J = 8.0 Hz, 2H, Ph), 7.06 (d, J = 8.0 Hz, 2H,
127.72, 127.55, 123.17 (Ph), 88.93 (d, J = 1.4 Hz, O-C-N), 64.76
(d, J = 1.4 Hz, OCH2Ph), 61.91 (d, J = 6.5 Hz, OCH2), 61.60 (d, J
30 = 6.5 Hz, OCH2), 36.55 (d, J = 140.0 Hz, C-P), 24.12 (CH3),
16.21 (d, J = 6.4 Hz,CH3), 16.09 (d, J = 6.4 Hz, CH3); 31P NMR
Ph), 4.56 (d, J = 11.0 Hz, 1H, OCH2Ph), 4.40 (d, J = 11.0 Hz, 1H,
OCH2Ph), 3.90-4.06 (m, 4H, 2OCH2), 3.63 (dd, J = 18.9, 15.7
Hz, 1H, CH2-P), 2.45 (dd, J = 18.9, 15.7 Hz, 1H, CH2-P), 2.26 (s,
3H, CH3), 2.25 (s, 3H, CH3), 1.18 (t, J = 7.1 Hz, 3H, CH3), 1.10
(162 MHz, CDCl3):
δ
24.34 (s). ESI-HRMS calcd for 90 (t, J = 7.1 Hz, 3H, CH3); 13C NMR (101 MHz, CDCl3): δ 168.68
[C22H26NO6P, M+Na]+: 454.1390; Found: 454.1393.
Diethyl(2-(1,3-dioxoisoindolin-2-yl)-2-((4-
(s, C=O), 137.25, 134.31, 134.06, 131.73, 128.99, 127.82, 123.12
(Ph), 88.85 (O-C-N), 64.70 (d, J = 2.6 Hz, OCH2Ar ), 61.88 (d, J
= 6.3 Hz, OCH2), 61.57 (d, J = 6.3 Hz, OCH2), 36.60 (d, J =
140.0 Hz, C-P), 24.10 (CH3), 21.09 (CH3), 16.20 (d, J = 6.5 Hz,
35 fluorobenzyl)oxy)propyl)phosphonate (8b). Light yellow oil;
1H NMR (400 MHz, CDCl3): δ 7.80-7.87 (m, 2H, Ph), 7.69-7.78
(m, 2H, Ph), 7.26-7.38 (m, 2H, Ph), 6.96 (t, J = 8.7 Hz, 2H, Ph), 95 CH3), 16.08 (d, J = 6.5 Hz, CH3); 31P NMR (162 MHz, CDCl3): δ
4.58 (d, J = 11.0 Hz, 1H, OCH2Ar), 4.41 (d, J = 11.0 Hz, 1H,
OCH2Ar), 3.91-4.09 (m, 4H, 2OCH2), 3.61 (dd, J = 18.9, 15.7
40 Hz, 1H, CH2-P), 2.47 (dd, J = 18.9, 15.7 Hz, 1H, CH2-P), 2.27 (s,
1H, CH3), 1.19 (t, J = 7.1 Hz, 3H, CH3), 1.11 (t, J = 7.1 Hz, 3H,
24.40 (s); ESI-HRMS calcd for [C23H28NO6P, M+Na]+:
468.1546; Found: 468.1545.
Diethyl(2-(1,3-dioxoisoindolin-2-yl)-2-((2,4,6-
trimethylbenzyl)oxy)propyl)phosphonate (8f). Colorless oil;
CH3); 13C NMR (101 MHz, CDCl3): δ 168.68 (C=O), 162.25 (d, 100 1H NMR (400 MHz, CDCl3): δ 7.86-7.91 (m, 2H, Ph), 7.73-7.79
J = 245.5 Hz, C-F), 134.20 (Ph), 133.14 (d, J = 3.0 Hz, Ar),
131.66 (Ph), 129.50 (d, J = 8.1 Hz, Ar), 123.18 (Ph), 115.16 (d, J
45 = 3.0 Hz, Ar), 88.94 (d, J = 1.5 Hz, O-C-N), 64.06 (d, J = 2.6 Hz,
OCH2Ph), 61.91 (d, J = 6.5 Hz, OCH2), 61.61 (d, J = 6.5 Hz,
(m, 2H, Ph), 6.82 (s, 2H, Ph), 4.63 (d, J = 9.4 Hz, 1H, OCH2Ar),
4.34 (d, J = 9.4 Hz, 1H, OCH2Ar), 3.93-4.10 (m, 4H, 2OCH2),
3.65-3.78 (m, 1H, CH2-P), 2.38-2.45 (m, 1H, CH2-P), 2.36 (s, 3H,
CH3), 2.29 (s, 6H, 2CH3), 2.23 (s, 1H, CH3), 1.18 (t, J = 7.0 Hz,
OCH2), 36.52 (d, J = 140.1 Hz, C-P), 24.10 (CH3), 16.20 (d, J = 105 3H, CH3), 1.10 (t, J = 7.0 Hz, 1H, CH3). 13C NMR (101 MHz,
6.4 Hz, CH3), 16.08 (d, J = 6.4 Hz, CH3); 31P NMR (162 MHz,
CDCl3): δ 24.20 (s); ESI-HRMS calcd for [C22H25FNO6P,
50 M+Na]+: 472.1296; Found: 472.1298.
CDCl3): δ 168.80 (C=O), 138.00, 137.88, 134.18, 131.73, 129.94,
129.04, 123.18 (Ph), 88.47 (O-C-N), 61.81 (d, J = 6.5 Hz, OCH2),
61.50 (d, J = 6.5 Hz, OCH2), 58.58 (d, J = 2.8 Hz, CH2Ar), 36.43
(d, J = 139.0 Hz, C-P), 23.77 (CH3), 20.96 (CH3), 19.35 (CH3),
Diethyl
(2-(1,3-dioxoisoindolin-2-yl)-2-((4-
nitrobenzyl)oxy)propyl)phosphonate (8c). Colorless oil; 1H 110 16.19 (d, J = 6.5 Hz, CH3), 16.09 (d, J = 6.5 Hz, CH3). 31P NMR
NMR (400 MHz, CDCl3): δ 8.17 (d, J = 7.7 Hz, 2H, Ph), 7.83-
7.87 (m, 2H, Ph), 7.71-7.78 (m, 2H, Ph), 7.55 (d, J = 7.7 Hz , 2H,
55 Ph), 4.74 (d, J = 12.7 Hz, 1H, OCH2Ar), 4.58 (d, J = 12.7 Hz, 1H,
OCH2Ar), 3.97-4.08 (m, 4H, 2OCH2), 3.64 (dd, J = 19.8 , 15.8
(162 MHz, CDCl3): δ 24.58 (s); ESI-HRMS calcd for
[C25H32NO6P, M+Na]+: 496.1859; Found: 496.1862.
Diethyl(2-(1,3-dioxoisoindolin-2-yl)-2-((4-
methoxybenzyl)oxy)propyl)phosphonate (8g). Colorless oil; 1H
Hz, 1H, CH2-P), 2.53 (dd, J = 19.8, 15.8, 1H, CH2-P), 2.29 (s, 115 NMR (400 MHz, CDCl3): δ 7.80-7.85 (m, 2H, Ph), 7.68-7.74 (m,
3H, CH3), 1.22 (t, J = 7.1 Hz, 3H, CH3), 1.14 (t, J = 7.1 Hz, 3H,
2H, Ph), 7.23 (d, J = 8.7 Hz, 2H, Ph), 6.79 (d, J = 8.7 Hz, 2H,
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Journal Name, [year], [vol], 00–00 | 5

Organic & Biomolecular Chemistry
Page 6 of 8
Ph), 4.54 (d, J = 10.8 Hz, 1H, OCH2Ph), 4.37 (d, J = 10.8 Hz, 1H,
CH2-P), 2.21 (s, 1H, CH3), 1.23 (t, J = 7.1 Hz, 3H, CH3), 1.12 (t,
OCH2Ph), 3.93-4.05 (m, 4H, 2OCH2), 3.74 (s, 3H, OMe), 3.61 60 J = 7.1 Hz, 3H, CH3); 13C NMR (101 MHz, CDCl3): δ 168.31
View Article Online
(dd, J = 18.9, 15.7 Hz, 1H, CH2-P), 2.45 (dd, J = 18.9, 15.7 Hz,
1H, CH2-P), 2.26 (s, 3H, CH3), 1.17 (t, J = 7.1 Hz, 3H, CH3),
1.09 (t, J = 7.1 Hz, 3H, CH3); 13C NMR (101 MHz, CDCl3): δ
168.68 (C=O), 159.12, 134.06, 131.75, 129.46, 129.32, 123.12,
(C=O), 134.41, 131.50, 123.41 (Ph), 89.22 D(NO-I:C1-0O.1)0,6319./9C63O(dB,4J09=41D
6.5 Hz, OCH2), 61.79 (d, J = 6.5 Hz, OCH2), 61.03 (d, J = 3.2
Hz, OCH2), 60.67 (d, J = 2.9 Hz, CF3), 35.93 (d, J = 140.8 Hz, C-
P), 23.84 (CH3), 16.21 (d, J = 6.3 Hz, CH3), 16.07 (d, J = 6.3 Hz,
5
113.75 (Ph), 88.84 (O-C-N), 64.50 (d, J = 2.4 Hz, OCH2Ar), 65 CH3); 31P NMR (162 MHz, CDCl3): δ 23.38 (s); ESI-HRMS
61.88 (d, J = 6.4 Hz, OCH2), 61.56 (d, J = 6.4 Hz, OCH2), 55.23
(OCH3), 36.62 (d, J = 139.8 Hz, C-P), 24.10 (CH3), 16.20 (d, J =
calcd for [C17H21F3NO6P, M+Na]+: 446.0951; Found: 446.0954.
Diethyl (2-butoxy-2-(1,3-dioxoisoindolin-2-
10 6.4 Hz, CH3), 16.08 (d, J = 6.4 Hz, CH3); 31P NMR (162 MHz,
yl)propyl)phosphonate (8l). Colorless oil; H NMR (400 MHz,
CDCl3): δ 7.82-7.86 (m, 2H, Ph), 7.70-7.74 (m, 2H, Ph), 3.93-
70 4.07 (m, 4H, 2OCH2), 3.49-3.59 (m, 2H, OCH2, CH2-P), 3.25 (dt,
J = 8.6, 6.6 Hz, 1H, OCH2), 2.38 (dd, J = 19.6, 15.5 Hz, 1H, CH2-
P), 2.15 (s, 3H, CH3), 1.48-1.55 (m, 2H, CH2), 1.28-1.34 (m, 2H,
CH2), 1.20 (t, J = 7.1 Hz, 3H, CH3), 1.10 (t, J = 7.1 Hz, 3H, CH3),
0.85 (t, J = 7.4 Hz, 3H, CH3); 13C NMR (101 MHz, CDCl3): δ
1
CDCl3):
M+Na]+: 484.1501; Found: 484.1504.
Diethyl (2-(1,3-dioxoisoindolin-2-yl)-2-
δ 24.37 (s); ESI-HRMS calcd for [C23H28NO7P,
1
methoxypropyl)phosphonate (8h). Colorless oil; H NMR (400
15 MHz, CDCl3): δ 7.83-7.86 (m, 2H, Ph), 7.70-7.74 (m, 2H, Ph),
3.94-4.07 (m, 4H, 2OCH2), 3.50 (dd, J = 19.6, 15.5 Hz, 1H, CH2-
P), 3.26 (s, 3H, OCH3), 2.38 (dd, J = 19.6, 15.5 Hz, 1H, CH2-P), 75 168.68 (C=O), 134.05, 131.71, 123.09 (Ph), 88.62 (O-C-N),
2.14 (s, 3H, CH3), 1.19 (t, J = 7.1 Hz, 3H, CH3), 1.11 (t, J = 7.1
Hz, 3H, CH3); 13C NMR (101 MHz, CDCl3): δ 168.72 (C=O),
20 134.14, 131.72, 123.18 (Ph), 89.08 (O-C-N), 61.88 (d, J = 6.6Hz,
OCH2), 61.60 (d, J = 6.6Hz, OCH2), 49.78 (d, J = 2.8 Hz, OCH3),
61.99 (OCH2), 61.78 (d, J = 6.5 Hz, OCH2), 61.50 (d, J = 6.5 Hz,
OCH2), 36.44 (d, J = 140.0 Hz, C-P), 31.65 (CH2), 23.87 (CH3),
19.24 (CH2), 16.18 (d, J = 6.4 Hz, CH3), 16.05 (d, J = 6.4 Hz,
CH3), 13.78 (CH3); 31P NMR (162 MHz, CDCl3): δ 24.56 (s);
36.31 (d, J = 140.7 Hz, C-P), 23.19 (CH3), 16.20 (d, J = 6.4 80 ESI-HRMS calcd for [C19H28NO6P, M+Na]+: 420.1546; Found:
Hz,CH3), 16.09 (d, J = 6.4 Hz, CH3); 31P NMR (162 MHz,
CDCl3): 24.36 (s); ESI-HRMS calcd for [C16H22NO6P,
25 M+Na]+: 378.1077; Found: 378.1073.
Diethyl (2-(1,3-dioxoisoindolin-2-yl)-2-
420.1543.
δ
Diethyl
(2-(1,3-dioxoisoindolin-2-yl)-2-
isobutoxypropyl)phosphonate (8m). Colorless oil; 1H NMR
(400 MHz, CDCl3): δ 7.82-7.85 (m, 2H, Ph), 7.70-7.74 (m, 2H,
ethoxypropyl)phosphonate (8i). Colorless oil; 1H NMR (400 85 Ph), 3.92-4.07 (m, 4H, 2OCH2), 3.59 (dd, J = 18.9, 15.7 Hz, 1H,
MHz, CDCl3): δ 7.82-7.85 (m, 2H, Ph), 7.70-7.73 (m, 2H, Ph),
3.90-4.09 (m, 4H, 2OCH2), 3.61 (dq, J = 14.1, 7.0 Hz, 1H,
30 OCH2), 3.50 (dd, J = 19.0, 15.6 Hz, 1H, CH2-P), 3.35 (dq, J =
14.1, 7.0 Hz, 1H, OCH2), 2.40 (dd, J = 19.0, 15.6 Hz, 1H, CH2-
CH2-P), 3.30 (dd, J = 8.4, 6.7 Hz, 1H, OCH2), 2.99 (dd, J = 8.4,
6.7 Hz, 1H, OCH2), 2.38 (dd, J = 18.9, 15.7 Hz, 1H, CH2-P), 2.15
(s, 3H, CH3), 1.73-1.84 (m, 1H, CH), 1.20 (t, J = 7.1 Hz, 3H,
CH3), 1.10 (t, J = 7.1 Hz, 3H, CH3), 0.86 (dd, J = 12.6, 6.7 Hz,
P), 2.15 (s, 3H, CH3), 1.19 (dt, J = 10.1, 7.0 Hz, 6H, 2CH3), 1.10 90 6H, 2CH3); 13C NMR (101 MHz, CDCl3): δ 168.72 (C=O),
(t, J = 7.1 Hz, 3H, CH3); 13C NMR (101 MHz, CDCl3): δ 168.71
(C=O), 134.08, 131.76, 123.14 (Ph), 88.77 (O-C-N), 61.84 (d, J =
35 6.4 Hz, OCH2), 61.56 (d, J = 6.4 Hz, OCH2), 57.85 (d, J = 2.5
Hz, OCH2), 36.54 (d, J = 139.9 Hz, C-P), 23.96 (CH3), 16.23 (d,
134.06, 131.72, 123.11 (Ph), 88.52 (O-C-N), 68.92 (d, J = 2.3 Hz,
OCH2), 61.77 (d, J = 6.4 Hz, OCH2), 61.50 (d, J = 6.4 Hz,
OCH2), 36.39 (d, J = 139.7 Hz, C-P), 28.36 (CH), 23.90 (CH3),
19.47 (CH3), 19.44(CH3), 16.20 (d, J = 6.5 Hz, CH3), 16.07 (d, J
J = 6.4 Hz, CH3), 16.10 (d, J = 6.4 Hz, CH3), 15.22 (CH3); 31P 95 = 6.5 Hz, CH3); 31P NMR (162 MHz, CDCl3): δ 24.64 (s); ESI-
NMR (162 MHz, CDCl3): δ 24.48 (s); ESI-HRMS calcd for
HRMS calcd for [C19H28NO6P, M+Na]+: 420.1552; Found:
420.1554.
[C17H24NO6P, M+Na]+: 392.1233; Found: 392.1231.
40 Diethyl
yl)propyl)phosphonate (8j). Colorless oil; H NMR (400 MHz,
CDCl3): δ 7.83-7.86 (m, 2H, Ph), 7.72-7.75 (m, 2H, Ph), 3.93- 100 (400 MHz, CDCl3): δ 7.83-7.88 (m, 2H, Ph), 7.71-7.75 (m, 2H,
(2-(2-chloroethoxy)-2-(1,3-dioxoisoindolin-2-
Diethyl
(2-(1,3-dioxoisoindolin-2-yl)-2-
1
(hexyloxy)propyl)phosphonate (8n). Colorless oil; 1H NMR
4.05 (m, 4H, 2OCH2), 3.76-3.83 (m, 1H, OCH2), 3.57-3.63 (m,
3H, OCH2, CH2Cl), 3.54 (dd, J = 13.8, 10.9 Hz, 1H, CH2-P), 2.40
45 (dd, J = 19.6, 15.5 Hz, 1H, CH2-P), 2.17 (s, 3H, CH3), 1.20 (t, J =
7.1 Hz, 3H, CH3), 1.11 (t, J = 7.1 Hz, 3H, CH3); 13C NMR (101
Ph), 3.94-4.07 (m, 4H, 2OCH2), 3.50-3.62 (m, 2H, OCH2, CH2-
P), 3.23-3.30 (m, 1H, OCH2), 2.39 (dd, J = 19.6, 15.4 Hz, 1H,
CH2-P), 2.17 (s, 3H, CH3), 1.50-1.60 (m, 2H, CH2), 1.19-1.30 (m,
9H, 3CH2, CH3), 1.12 (t, J = 7.1 Hz, 3H, CH3), 0.84 (t, J = 6.9
MHz, CDCl3): δ 168.57 (C=O), 134.22, 131.66, 123.24 (Ph), 105 Hz, 3H, CH3); 13C NMR (101 MHz, CDCl3): δ 168.71 (C=O),
88.93 (O-C-N), 63.01 (d, J = 2.7 Hz, OCH2), 61.87 (d, J = 6.3
Hz, OCH2), 61.66 (d, J = 6.3 Hz, OCH2), 42.38 (CH2Cl), 36.25
50 (d, J = 140.4 Hz, C-P), 24.01 (CH3), 16.22 (d, J = 6.5 Hz, CH3),
16.09 (d, J = 6.5 Hz, CH3); 31P NMR (162 MHz, CDCl3): δ 24.03
134.05, 131.74, 123.10 (Ph), 88.65 (O-C-N), 62.32 (d, J = 2.2 Hz,
OCH2), 61.80 (d, J = 6.4 Hz, OCH2), 61.53 (d, J = 6.4 Hz,
OCH2), 36.46 (d, J = 139.8 Hz, C-P), 31.52 (CH2), 29.55 (CH2),
25.68 (CH2), 23.91 (CH3), 22.53 (CH2), 16.21 (d, J = 6.5 Hz,
(s); ESI-HRMS calcd for [C17H23ClNO6P, M+Na]+: 426.0844; 110 CH3), 16.07 (d, J = 6.5 Hz, CH3), 13.98 (CH3); 31P NMR (162
Found: 426.0839.
Diethyl
MHz, CDCl3): δ 24.57 (s); ESI-HRMS calcd for [C21H32NO6P,
(2-(1,3-dioxoisoindolin-2-yl)-2-(2,2,2-
M+Na]+: 448.1859; Found: 448.1851.
55 trifluoroethoxy)propyl)phosphonate (8k). Colorless oil; 1H
NMR (400 MHz, CDCl3): δ 7.84-7.90 (m, 2H, Ph), 7.73-7.80 (m,
Diethyl
(2-(decyloxy)-2-(1,3-dioxoisoindolin-2-
1
yl)propyl)phosphonate (8o). Colorless oil; H NMR (400 MHz,
2H, Ph), 3.90-4.13 (m, 5H, 2OCH2, OCH2CF3), 3.75-3.84 (m, 115 CDCl3): δ 7.81-7.85 (m, 2H, Ph), 7.69-7.73 (m, 2H, Ph), 3.92-
1H, OCH2CF3), 3.61-3.72 (m, 1H, CH2-P), 2.37-2.50 (m, 1H,
4.06 (m, 4H, 2OCH2), 3.48-3.60 (m, 2H, OCH2, CH2-P), 3.21-
6
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Organic & Biomolecular Chemistry
3.28 (m, 1H, OCH2), 2.37 (dd, J = 19.7, 15.5 Hz, 1H, CH2-P),
(s, 3H, CH3); 13C NMR (101 MHz, CDCl3): δ 168.72 (C=O),
2.15 (s, 3H, CH3), 1.48-1.58 (m, 2H, CH2), 1.15-1.31 (m, 17H, 60 137.32, 134.17, 131.62, 128.34, 127.71, 127.57, 123.20 (Ph),
7CH2, CH3), 1.10 (t, J = 7.1 Hz, 3H, CH3), 0.87 (t, J = 6.9 Hz,
3H, CH3); 13C NMR (101 MHz, CDCl3): δ 168.72 (C=O), 134.03,
131.78, 123.12 (Ph), 88.68 (O-C-N), 62.34 (d, J = 2.0 Hz, OCH2),
61.80 (d, J = 6.5 Hz, OCH2), 61.53 (d, J = 6.5 Hz, OCH2), 36.50
88.91 (O-C-N), 64.90 (d, J = 2.5 Hz, OCDHO2IP:h1)0,.15023V.95ie/5wC(3AdOr,tBicJ4le0=O9n46l1.in5De
Hz, OCH3), 52.33 (d, J = 6.5 Hz, OCH3), 35.58 (d, J = 140.2 Hz,
C-P), 24.19 (CH3); 31P NMR (162 MHz, CDCl3): δ 27.09 (s);
ESI-HRMS calcd for [C20H22NO6P, M+Na]+: 426.1077; Found:
5
(d, J = 140.0 Hz, C-P), 31.88 (CH2), 29.61 (CH2), 29.54 (CH2), 65 426.1076.
29.35 (CH2), 29.29 (CH2), 26.02 (CH2), 23.93 (CH3), 22.66
Dimethyl
(2-(1,3-dioxoisoindolin-2-yl)-2-((4-
(CH2), 16.23 (d, J = 6.5 Hz, CH3), 16.09 (d, J = 6.5 Hz, CH3),
fluorobenzyl)oxy)propyl)phosphonate (8u). Colorless oil; 1H
NMR (400 MHz, CDCl3): δ 7.82-7.87 (m, 2H, Ph), 7.71-7.77 (m,
2H, Ph), 7.25-7.35 (m, 2H, Ph), 6.93-7.01 (m, 2H, Ph), 4.58 (d, J
70 = 11.0 Hz, 1H, OCH2Ar), 4.43 (d, J = 11.0 Hz, 1H, OCH2Ar),
3.66 (d, J = 11.0 Hz, 3H, OCH3), 3.61 (d, J = 11.0 Hz, 3H,
OCH3), 3.55 (dd, J = 16.6, 13.5 Hz, 1H, CH2-P), 2.56 (dd, J =
19.7, 15.5 Hz, 1H, CH2-P), 2.27 (s, 3H, CH3); 13C NMR (101
MHz, CDCl3): δ 168.70 (C=O), 162.27 (d, J = 245.6 Hz, Ph),
10 14.11 (CH3); 31P NMR (162 MHz, CDCl3): δ 24.59 (s); ESI-
HRMS calcd for [C25H40NO6P, M+Na]+: 504.2485; Found:
504.2487.
Diethyl
(2-(1,3-dioxoisoindolin-2-yl)-2-
isopropoxypropyl)phosphonate (8p). Colorless oil; 1H NMR
15 (400 MHz, CDCl3): δ 7.82-7.87 (m, 2H), 7.69-7.75 (m, 2H),
3.92-4.08 (m, 5H, 2OCH2, CH), 3.61-3.75 (dd, J = 19.7, 15.5 Hz,
1H, CH2-P), 2.33 (dd, J = 19.7, 15.5 Hz, 1H, CH2-P), 2.20 (s, 3H, 75 134.24 (Ph), 133.06 (d, J = 3.1 Hz, Ar), 131.57 (s, Ph), 129.50 (d,
CH3), 1.21 (t, J = 6.8 Hz, 6H, 2CH3), 1.09 (t, J = 7.0 Hz, 3H,
CH3), 1.01 (d, J = 6.1 Hz, 3H, CH3); 13C NMR (101 MHz,
20 CDCl3): δ 169.02 (C=O), 134.08, 131.79, 123.13 (Ph), 88.55 (O-
C-N), 65.82 (d, J = 2.6 Hz, OCH), 61.74 (d, J = 6.5 Hz, OCH2),
J = 7.9 Hz, Ar), 123.22 (Ph), 115.18 (d, J = 21.5 Hz, Ar), 88.92
(O-C-N), 64.22 (d, J = 2.2 Hz, OCH2Ar), 52.56 (d, J = 6.6 Hz,
OCH3), 52.34 (d, J = 6.6 Hz, OCH3), 35.55 (d, J = 140.3 Hz, C-
P), 24.17 (CH3); 31P NMR (162 MHz, CDCl3): δ 26.95 (s); ESI-
61.46 (d, J = 6.5 Hz, OCH2), 36.88 (d, J = 139.2 Hz, C-P), 25.00 80 HRMS calcd for [C20H21FNO6P, M+Na]+: 444.0983; Found:
(CH3), 24.55 (CH3), 23.60 (CH3), 16.23 (d, J = 6.4 Hz, CH3),
16.07 (d, J = 6.4 Hz, CH3). 31P NMR (162 MHz, CDCl3): δ 24.55
25 (s); ESI-HRMS calcd for [C18H26NO6P, M+Na]+: 406.1390;
Found: 406.1394.
444.0982.
Diethyl
(2-(1,3-dioxoisoindolin-2-yl)-2-methoxy-3-
1
phenylpropyl)phosphonate (8v). Colorless oil; H NMR (400
MHz, CDCl3): δ 7.82-7.90 (m, 2H, Ph), 7.73-7.80 (m, 2H, Ph),
Diethyl
(2-(cyclohexyloxy)-2-(1,3-dioxoisoindolin-2- 85 7.40 (d, J = 6.9 Hz, 1H, Ph), 7.25-7.30 (m, 3H, Ph), 3.97-4.17 (m,
1
yl)propyl)phosphonate (8q). Colorless oil; H NMR (400 MHz,
CDCl3): δ 7.84-7.87 (m, 2H, Ph), 7.70-7.73 (m, 2H, Ph), 3.92-
30 4.08 (m, 4H, 2OCH2), 3.58-3.76 (m, 2H, CH, CH2P), 2.34 (dd, J
= 19.2, 16.0, Hz, 1H, CH2P), 2.20 (s, 3H, CH3), 1.29-1.88 (m,
6H, 2OCH2, CH2Ph), 3.45 (s, 3H, OCH3), 3.18-3.31 (m, 1H,
CH2-P), 2.52-2.68 (m, 1H, CH2-P), 1.29 (t, J = 7.0 Hz, 3H, CH3),
1.18 (t, J = 7.0 Hz, 3H, CH3); 13C NMR (101 MHz, CDCl3): δ
168.60 (C=O), 135.75, 134.24, 131.51, 130.89, 128.27, 126.92,
8H, 4CH2). 1.07-1.22 (m, 8H, CH2, 2CH3); 13C NMR (101 MHz, 90 123.24 (Ph), 92.91 (N-C-O), 61.97 (d, J = 6.5 Hz, OCH2), 61.53
CDCl3): δ 169.01 (C=O), 134.05, 131.81, 123.14 (Ph), 88.50 (O-
C-N), 71.86 (CH), 61.73 (d, J = 6.3 Hz, OCH2), 61.44 (d, J = 6.3
35 Hz, OCH2), 36.91 (d, J = 138.7 Hz, C-P), 34.69 (CH2), 33.73
(CH2), 25.35 (CH2), 25.07 (CH2), 24.52 (CH2), 24.48 (CH3),
(d, J = 6.5 Hz, OCH2), 50.45 (s, OCH3), 38.88 (CH2Ph), 31.12 (d,
J = 141.4 Hz, C-P), 16.34 (d, J = 6.3 Hz, CH3), 16.16 (d, J = 6.3
Hz, CH3); 31P NMR (162 MHz, CDCl3): δ 24.40 (s); ESI-HRMS
calcd for [C22H26NO6P, M+Na]+: 454.1390; Found: 454.1394.
16.23 (d, J = 6.4 Hz, CH3), 16.07 (d, J = 6.4 Hz, CH3); 31P NMR 95 Diethyl
(2-(1,3-dioxoisoindolin-2-yl)-2-methoxy-3-
(162 MHz, CDCl3):
[C21H30NO6P, M+Na]+: 446.1703; Found: 446.1702.
40 Dimethyl (2-(1,3-dioxoisoindolin-2-yl)-2-
methoxypropyl)phosphonate (8s). Colorless oil; H NMR (400
δ
24.63 (s); ESI-HRMS calcd for
methylbutyl)phosphonate (8w). Colorless oil; 1H NMR (400
MHz, CDCl3): δ 7.81-7.86 (m, 2H, Ph), 7.70-7.74 (m, 2H, Ph),
4.05-4.19 (m, 4H, 2OCH2), 3.51 (s, 3H, OCH3), 3.26 (dd, J =
20.3, 16.1 Hz, 1H, CH2-P), 2.83-3.00 (m, 2H, CH2-P, CH), 1.29
1
MHz, CDCl3): δ 7.82-7.87 (m, 2H, Ph), 7.71-7.75 (m, 2H, Ph), 100 (t, J = 7.0 Hz, 6H, 2CH3), 1.07 (t, J = 7.0 Hz, 6H, 2CH3); 13C
3.67 (d, J = 11.0 Hz, 3H, OCH3), 3.61 (d, J = 11.0 Hz, 3H,
OCH3), 3.44 (dd, J = 19.1, 15.6 Hz, 1H, CH2-P), 3.27 (s, 3H,
45 OCH3), 2.47 (dd, J = 19.1, 15.6 Hz, 1H, CH2-P), 2.14 (s, 3H,
CH3); 13C NMR (101 MHz, CDCl3): δ 168.74 (C=O), 134.20,
NMR (101 MHz, CDCl3): δ 169.18 (C=O), 133.97, 131.78,
123.00 (Ph), 96.61 (O-C-N), 61.87 (d, J = 6.4 Hz, OCH2), 61.53
(d, J = 6.4 Hz, OCH2), 53.04 (OCH3), 37.25 (d, J = 5.7 Hz, CH),
30.99 (d, J = 142.1 Hz, C-P), 18.05 (CH3), 17.40 (CH3), 16.33 (d,
131.63, 123.22 (Ph), 89.08 (O-C-N), 52.54 (d, J = 6.5 Hz, OCH3), 105 J = 5.5 Hz, CH3), 16.28 (d, J = 5.5 Hz, CH3); 31P NMR (162
52.34 (d, J = 6.5 Hz, OCH3), 49.96 (d, J = 2.6 Hz, OCH3), 35.35
(d, J = 141.0 Hz, C-P), 23.31 (CH3); 31P NMR (162 MHz,
MHz, CDCl3): δ 25.56 (s); ESI-HRMS calcd for [C18H26NO6P,
M+Na]+: 406.1390; Found: 406.1392.
50 CDCl3):
δ
27.08 (s); ESI-HRMS calcd for [C14H18NO6P,
M+Na]+: 350.0764; Found: 350.0763.
Dimethyl (2-(benzyloxy)-2-(1,3-dioxoisoindolin-2- 110 MHz, CDCl3): δ 7.83-7.87 (m, 2H, Ph), 7.73-7.76 (m, 2H, Ph),
Diethyl
(2-(1,3-dioxoisoindolin-2-yl)-2-methoxy-4-
methylpentyl)phosphonate (8x). Colorless oil; 1H NMR (400
1
yl)propyl)phosphonate (8t). Colorless oil; H NMR (400 MHz,
CDCl3): δ 7.81-7.85 (m, 2H, Ph), 7.68-7.74 (m, 2H, Ph), 7.32 (d,
55 J = 7.2 Hz, 2H, Ph), 7.24-7.28 (m, 2H, Ph), 7.20 (t, J = 7.1 Hz,
1H, Ph), 4.61 (d, J = 11.2 Hz, 1H, OCH2Ph), 4.45 (d, J = 11.2 Hz,
3.99-4.11 (m, 4H, 2OCH2), 3.46 (dd, J = 19.1, 16.5 Hz, 1H, CH2-
P), 3.27 (s, 3H, OCH3), 2.67-2.84 (m, 2H, CH2-P, CH2), 2.52 (dd,
J = 15.1, 7.2, Hz, 1H, CH2), 1.92-2.01 (m, 1H, CH), 1.24 (t, J =
7.1 Hz, 3H, CH3), 1.20 (t, J = 7.1 Hz, 3H, CH3), 1.07 (d, J = 6.6
1H, OCH2Ph), 3.64 (d, J = 11.0 Hz, 3H, OCH3), 3.53-3.62 (m, 115 Hz, 3H, CH3), 1.03 (d, J = 6.6 Hz, 3H, CH3); 13C NMR (101
4H, OCH3, CH2-P), 2.55 (dd, J = 19.7, 15.5 Hz, 1H, CH2-P), 2.26
MHz, CDCl3): δ 168.90 (C=O), 134.12, 131.59, 123.14 (Ph),
This journal is © The Royal Society of Chemistry [year]
Journal Name, [year], [vol], 00–00 | 7

Organic & Biomolecular Chemistry
Page 8 of 8
65
70
75
80
85
90
95
H. Xie and Q. L. Zhou, Nature Chem., 2010, 2, 546; (h) T. C. Maier
and G. C. Fu, J. Am. Chem. Soc., 2006, 128, 4594.
R. H. Crabtree, The Organometallic Chemistry of the Transition
93.38 (O-C-N), 61.76 (d, J = 6.5 Hz, OCH2), 61.56 (d, J = 6.5
Hz, OCH2), 49.99 (d, J = 2.0 Hz, OCH3), 40.66 (CH2), 31.59 (d, J
= 142.3 Hz, C-P), 24.40 (CH3), 24.22 (CH3), 23.10 (CH), 16.29
(d, J = 6.5 Hz, CH3), 16.20 (d, J = 6.5 Hz, CH3); 31P NMR (162
MHz, CDCl3): δ 24.52 (s); ESI-HRMS calcd for [C19H28NO6P,
M+Na]+: 420.1546; Found: 420.1550.
5
6
View Article Online
DOI: 10.1039/C3OB40941D
Metals; 4th ed.; Wiley-Interscience, 2005, Vol. 11.
For recent review see the following: (a) F. Palacios, C. Alonso and
J. M. de los Santos, Chem. Rev., 2005, 105, 899; (b) F. Palacios, C.
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5
Acknowledgments
7
We thank the National Natural Science Foundation of China
(21072102), the Committee of Science and Technology of
10 Tianjin (11JCYBJC04200) and State Key Laboratory of
Elemento-Organic Chemistry in Nankai University for financial
support.
8
9
Notes and references
a
State Key Laboratory and Institute of Elemento-Organic Chemistry,
15 Nankai University, Tianjin 300071, China. Fax: +86 2350 2351; Tel:
+86 2350 4783; E-mail: miaozhiwei@nankai.edu.cn
b Key Laboratory of Bioorganic Phosphorus Chemistry & Chemical
Biology (Ministry of Education), Tsinghua University, Beijing 100084,
China
20 † Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/b000000x/
‡ In Memory of Prof. Ruyu Chen in Response to her contribution of
organophosphorus chemistry in China.
25 1
Selected recent reviews on C-H activation see: (a) D. A. Colby, R.
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35
13 It is well documented that most transition metal alkyl carbenes
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In some cases the use of low reaction temperatures and sterically
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hydride elimination. For recent successful Rh(I)-catalyzed reactions
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14 See the supporting information for details on the crystal structure of
9a. Crystallographic data for the structural analysis of compound 9a
has been deposited at the Cambridge Crystallographic Data Centre
as No. CCDC 893994. These data can be obtained free of charge by
contacting The Cambridge Crystallographic Data Centre, 12, Union
Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033; E-mail:
deposit@ccdc.cam.ac.uk.
2
For reviews see: (a) M. P. Doyle, R. Duffy, M. Ratnikov, L. Zhou
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3
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50
125 15 M. P. Doyle, L. J. Westrum, W. N. E. Wolthuis, M. M. See, W. P.
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55 4
For representative recent examples of O-H insertion see: (a) H. E.
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60
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