Controllable phosphorylation of thioesters: Selective synthesis of aryl and benzyl phosphoryl compounds

Article abstract of DOI:10.1021/acs.joc.0c01557

The controllable phosphorylations of thioesters were developed. When the reaction was catalyzed by a palladium catalyst, aryl or alkenyl phosphoryl compounds were generated through decarbonylative coupling, while the benzyl phosphoryl compounds were produced through deoxygenative coupling when the reaction was carried out in the presence of only a base.

Full text of DOI:10.1021/acs.joc.0c01557

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Article
Controllable Phosphorylation of Thioesters: Selective
Synthesis of Aryl and Benzyl Phosphoryl Compounds
Kaiqiang Xu, Long Liu, Zhaohui Li, Tianzeng Huang, Kang Xiang, and Tieqiao Chen
J. Org. Chem., Just Accepted Manuscript • Publication Date (Web): 14 Sep 2020
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The Journal of Organic Chemistry
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Controllable Phosphorylation of Thioesters: Selective Synthesis of
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Aryl and Benzyl Phosphoryl Compounds
Kaiqiang Xu,† Long Liu,† Zhaohui Li, Tianzeng Huang, Kang Xiang, and Tieqiao Chen*
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Key Laboratory of Ministry of Education for Advanced Materials in Tropical Island Resources, Hainan Provincial Key Lab
of Fine Chem, Hainan Provincial Fine Chemical Engineering Research Center, Hainan University, Haikou, 570228, China.
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† K.X. and L.L. contributed equally to this work.
cat. [Pd]
- CO
24 examples
up to 96 % yield
Ar P(O)Z1Z2
O
HP(O)Z1Z2
Ar
SR
base
24 examples
up to 95 % yield
Ar
P(O)Z1Z2
ABSTRACT
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The controllable phosphorylations of thioesters were developed. When the reaction was catalyzed by a palladium
catalyst, aryl or alkenyl phosphoryl compounds were generated through decarbonylative coupling; while the benzyl
phosphoryl compounds would be produced through deoxygenative coupling when the reaction was carried out in the
presence of only a base.
INTRODUCTION
Thioesters widely occur in natural products. They are also readily available in the synthetic world. Naturally,
thioesters are important active intermediates of citric acid cycle and acyl transfer in biochemical process.1 Perhaps
being inspired by the cognition, synthetic chemists activated carboxylic acids by pre-transforming them into thioesters,
which were then used in organic synthesis.2 This imagination would not only enable the readily available carboxylic
acids as the indirect building blocks, but also greatly facilitate direct modification of functional molecules bearing
thioester units. However, probably due to the strong metal-sulfur bonds easily leading to deactivation of metal
catalysts,3 the research in this field is relatively limited. Nevertheless, many reactions for synthesizing ketones,4
aldehydes,5 and amides6 were developed with the strategy (Scheme 1A). Through transition metal catalysis, aromatic
thioesters could also undergo intramolecular decarbonylation producing the corresponding thioethers (Scheme 1B).7
The decarbonylative borylation forming aryl or alkenyl borons was also achieved through rhodium catalysis by Hosoya
and Niwa in 2017 (Scheme 1B).8 More effort is still required to enrich the chemistry of thioesters.
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A. Non-decarbonylative process
B. Decarbonylative process
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cat. M
ketones
O
Ar SAr
Ar Bpin
O
cat. M
aldehydes
cat. Rh
(Bpin)2
Ar
SAr
R
SR1
amides
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D. Transformation of carboxylic acids
and their derivatives
C. Tradditional methods forming
P(O)-C bonds
For aryl phosphoryl compounds
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O
P(O)-X
Li or Mg
P(O)-H
R-Li or RMgX
P(O)-Ar
cat. M
Ar
ZR
1) Activated amides: Ni or Pd, 160 oC
2) Naphthelene- and electron-deficient
benzene-carboxylates: Ni, 150-170 oC
3) Carboxylic acids: Pd, Piv2O, 160 oC
P(O)(OR)
R-X
P(O)-R
High temperature
For benzyl phosphoryl compounds
P(O)-H
cat. M
O
P(O)-H
P(O)-CH2Ar
Pd, 150 oC
Ar
OPh
moderate yields
E. This work: Controlled phosphorylation
O
O
Z1
Z2
O
O
P
Z1
Z2
base
Z1
cat. Pd
130 oC
Ar
P
P H
Ar
120 oC
Z2
Ar
SR1
24 examples
up to 96 % yield
24 examples
up to 95 % yield
Deoxygenative phosphorylation
Decarbonylative phosphorylation
vs
Scheme 1. Transformation of thioesters and P(O)-C bonds formation
Organophosphorus compounds play an important role in chemistry, biology and material science.9 Their traditional
synthesis was highly dependent on the transformation of organohalides such as nucleophilic substitution of P(O)X with
organometals (Li or Mg), and Michealis-Arbuzov reaction of alkyl halides with phosphites at a high reaction
temperature (Scheme 1C).10 Obviously, the relatively harsh reaction conditions were difficult to meet the requirement
for the diverse synthesis of organophosphorus compounds. In 1980s, Hirao reported a Pd-catalyzed phosphorylation of
aryl halides with P(O)H compounds.11 This reaction was remarked as a milestone in this field and subsequently led to
many efficient variations.12 Carboxylic acids and their derivatives are abundant in both natural and synthetic world.
The direct use of these chemicals would shorten the synthetic scheme and decrease the cost, thus enhancing the
synthetic efficiency. The strategy has attracted much attention of chemists and recently has been extended to the
synthesis of organophosphorus compounds (Scheme 1D).13 Thus, Szostak reported a P(O)-C bond-forming reaction
from activated amides at 160 C through Pd and Ni catalysis.13a Yamaguchi achieved the conversion of naphthalene-
o
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and electron-deficient benzene-carboxylates into the corresponding aryl phosphoryl compounds at 150 oC-170 oC with
a nickel catalyst.13b In 2019, Szostak demonstrated the Pd-catalyzed synthesis of aryl phosphoryl compounds from
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5
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carboxylic acids using Piv2O as an in situ activating reagent at 160 C.13c Our Group also reported a similar reaction
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but with relatively low yields.13d As for the synthesis of benzyl phosphoryl compounds, Yamaguchi realized out the
deoxygenative phosphorylation of arene-carboxylates at 150 oC over Pd catalysis with moderate yields very recently.13e
Despite the advance, more synthetic methods are still desirable for the synthesis of organophosphorus compounds.
Herein, we reported the controllable phosphorylations of thioesters with P(O)H compounds (Scheme 1E). Catalyzed
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by a palladium catalyst, decarbonylative coupling took place at 130 C to produce aryl or alkenyl phosphoryl
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compounds, while deoxygenative coupling occurred at 120 C in the presence of only a base to yield benzyl
phosphoryl compounds. This reaction not only provided an alternative method for the synthesis of both aryl and benzyl
phosphoryl compounds, but also enriched the toolbox for transformation of thioesters. Moreover, to the best of our
knowledge, this is the first metal-free example on the transformation of carboxylic acid derivatives into benzyl
phosphoryl compounds.
RESULTS AND DISCUSSION
We started the work by investigating the decarbonylative coupling between thioesters and P(O)H compounds and the
obtained results were compiled in Table 1. It was found that the reaction of 1a with 2a would take place readily to
produce the corresponding product 3a in 92% yield in the presence of a catalytic amount of Pd(dppp)Cl2 (entry 1). A
nickel catalyst could not promote the reaction (entry 2). No 3a was detected in the absence of the palladium catalyst
(entry 3). The combinations of palladium complexes with varied phosphine ligands could also mediate the reaction,
though the yields would decrease to some extent (entries 4-7). It should be noted that the phosphine ligand was
essential to this reaction. Without phosphine ligand, only a trace amount of 3a was detected (entries 8 and 9). The base
was subsequently screened. Na2CO3 and K2CO3 also worked well, while the yield decreased dramatically with Et3N,
NaOH or in the absence of a base (entries 10-14). This reaction could also proceed in other solvents with 1,3-DCP
being the best choice (entries 15-19). With 5 mol% catalyst, the yield of 3a decreased to 69% (entry 20). Lowering the
o
reaction temperature to 120 C also resulted in slight decrease of the yield (entry 21). Further elevating the reaction
temperature could also not increase the reaction efficiency (entry 22).
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Table 1. Optimization of the decarbonylative coupling’s reaction conditionsa
1
2
3
O
cat. (10 mol%)
4
5
6
SR
HP(O)Ph2
base (3.5 equiv), N2
solvent, 130 oC, 1 h
P(O)Ph2
2a
3a
1a
, R = p-tolyl
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8
9
Entry
1
Catalyst
Base
Solvent
Yield [%]b
92
Pd(dppp)Cl2
Ni(dppp)Cl2
-
NaHCO3
NaHCO3
NaHCO3
NaHCO3
NaHCO3
NaHCO3
NaHCO3
NaHCO3
NaHCO3
Na2CO3
K2CO3
1,3-DCP
1,3-DCP
1,3-DCP
1,3-DCP
1,3-DCP
1,3-DCP
1,3-DCP
1,3-DCP
1,3-DCP
1,3-DCP
1,3-DCP
1,3-DCP
1,3-DCP
1,3-DCP
DMF
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2
n.d.
n.d.
88
3
4c
Pd2(dba)3/dppp
PdCl2/dppp
PdCl2/dppm
PdCl2/TFP
5
81
6
45
7d
40
8
PdCl2
Trace
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9
PdCl2/Neocuproine
Pd(dppp)Cl2
Pd(dppp)Cl2
Pd(dppp)Cl2
Pd(dppp)Cl2
Pd(dppp)Cl2
Pd(dppp)Cl2
Pd(dppp)Cl2
Pd(dppp)Cl2
Pd(dppp)Cl2
Pd(dppp)Cl2
Pd(dppp)Cl2
Pd(dppp)Cl2
Pd(dppp)Cl2
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11
12
13
14
15
16
17
18
19
20 c
21e
22f
89
82
Et3N
39
NaOH
8
-
8
NaHCO3
NaHCO3
NaHCO3
NaHCO3
NaHCO3
NaHCO3
NaHCO3
NaHCO3
40
Dioxane
THF
38
42
DCE
76
Toluene
1,3-DCP
1,3-DCP
1,3-DCP
30
69
78
90
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aReaction conditions: 1a (0.2 mmol), 2a (0.4 mmol), catalyst (10 mol %), base (3.5 equiv), solvent (3.0 mL), N2, 130
1
2
3
4
5
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7
b
c
d
e
o
f
o
oC, 1 h. GC yield using tridecane as an internal standard. Catalyst (5 mol %). TFP (20 mol %). 120 C. 140 C.
DCE: dichloroethane, 1,3-DCP: 1,3-dichloropropane, dppp: 1,3-Bis(diphenylphosphino)propane, dppm:
Bis(diphenylphosphino)methane, TFP: tri(2-furyl)phosphine.
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Table 2. Substrate scope of decarbonylative couplinga,b
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O
O
P
Z1
Z2
O
P
Pd(dppp)Cl2
Z1
Z2
SR
H
Ar
Ar
NaHCO3, 1,3-DCP
1
, R = p-tolyl
2
3
Me
P(O)Ph2
Me
MeO
P(O)Ph2
3c
, 83%
P(O)Ph2
, 94%
3a
3d
3b
3e
, 90%
Me
t-Bu
P(O)Ph2
, 79%
P(O)Ph2
, 88%
P(O)Ph2
P(O)Ph2
, 94%
3f
3i
Ph
F
P(O)Ph2
P(O)Ph2
, 78%
3g
3h
3k
3n
, 69%
, 58%
Cl
P(O)Ph2
O
P(O)Ph2
, 83%
P(O)Ph2
, 68%
3j
3l
, 59%
P(O)Ph2
P(O)Ph2
, 64%
S
P(O)Ph2
, 45%
N
3m
3o
, 54%
P(O)Ar2
Ar = 4-MeC6H4
P(O)Ph(Bu-n)
P(O)Ph(OEt)
3r
, 81%
3p
3q
, 96%
, 65%
P(O)(OEt)2
, 48%
P(O)(OPr-i)2
P(O)(OBu-n)2
3s
3t
3u
, 45%
, 55%
aReaction conditions: 1 (0.2 mmol), 2 (0.4 mmol), Pd(dppp)Cl2 (10 mol %), NaHCO3 (3.5 equiv), 1,3-DCP (3.0 mL),
N2, 130 oC, 1 h. bIsolated yields.
With the optimal reaction conditions in hand, the substrate scope was subsequently investigated. As shown in Table
2, benzothioates bearing electron-donating groups such as 4-Me, 3-Me, 2-Me, 4-t-Bu and 4-MeO all coupled readily
with Ph2P(O)H to produce the corresponding products in high yields (3a-3f). The -extended derivatives also worked
well, furnishing the coupling products in good yields (3g-3i). Halo groups like F and Cl survived well, facilitating
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further functionalization of products (3j and 3k). Heterocyclic substrates also proved to be efficient under the reaction
conditions (3l-3n). (E)-3-phenylprop-2-enethioate was also phosphorylated, despite with a relatively low yield (3o). To
our delight, all the three kinds of P(O)H compounds served well in the current catalytic system. Thus, other secondary
phosphine oxides (p-tolyl)2P(O)H and (n-Bu)PhP(O)H reacted with 1a to give 3p and 3q in 96% and 65% yields,
respectively. H-phosphinate (EtO)PhP(O)H and H-phosphonates (EtO)2P(O)H, (i-PrO)2P(O)H, (n-BuO)2P(O)H also
underwent decarbonylative coupling with 1a under the reaction conditions, generating the expected products in good
yields (3r-3u).
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Table 3. Optimization of the deoxygenative coupling’s reaction conditionsa
O
Add,. (3.5 eq)
SR
HP(O)Ph2
P(O)Ph2
Base (1.5 eq), N2
Solvent, 120 oC, 1 h
2 a
4 a
1 a
, R = p-tolyl
Entry
1
Additive
Base
K2CO3
K2CO3
K2CO3
K2CO3
Na2CO3
NaHCO3
Et3N
Solvent
Yield [%]b
NaH2PO2
-
DMF
DMF
97
65
72
71
90
83
20
45
34
84
82
73
28
81
85
2
3
NaHSO3
HCOONa
NaH2PO2
NaH2PO2
NaH2PO2
NaH2PO2
NaH2PO2
NaH2PO2
NaH2PO2
NaH2PO2
NaH2PO2
NaH2PO2
NaH2PO2
DMF
4
DMF
5
DMF
6
DMF
7
DMF
8
NaOH
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
DMF
9
1,3-DCP
dioxane
THF
10
11
12
13
14c
15d
toluene
DCE
DMF
DMF
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aReaction conditions: 1a (0.2 mmol), 2a (0.4 mmol), additive (2.5 equiv), base (1.5 equiv), solvent (1.5 mL), N2, 120
1
2
3
b
c
o
d
o
oC, 10 h. GC yield using tridecane as an internal standard. 110 C. 130 C. DCE: dichloroethane, 1,3-DCP:
4
5
1,3-dichloropropane.
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During studies on the control experiments, we found that when the reaction was conducted in the absence of any
metal catalyst, 14% yield of benzyl phosphoryl compound 4a was produced instead (Table 1, entry 3). We were
interested in the result and envisioned that a deoxygenative coupling forming benzyl phosphoryl compounds might be
reachable. Indeed, after an extensive condition optimization, the yield of 4a reached 97% when the reaction was
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performed in the presence of 1.5 equiv K2CO3, 2.5 equiv NaH2PO2 at 120 C in DMF (Table 3, entry 1). Without
NaH2PO2, only 65% yield of 4a was obtained (Table 3, entry 2). Reductant NaHSO3 and HCOONa could not promote
the reaction (Table 3, entries 3 and 4). The base was subsequently screened, Na2CO3 and NaHCO3 also worked well,
while the yield decreased dramatically with Et3N and NaOH (Table 3, entries 5-8). As for the solvent, DMF was the
best choice (Table 3, entries 9-13). Either lowering or elevating the reaction temperature resulted in the decrease of
yield (Table 3, entries 14 and 15).
Table 4. Substrate scope of deoxygenative couplinga,b
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O
Z2
Z1
1
2
3
4
O
Z1
Z2
P
K2CO3, NaH2PO2
H
P
SR
Ar
DMF, 120 oC, 10 h
Ar
O
1
2
4
, R = p-tolyl
5
Me
6
7
8
9
P(O)Ph2
P(O)Ph2
P(O)Ph2
P(O)Ph2
P(O)Ph2
, 92%
Me
MeO
4b
4c
, 91%
4a
, 94%
Me
t-Bu
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P(O)Ph2
P(O)Ph2
4d
4e
4f
, 87%
, 91%
P(O)Ph2
, 96%
Ph
F
P(O)Ph2
4g
4h
4k
4i
, 81%
, 93%
, 95%
Br
Cl
P(O)Ph2
P(O)Ph2
P(O)Ph2
P(O)Ph2
P(O)Ph2
4j
4l
, 45%
, 61%
, 36%
NC
F3C
P(O)Ph2
O
4m
, 87%
4n
4q
4o
, 93%
, 91%
P(O)Ph2
P(O)Ar2
Ar = 4-MeC6H4
S
P(O)Ph2
N
4p
4r
, 80%
, 70%
, 91%
P(O)Ph(Bu-n)
, 69%
P(O)Ph(OEt)
, 38%
P(O)(OEt)2
4s
4t
4u
, 0%
aReaction conditions: 1 (0.2 mmol), 2 (0.4 mmol), K2CO3 (1.5 equiv), NaH2PO2 (2.5 equiv), DMF (1.5 mL), N2, 120
oC, 10 h. bIsolated yields.
The substrate scope of benzotioates was also general (Table 4). Both electron-rich and electron-deficient derivatives
could be phosphorylated forming the deoxygenative coupling products. High yields were obtained from benzothioates
bearing 4-Me, 3-Me, 2-Me, 4-n-Bu and 4-MeO (4a-4f). -Extended substrates were also transformed into the
corresponding products in high yields (4g-4i). Halo groups such as F, Cl and Br survived well under the reaction
conditions (4j-4l). Derivatives bearing electron-withdrawing groups like CN and CF3 proved to be efficient, furnishing
the products in high yields (4m and 4n). Heterocyclic substrates also worked well (4o-4q). As for the hydrogen
phosphoryl compounds, other secondary phosphine oxides (p-tolyl)2P(O)H and (n-Bu)PhP(O)H also acted as good
substrates (4r and 4s). H-phosphinate (EtO)PhP(O)H gave a low yield (4t), while H-phosphonate did not work under
the reaction conditions (4u).
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The S-substitution was subsequently investigated. As shown in Scheme 2, for both coupling reactions, S-Ar
1
2
benzothioates worked well under the indicated optimized reaction conditions, furnishing the corresponding products in
high yields. S-methyl benzothioate could also be phosphorylated, however, the yields decreased for both reactions. It
was deduced that the weaker electron-donating but stronger leaving performances of ArS group facilitated the
oxidative addition of acyl C-S bonds with low valent metals and subsequent ligand exchange as well as the addition
elimination process with nucleophiles, thus, similar reactivity was observed in both reactions (for the proposed
mechanism, see below).14
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O
Decarbonylative
couplinga
Deoxygenative
couplingb
HP(O)Ph2
SR
P(O)Ph2
O
P(O)Ph2
3a
1
2a
4a
Me
OMe
Cl
O
O
O
S
Me
S
S
S
1a
1b
1c
1d
3a
4a
90%
94%
96%
95%
89%
92%
45%
27%
Scheme 2. The effect of S-substituents. aReaction conditions: 1 (0.2 mmol), 2 (0.4 mmol), Pd(dppp)Cl2 (10 mol %), NaHCO3 (3.5
equiv), 1,3-DCP (3.0 mL), N2, 130 oC, 1 h. bReaction conditions: 1 (0.2 mmol), 2 (0.4 mmol), K2CO3 (1.5 equiv), NaH2PO2 (2.5
equiv), DMF (1.5 mL), N2, 120 oC, 10 h. Isolated yields.
On the basis of previous literatures,3-8,13 the decarbonylative coupling would take place through a classic catalytic
cycle involving oxidative addition, decarbonylation, ligand exchange and reductive elimination (Scheme 3). As for the
mechanism on the deoxygenative coupling, we proposed that benzothioates would undergo nucleophilic substitution
with P(O)H compounds by the aid of a base to produce compound B, followed by nucleophilic addition and
isomerization to generate compound D. The resulting D could be in situ reduced by NaH2PO2 and P(O)H compounds
to yield the benzyl phosphoryl compounds.
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HP(O)Z1Z2
1
2
3
4
5
6
7
8
1
+
Ar P(O)Z1Z2
NaH2PO2
3
O P(O)Z1Z2
PdIIL
Ar
Reductive
elimination
P(O)Z1Z2
D
Ar
P(O)Z1Z2
Pd0L
Ar
PdII
P(O)Z1Z2
IV
4
L
I
HSR
P(O)Z1Z2
P(O)Z1Z2
O
HO
Ar
Ligand
exchange
Oxidative
addition
base
Ar SR
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1
C
2
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2
base
RS
2
RS
O
O
PdIIAr
PdII
Ar
O
Ar P(O)Z1Z2
Decarbonylation
L
III
Ar
L
P(O)Z1Z2
RS
B
II
A
CO
Decarbonylative Coupling
Deoxygenative Coupling
Scheme 3. Proposed mechanism
It should be noted that compound B might undergo oxidative addition with Pd(0) complex, followed by
decarbonylation and reductive elimination to produce the aryl phosphoryl compound 3.15 We synthesized compound
B1.16 It was found that compound B1 could not be transformed into 3s under the current palladium-catalyzed reaction
conditions (Scheme 4, eqn 1). The result indicated that the proposed path through formation of compound B for the
decarbonylative coupling would not be favoured. Meanwhile, compound B1 could also not be converted into 4u
(Scheme 4, eqn 2), which was consistent with the experimental result (see Table 3).
O
10 mol% Pd(dppp)Cl2
3.5 equiv NaHCO3
P(O)(OEt)2
(1)
(2)
P(O)(OEt)2
P(O)(OEt)2
1,3-DCP, 130 oC, 1 h, N2
B1
3s
HP(O)(OEt)2
0/1/2 equiv
not detected
O
1.5 equiv K2CO3
2.5 equiv NaH2PO2
DMF, 120 oC, 10 h, N2
P(O)(OEt)2
4u
HP(O)(OEt)2
0/1/2 equiv
B1
not detected
OP(O)Ph2
P(O)Ph2
O
O
Ph2P(O)H
O
Ph2P(O)H
(3)
(4)
P(O)Ph2
2
D1
, 43%
B2
, not isolated
1
OP(O)Ph2
1.5 equiv K2CO3
DMF, 120 oC, 10 h, N2
P(O)Ph2
P(O)Ph2
4a
D1
45% GC yield
37% GC yield
1 equiv HP(O)Ph2
2.5 equiv NaH2PO2
Scheme 4. Control experiments
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We also tried to synthesize compound B2 from benzoic anhydride and Ph2P(O)H, but we failed, a product D1
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5
6
7
generated from addition of Ph2P(O)H to B2 was obtained instead (Scheme 4, eqn 3).13e It was found that compound D1
could be reduced by both Ph2P(O)H and NaH2PO2 to produce 4a under the deoxygenative coupling reaction conditions
(Scheme 4, eqn 4).17 These results well supported the proposed mechanism for the deoxygenative coupling.
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CONCLUSIONS
In summary, the phosphorylation of thioesters with P(O)H compounds was first achieved. The products were
controllable by adjusting the reaction conditions. When the reaction was mediated by a palladium catalyst,
decarbonylative coupling would occur to produce the corresponding aryl or alkenyl phosphoryl compounds; while the
deoxygenative coupling would take place to yield the benzyl phosphoryl compounds. This reaction provided an
alternative method for benzyl, alkenyl and aryl phosphoryl compounds and also extended the use of thioesters.
EXPERIMENTAL SECTION
General information: The reactions were carried out in Schlenk tubes of 25 mL under N2 atmosphere. For reactions
that require heating, heating mantle was used as the heat source. Reagents were used as received unless otherwise
noted, and solvents were purified according to standard operation procedures. Column chromatography was performed
using Silica Gel 60 (300-400 mesh). The reactions were monitored by GC and GC-MS, GC-MS results were recorded
on GC-MS QP2010, and GC analysis was performed on GC 2014. The 1H, 13C and 31P NMR spectra were recorded on
a Brucker ADVANCE III spectrometer at 400 MHz, 100 MHz, and 162 MHz respectively, and chemical shifts were
reported in parts per million (ppm). All solvents and reagents were purchased from Tansoole, Meryer, Heowns, Energy
Chemical, Alfa Aesar, and Aladdin.
General procedure I for synthesis of thioesters: The aromatic acid (10.0 mmol), thionyl chloride (1.1 mL, 15 mmol),
and 3 drops of DMF were heated in DCM (20 mL) at 55 °C for 5 h. After the reaction, DCM and excess of thionyl
chloride were removed under vacuo and the crude product was used without any purification. The thiophenol
compounds (10.0 mmol) and Et3N (4.0 mL, 30.0 mmol) in dry DCM (20 mL) were slowly added to the solution of the
acylchloride (10.0 mmol) in DCM (5.0 mL) at 0 °C. The reaction mixture was stirred at room temperature overnight.
After completion, the reaction mixture was diluted with DCM (20 mL) and filtered. The collected solution was then
washed by saturated NaHCO3 solution (20 mL), saturated NaCl solution (20 mL), dried over anhydrous MgSO4,
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filtered and concentrated under vacuo. The crude product was purified by column chromatography over silica gel
(300-400 mesh) using petroleum ether/ethyl acetate as an eluent to give analytically pure product.
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Synthesis of S-methyl benzothioate: A mixture of a well-powdered benzoic anhydride (6.0 mmol), thiourea (6.5
mmol) and Et3N (2.5 mL) was stirred at 40 °C until the starting anhydride was completely consumed and a two-phase
system containing Et3N and a thick brick-red liquid was formed. Then, water (5.0 mL) and CH3I (5.0 mmol) were
added to the mixture and stirring was continued at room temperature. After consumption of starting CH3I (3 h), the
crude product was extracted with EtOAc (15 mL × 2). The crude product was purified by column chromatography over
silica gel (300-400 mesh) using petroleum ether/ethyl acetate as an eluent to give analytically pure product.
Synthesis of di-p-tolylphosphine oxide: A dried 250 mL flask was charge with p-tolylmagnesium bromide (33 mmol,
1.0 mol/L in THF) in water-ice bath under N2. A solution of diethylphosphite (1.3 mL, 10.0 mmol) in anhydrous THF
(5.0 mL) was then added dropwise over 30 min. The mixture was further stirred at ambient temperature overnight.
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o
After then, the reaction mixture was cooled to 0 C again and HCl (100 mL 0.1 N) was added dropwise. The mixture
was extracted with dichloromethane (100 mL × 3), the combined organic phase was washed with saturated NaCl
solution, dried over anhydrous MgSO4 filtered and concentrated under vacuo. The crude product was purified by
column chromatography (EtOAc) to give the desired product.
n
Synthesis of butyl(phenyl)phosphine oxide: A dried 250 mL flask was charge with butylmagnesium chloride (20.0
mmol, 2 mol/L in THF) in water-ice bath under N2. A solution of ethyl phenylphosphinate (10.0 mmol) in anhydrous
THF (5 mL) was then added dropwise over 30 min. Then the mixture was further stirred at ambient temperature
o
overnight, and then cooled to 0 C again. HCl (100 mL, 0.1 N) was then added dropwise. The mixture was extracted
with dichloromethane (100 mL × 3), the combined organic phase was washed with saturated NaCl solution, dried over
anhydrous MgSO4, filtered and concentrated under vacuo. The crude product was purified by column chromatography
(EtOAc) to give the desired product.
Synthesis of compound diethyl phenylphosphonate (B1)18: A dried 25 mL flask was charge with triethyl phosphite
(11.0 mmol, 1.27 mL) and benzoyl chloride (10.0 mmol, 1.72 mL). After stirring the mixture for 12 h at room
temperature, the crude product was purified by column chromatography over silica gel (300-400 mesh) using CH2Cl2
as an eluent to give analytically pure product. Compound B1: 1H NMR (400 MHz, CDCl3) δ 8.28 (d, J = 7.6 Hz, 2H),
7.64 (dd, J1 = J2 = 6.0 Hz, 1H), 7.53-7.49 (m, 2H), 4.34-4.27 (m, 4H), 1.41-1.37 (m, 6H).
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Synthesis of (diphenylphosphoryl)(phenyl)methyl diphenylphosphinate (D1)19: In an oven dried 25 mL Schlenk
tube was charged with Ph2P(O)H (10.0 mol) and KOH (1.1 mol), CH2Cl2 (2.5 mL) was added in N2 atmosphere. To
this solution was slowly added benzoic anhydride (11.0 mol, 1.1 equiv) dissolved in CH2Cl2 (3.0 mL). The reaction
mixture was reacted to reflux 70 °C for 20 h. After then, the mixture was cooled to room temperature and concentrated
in vacuo. The residue was isolated by column chromatography over silica gel (300-400 mesh) using petroleum ether:
ethyl acetate = 5:1 (v:v) as eluent. The light yellow liquid was obtained and recrystallized with petroleum ether to
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obtain the required product. Compound D1: H NMR (400 MHz, CDCl3) δ 8.03-7.99 (m, 2H), 7.62-7.52 (m, 3H),
7.49-7.24 (m, 13H), 7.17-7.08 (m, 5H), 7.02 (dd, J1 = J2 = 7.6 Hz, 2H), 6.31 (dd, J1 = 10.4 Hz, J2 = 2.4 Hz, 1H);
13C{1H} NMR (100 MHz, CDCl3) δ 132.4 (d, JC-P = 8.8 Hz), 132.2 (d, JC-P = 2.7 Hz), 132.1 (dd, J1C-P = J2C-P = 2.8
Hz), 131.9 (d, JC-P = 2.8 Hz), 131.7 (d, JC-P = 10.8 Hz), 131.6 (d, JC-P = 9.0 Hz), 131.2 (d, JC-P = 10.5 Hz), 131.1 (d,
JC-P = 76.5 Hz), 130.7 (d, JC-P = 131.8 Hz), 130.1 (d, JC-P = 138.5 Hz), 129.4 (d, JC-P = 65.6 Hz),129.2 (d, JC-P = 5.0
Hz), 128.6 (d, JC-P = 1.9 Hz), 128.391 (d, JC-P = 23.5 Hz), 128.390, 128.2 (d, JC-P = 13.6 Hz), 127.8 (d, JC-P = 13.2 Hz),
127.7 (d, JC-P = 1.2 Hz), 74.7 (dd, JC-P = 85.5, 7.5 Hz); 31P NMR (162 MHz, CDCl3) δ 35.5, 35.4, 29.0, 28.9.
General procedure II for Procedure of Decarbonylative Coupling : Into an oven dried 25 mL Schlenk tube was
charged with 1 (0.2 mmol), 2 (0.4 mmol), Pd(dppp)Cl2 (0.02 mmol, 10 mol %) and NaHCO3 (0.7 mmol, 3.5 equiv),
1,3-dichloropropane (3.0 mL) was added under a N2 atmosphere. The reaction mixture was reacted at 130 °C for 1 h.
After completion of the reaction, the reaction mixture was concentrated under vacuo. The desired product was isolated
by column chromatography over silica gel (300-400 mesh) using petroleum ether-ethyl acetate-dichloromethane as
eluent.
General procedure III for Procedure of Deoxygenative Coupling : Into an oven dried 25 mL Schlenk tube was
charged with 1 (0.2 mmol), 2 (0.4 mmol), K2CO3 (0.3 mmol, 1.5 equiv) and NaH2PO2 (0.5 mmol, 2.5 equiv), DMF
(1.5 mL) was added under a N2 atmosphere. The reaction mixture was reacted at 120 °C for 10 h. After completion of
the reaction, the reaction mixture was concentrated under vacuo. The desired product was isolated by column
chromatography over silica gel (300-400 mesh) using petroleum ether-ethyl acetate-dichloromethane as eluent.
Larger Scale Synthesis (2 mmol scale). For Decarbonylative Coupling to Produce 3a: Into an oven dried 100 mL
Schlenk tube was charged with 1a (2 mmol), 2a (4 mmol), Pd(dppp)Cl2 (0.2 mmol, 10 mol %) and NaHCO3 (7 mmol,
3.5 equiv), 1,3-dichloropropane (30 mL) was added under a N2 atmosphere. The reaction mixture was heated at 130 °C
for 5 h. After completion of the reaction, the reaction mixture was concentrated under vacuo. The desired product was
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isolated by column chromatography over silica gel and eluted with petroleum ether: ethyl acetate: dichloromethane =
2:2:1 (v:v:v) to afford a white solid in 75% yield (417.5 mg). For Deoxygenative Coupling to Produce 4a: Into an
oven dried 100 mL Schlenk tube was charged with 1a (2 mmol), 2a (4 mmol), K2CO3 (3 mmol, 1.5 equiv) and
NaH2PO2 (5 mmol, 2.5 equiv), DMF (15 mL) was added under a N2 atmosphere. The reaction mixture was reacted at
120 °C for 36 h. After completion of the reaction, the reaction mixture was concentrated under vacuo. The desired
product was isolated by column chromatography over silica gel and eluted with petroleum ether: ethyl acetate:
dichloromethane = 2:2:1 (v:v:v) to afford a white solid in 73% yield (426.7 mg).
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triphenylphosphine oxide (3a)20. The title compound was prepared according to the general procedure II and
purified by column chromatography on silica gel and eluted with petroleum ether: ethyl acetate: dichloromethane =
1
2:2:1 (v:v:v) to afford a white solid in 90% yield (50.2 mg). H NMR (400 MHz, CDCl3) δ 7.69-7.64 (m, 6H),
7.55-7.51 (m. 3H), 7.47-7.43 (m, 6H); 13C{1H} NMR (100 MHz, CDCl3) δ 132.5 (d, JC-P = 104.1 Hz), 132.0 (d, JC-P
9.7 Hz), 131.9 (d, JC-P = 2.6 Hz), 128.4 (d, JC-P = 12.2 Hz); 31P NMR (162 MHz, CDCl3) δ 29.1.
=
diphenyl(p-tolyl)phosphine oxide (3b)20. The title compound was prepared according to the general procedure II
and purified by column chromatography on silica gel and eluted with petroleum ether: ethyl acetate: dichloromethane =
1
2:2:1 (v:v:v) to afford a white solid in 94% yield (55.0 mg). H NMR (400 MHz, CDCl3) δ 7.61-7.56 (m, 4H),
13
7.48-7.43 (m, 4H), 7.39-7.36 (m, 4H), 7.20-7.18 (m, 2H), 2.32 (s, 3H); C{1H} NMR (100 MHz, CDCl3) δ 142.4 (d,
JC-P = 2.7 Hz), 132.8 (d, JC-P = 103.4 Hz), 133.0, 132.1 (d, JC-P = 10.2 Hz), 132.01 (d, JC-P = 9.9 Hz), 131.98, 131.9 (d,
JC-P = 2.7 Hz), 131.8 (d, JC-P = 2.7 Hz), 129.2 (d, JC-P = 12.5 Hz), 129.1 (d, JC-P = 105.7 Hz), 128.44 (d, JC-P = 11.9 Hz),
128.38 (d, JC-P = 12.1 Hz), 21.6; 31P NMR (162 MHz, CDCl3) δ 29.1.
diphenyl(3-tolyl)phosphine oxide (3c)21. The title compound was prepared according to the general procedure II
and purified by column chromatography on silica gel and eluted with petroleum ether: ethyl acetate: dichloromethane =
1
2:2:1 (v:v:v) to afford a white solid in 83% yield (48.5 mg). H NMR (400 MHz, CDCl3) δ 7.62-7.57 (m, 4H),
13
7.52-7.45 (m, 3H), 7.41-7.37 (m, 4H), 7.33-7.24 (m, 3H), 2.29 (s, 3H); C{1H} NMR (100 MHz, CDCl3) δ 138.5 (d,
JC-P = 11.8 Hz), 132.8 (d, JC-P = 2.7 Hz), 132.6 (d, JC-P = 95.6 Hz), 132.5 (d, JC-P = 9.4 Hz), 132.1 (d, JC-P = 9.8 Hz),
131.9 (d, JC-P = 2.5 Hz), 129.2 (d, JC-P = 10.3 Hz), 128.5 (d, JC-P = 11.9 Hz), 128.3 (d, JC-P = 12.7 Hz), 21.4; 31P NMR
(162 MHz, CDCl3) δ 29.5.
diphenyl(2-tolyl)phosphine oxide (3d)21. The title compound was prepared according to the general procedure II
and purified by column chromatography on silica gel and eluted with petroleum ether: ethyl acetate: dichloromethane =
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1
2:2:1 (v:v:v) to afford a white solid in 79% yield (46.2 mg). H NMR (400 MHz, CDCl3) δ 7.62-7.57 (m, 4H),
1
2
3
13
7.49-7.44 (m, 2H), 7.40-7.36 (m, 5H), 7.32-7.24 (m, 3H), 2.28 (s, 3H); C{1H} NMR (100 MHz, CDCl3) δ 138.4 (d,
4
5
JC-P = 11.8 Hz), 132.7 (d, JC-P = 2.3 Hz), 132.6 (d, JC-P = 103.3 Hz), 132.434 (d, JC-P = 107.7 Hz), 132.430 (d, JC-P
=
6
7
8
9
9.4 Hz), 132.0 (d, JC-P = 9.9 Hz), 131.8 (d, JC-P = 2.8 Hz), 129.1 (d, JC-P = 10.2 Hz), 128.44 (d, JC-P = 12.1 Hz), 128.41
(d, JC-P = 11.9 Hz), 128.2 (d, JC-P = 12.9 Hz), 21.4; 31P NMR (162 MHz, CDCl3) δ 29.3.
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(4-(tert-butyl)phenyl)diphenylphosphine oxide (3e)21. The title compound was prepared according to the general
procedure II and purified by column chromatography on silica gel and eluted with petroleum ether: ethyl acetate:
1
dichloromethane = 2:2:1 (v:v:v) to afford a white solid in 88% yield (58.8 mg). H NMR (400 MHz, CDCl3) δ
7.71-7.66 (m, 4H), 7.62-7.57 (m, 2H), 7.52-7.42 (m, 8H), 1.32 (s, 9H); 13C{1H} NMR (100 MHz, CDCl3) δ 156.3,
132.6 (d, JC-P = 103.3 Hz), 131.9 (d, JC-P = 9.7 Hz), 131.8 (d, JC-P = 10.3 Hz), 131.7 (d, JC-P = 2.8 Hz), 128.9 (d, JC-P
105.8 Hz), 128.3 (d, JC-P = 11.9 Hz), 125.4 (d, JC-P = 12.3 Hz), 34.8, 31.0; 31P NMR (162 MHz, CDCl3) δ 29.1.
=
(4-methoxyphenyl)diphenylphosphine oxide (3f)20. The title compound was prepared according to the general
procedure II and purified by column chromatography on silica gel and eluted with petroleum ether: ethyl acetate:
1
dichloromethane = 2:2:1 (v:v:v) to afford a white solid in 94% yield (57.8 mg). H NMR (400 MHz, CDCl3) δ
7.61-7.56 (m, 4H), 7.53-7.48 (m, 2H), 7.45-7.43 (m, 2H), 7.39-7.35 (m, 4H), 6.90-6.87 (m, 2H), 3.76 (s, 3H); 13C{1H}
NMR (100 MHz, CDCl3) δ 162.4 (d, JC-P = 2.7 Hz), 133.9 (d, JC-P = 11.3 Hz), 132.9 (d, JC-P = 103.9 Hz), 132.0 (d, JC-P
= 9.9 Hz), 131.7 (d, JC-P = 2.6 Hz), 128.4 (d, JC-P = 11.8 Hz), 123.5 (d, JC-P = 109.7 Hz), 114.0 (d, JC-P = 13.2 Hz), 55.3;
31P NMR (162 MHz, CDCl3) δ 29.0.
[1,1'-biphenyl]-4-yldiphenylphosphine oxide (3g)20. The title compound was prepared according to the general
procedure II and purified by column chromatography on silica gel and eluted with petroleum ether: ethyl acetate:
1
dichloromethane = 2:2:1 (v:v:v) to afford a white solid in 78% yield (55.2 mg). H NMR (400 MHz, CDCl3) δ
7.69-7.60 (m, 8H), 7.54-7.47 (m, 4H), 7.43-7.37 (m, 6H), 7.33-7.30 (m, 1H); 13C{1H} NMR (100 MHz, CDCl3) δ
144.7 (d, JC-P = 2.2 Hz), 139.9, 132.6 (d, JC-P = 10.1 Hz), 132.5 (d, JC-P = 102.2 Hz), 132.1 (d, JC-P = 9.9 Hz), 132.0 (d,
JC-P = 2.3 Hz), 131.0 (d, JC-P = 104.6 Hz), 128.9, 128.5 (d, JC-P = 12.1 Hz), 128.1, 127.20, 127.18 (d, JC-P = 13.5 Hz);
31P NMR (162 MHz, CDCl3) δ 29.1.
naphthalen-1-yldiphenylphosphine oxide (3h)22. The title compound was prepared according to the general
procedure II and purified by column chromatography on silica gel and eluted with petroleum ether: ethyl acetate:
dichloromethane = 2:2:1 (v:v:v) to afford a white solid in 69% yield (45.4 mg). 1H NMR (400 MHz, CDCl3) δ 8.59 (d,
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J = 8.4 Hz, 1H), 8.01 (d, J = 8.0 Hz, 1H), 7.88 (d, J = 8.0 Hz, 1H), 7.71-7.66 (m, 4H), 7.56-7.43 (m, 8H), 7.40-7.35 (m,
1H), 7.33-7.27 (m, 1H); 13C{1H} NMR (100 MHz, CDCl3) δ 133.763, 133.761 (d, JC-P = 7.9 Hz), 133.5 (d, JC-P = 34.0
Hz), 133.2 (d, JC-P = 2.8 Hz), 132.3, 132.0 (d, JC-P = 9.7 Hz), 131.8 (d, JC-P = 2.7 Hz), 128.9 (d, JC-P = 101.3 Hz), 128.7,
128.5 (d, JC-P = 12.1 Hz), 127.6 (d, JC-P = 5.8 Hz), 127.3, 126.4, 124.1 (d, JC-P = 14.3 Hz); 31P NMR (162 MHz, CDCl3)
δ 32.3.
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naphthalen-2-yldiphenylphosphine oxide (3i)20. The title compound was prepared according to the general
procedure II and purified by column chromatography on silica gel and eluted with petroleum ether: ethyl acetate:
dichloromethane = 2:2:1 (v:v:v) to afford a white solid in 58% yield (38.1 mg). 1H NMR (400 MHz, CDCl3) δ 8.28 (d,
J = 14.0 Hz, 1H), 7.92-7.87 (m, 3H), 7.74-7.69 (m, 4H), 7.67-7.64 (m, 1H), 7.60-7.53 (m, 4H), 7.50-7.45 (m, 4H);
13C{1H} NMR (100 MHz, CDCl3) δ 134.6 (d, JC-P = 2.4 Hz), 133.9 (d, JC-P = 9.2 Hz), 132.5 (d, JC-P = 105.6 Hz), 132.3
(d, JC-P = 13.1 Hz), 132.1 (d, JC-P = 10.0 Hz), 131.9 (d, JC-P = 2.8 Hz), 129.5 (d, JC-P = 103.7 Hz), 128.9, 128.5 (d, JC-P
= 12.1 Hz), 128.4, 128.23 (d, JC-P = 10.3 Hz), 128.18, 127.7, 126.9, 126.8 (d, JC-P = 10.6 Hz); 31P NMR (162 MHz,
CDCl3) δ 29.3.
(4-fluorophenyl)diphenylphosphine oxide (3j)20. The title compound was prepared according to the general
procedure II and purified by column chromatography on silica gel and eluted with petroleum ether: ethyl acetate:
1
dichloromethane = 2:2:1 (v:v:v) to afford a white solid in 83% yield (49.1 mg). H NMR (400 MHz, CDCl3) δ
7.69-7.63 (m, 6H), 7.58-7.54 (m, 2H), 7.49-7.47 (m, 4H), 7.18-7.14 (m, 2H); 13C{1H} NMR (100 MHz, CDCl3) δ
165.0 (dd, JC-F = 252.0 Hz, JC-P = 3.0 Hz), 134.5 (dd, JC-P = 11.3 Hz, JC-F = 8.8 Hz), 132.2 (d, JC-P = 104.3 Hz), 132.1
(d, JC-P = 2.7 Hz), 132.0 (d, JC-P = 9.9 Hz), 128.6 (d, JC-P = 12.1 Hz), 128.5 (dd, JC-P = 105.8 Hz, JC-F = 3.4 Hz), 115.9
(dd, JC-F = 21.2, JC-P = 13.1 Hz); 31P NMR (162 MHz, CDCl3) δ 28.5.
(4-chlorophenyl)diphenylphosphine oxide (3k)20. The title compound was prepared according to the general
procedure II and purified by column chromatography on silica gel and eluted with petroleum ether: ethyl acetate:
1
dichloromethane = 2:2:1 (v:v:v) to afford a white solid in 68% yield (42.5 mg). H NMR (400 MHz, CDCl3) δ
7.60-7.47 (m, 8H), 7.42-7.35 (m, 6H); 13C{1H} NMR (100 MHz, CDCl3) δ 138.6 (d, JC-P = 3.5 Hz), 133.4 (d, JC-P
=
10.7 Hz), 132.1 (d, JC-P = 2.6 Hz), 131.97 (d, JC-P = 104.4 Hz), 131.96 (d, JC-P = 9.8 Hz), 131.0 (d, JC-P = 104.0 Hz),
128.8 (d, JC-P = 12.5 Hz), 128.6 (d, JC-P = 12.3 Hz); 31P NMR (162 MHz, CDCl3) δ 28.5.
benzofuran-2-yldiphenylphosphine oxide (3l)23. The title compound was prepared according to the general
procedure II and purified by column chromatography on silica gel and eluted with petroleum ether: ethyl acetate:
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1
dichloromethane = 2:2:1 (v:v:v) to afford a white solid in 59% yield (37.5 mg). H NMR (400 MHz,CDCl3) δ
7.77-7.71 (m, 4H), 7.57 (d, J = 7.6 Hz, 1H), 7.53-7.48 (m, 2H), 7.46-7.39 (m, 5H), 7.37-7.34 (m, 1H), 7.33-7.29 (m,
1H), 7.22-7.18 (m, 1H); 13C{1H} NMR (100 MHz, CDCl3) δ 157.8 (d, JC-P = 8.0 Hz), 150.2 (d, JC-P = 129.7 Hz), 132.4
(d, JC-P = 2.7 Hz), 131.6 (d, JC-P = 10.6 Hz), 130.9 (d, JC-P = 110.4 Hz), 128.5 (d, JC-P = 12.7 Hz), 126.6, 126.4 (d, JC-P
= 9.1 Hz), 123.5, 122.3, 119.4 (d, JC-P = 17.5 Hz), 112.0; 31P NMR (162 MHz, CDCl3): δ 17.5.
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benzo[b]thiophen-2-yldiphenylphosphine oxide (3m)23. The title compound was prepared according to the general
procedure II and purified by column chromatography on silica gel and eluted with petroleum ether: ethyl acetate:
1
dichloromethane = 2:2:1 (v:v:v) to afford a white solid in 64% yield (42.8 mg). H NMR (400 MHz, CDCl3) δ
7.84-7.73 (m, 7H), 7.58-7.40 (m, 8H); 13C{1H} NMR (100 MHz, CDCl3) δ 143.8 (d, JC-P = 5.5 Hz), 139.2 (d, JC-P
=
13.9 Hz), 134.7 (d, JC-P = 106.3 Hz), 134.3 (d, JC-P = 9.0 Hz), 132.33 (d, JC-P = 2.7 Hz), 132.29 (d, JC-P = 106.9 Hz),
131.8 (d, JC-P = 10.4 Hz), 128.5 (d, JC-P = 12.6 Hz), 126.3, 125.0, 124.9, 122.4; 31P NMR (162 MHz, CDCl3) δ 22.7.
diphenyl(quinolin-6-yl)phosphine oxide (3n)12a. The title compound was prepared according to the general
procedure II and purified by column chromatography on silica gel and eluted with petroleum ether: ethyl acetate:
dichloromethane = 1:2:2 (v:v:v) to afford a white solid in 54% yield (35.7 mg). 1H NMR (400 MHz, CDCl3) δ 9.02 (dd,
J1= 4.0 Hz, J2= 1.6 Hz, 1H), 8.37 (dd, J1= 13.2, J2= 1.6 Hz, 1H), 8.23-8.21 (m, 1H), 8.17 (dd, J1 = 8.4, J2= 2.4 Hz, 1H),
7.87-7.82 (m, 1H), 7.74-7.69 (m, 4H), 7.60-7.56 (m, 2H), 7.52-7.47 (m, 5H); 13C{1H} NMR (100 MHz, CDCl3) δ
152.5, 149.2 (d, JC-P = 2.6 Hz), 137.0, 134.1 (d, JC-P = 9.3 Hz), 132.2 (d, JC-P = 2.7 Hz), 132.03 (d, JC-P =9.8 Hz),
132.01 (d, JC-P =104.1 Hz), 130.8 (d, JC-P =102.3 Hz), 129.8 (d, JC-P =10.0 Hz), 129.7 (d, JC-P =11.8 Hz), 128.6 (d, JC-P
= 12.1 Hz), 127.5 (d, JC-P = 13.5 Hz), 122.1; 31P NMR (162 MHz, CDCl3) δ 28.5.
(E)-diphenyl(styryl)phosphine oxide (3o)24. The title compound was prepared according to the general procedure II
and purified by column chromatography on silica gel and eluted with petroleum ether: ethyl acetate: dichloromethane =
1
2:2:1 (v:v:v) to afford a white solid in 45% yield (27.3 mg). H NMR (400 MHz, CDCl3) δ 7.79-7.73 (m, 4H),
7.55-7.46 (m, 9H), 7.40-7.37 (m, 3H), 6.84 (dd, J1 = 17.6 Hz, J2 = 22.4 Hz, 1H); 13C{1H} NMR (100 MHz, CDCl3) δ
147.5 (d, JC-P = 3.6 Hz), 135.1 (d, JC-P = 17.8 Hz), 132.9 (d, JC-P = 105.2 Hz), 131.9 (d, JC-P = 2.7 Hz), 131.4 (d, JC-P
=
10.0 Hz), 130.1, 128.8, 128.6 (d, JC-P = 11.9 Hz), 127.8, 119.2 (d, JC-P = 103.9 Hz); 31P NMR (162 MHz, CDCl3) δ
24.6.
phenyldi-p-tolylphosphine oxide (3p)21. The title compound was prepared according to the general procedure II and
purified by column chromatography on silica gel and eluted with petroleum ether: ethyl acetate: dichloromethane =
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2:2:1 (v:v:v) to afford a white solid in 96% yield (58.7 mg). H NMR (400 MHz, CDCl3) δ 7.59-7.54 (m, 2H),
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7.48-7.41 (m, 5H), 7.37-7.32 (m, 2H), 7.20-7.16 (m, 4H), 2.30 (s, 6H); C{1H} NMR (100 MHz, CDCl3) δ 142.2 (d,
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JC-P =2.7 Hz), 132.8 (d, JC-P = 103.5 Hz), 131.94 (d, JC-P = 10.2 Hz), 131.87 (d, JC-P = 10.0 Hz), 131.6 (d, JC-P = 2.6
Hz), 129.12 (d, JC-P = 106.0 Hz), 129.09 (d, JC-P = 12.1 Hz), 128.3 (d, JC-P = 12.0 Hz), 21.5; 31P NMR (162 MHz,
CDCl3) δ 29.7.
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butyldiphenylphosphine oxide (3q)25. The title compound was prepared according to the general procedure II and
purified by column chromatography on silica gel and eluted with petroleum ether: ethyl acetate: dichloromethane =
1
2:2:1 (v:v:v) to afford a white solid in 65% yield (33.5 mg). H NMR (400 MHz, CDCl3) δ 7.77-7.73 (m, 4H),
7.50-7.44 (m, 6H), 2.30-2.23 (m, 2H), 1.66-1.56 (m, 2H), 1.45-1.39 (m, 2H), 0.90-0.86 (m, 3H); 13C{1H} NMR (100
MHz, CDCl3) δ 132.9 (d, JC-P = 97.1 Hz), 131.4 (d, JC-P = 2.6 Hz), 130.5 (d, JC-P = 9.2 Hz), 128.4 (d, JC-P = 11.5 Hz),
29.2 (d, JC-P = 71.8 Hz), 23.9 (d, JC-P = 15.0 Hz), 23.2 (d, JC-P = 4.0 Hz), 13.4; 31P NMR (162 MHz, CDCl3) δ 32.6.
ethyl diphenylphosphinate (3r)20. The title compound was prepared according to the general procedure II and
purified by column chromatography on silica gel and eluted with petroleum ether: ethyl acetate: dichloromethane =
1
2:2:1 (v:v:v) to afford a white solid in 81% yield (39.8 mg). H NMR (400 MHz, CDCl3) δ 7.74-7.68 (m, 4H),
7.38-7.27 (m, 6H), 4.02-3.94 (m, 2H), 1.25-1.21 (m, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ 131.7 (d, JC-P = 2.7 Hz),
131.3 (d, JC-P = 135.9 Hz), 131.2 (d, JC-P = 10.1 Hz), 128.2 (d, JC-P = 13.0 Hz), 60.7 (d, JC-P = 5.8 Hz), 16.4 (d, JC-P
6.6 Hz); 31P NMR (162 MHz, CDCl3) δ 31.1.
=
diethyl phenylphosphonate (3s)20. The title compound was prepared according to the general procedure II and
purified by column chromatography on silica gel and eluted with petroleum ether: ethyl acetate = 2:1 (v:v) to afford a
colorless oil in 48% yield (20.6 mg). 1H NMR (400 M, CDCl3) δ 7.85-7.79 (m, 2H), 7.57-7.53 (m, 1H), 7.49-7.44 (m,
2H), 4.20-4.03 (m, 4H), 1.34-1.31 (m, 6H); 13C{1H} NMR (100 MHz, CDCl3) δ 132.2 (d, JC-P = 3.0 Hz), 131.6 (d, JC-P
= 9.8 Hz), 128.3 (d, JC-P = 14.9 Hz), 128.1 (d, JC-P = 186.6 Hz), 61.9 (d, JC-P = 5.4 Hz), 16.1 (d, JC-P = 6.4 Hz); 31P
NMR (162 MHz, CDCl3) δ 18.8.
diisopropyl phenylphosphonate (3t)26. The title compound was prepared according to the general procedure II and
purified by column chromatography on silica gel and eluted with petroleum ether: ethyl acetate = 2:1 (v:v) to afford a
colorless oil in 55% yield (26.7 mg). 1H NMR (400 M, CDCl3) δ 7.77-7.71 (m, 2H), 7.47-7.43 (m, 1H), 7.39-7.34 (m,
2H), 4.67-4.57 (m, 2H), 1.29 (d, J = 6.0 Hz, 6H), 1.15 (d, J = 6.4 Hz, 6H); 13C{1H} NMR (100 MHz, CDCl3) δ 132.0
(d, JC-P = 3.2 Hz), 131.6 (d, JC-P = 9.7 Hz), 129.8 (d, JC-P = 187.4 Hz), 128.2 (d, JC-P = 14.8 Hz), 70.6 (d, JC-P = 5.5 Hz),
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24.0 (d, JC-P = 4.0 Hz), 23.7 (d, JC-P = 4.6 Hz); 31P NMR (162 MHz, CDCl3) δ 16.6.
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dibutyl phenylphosphonate (3u)26. The title compound was prepared according to the general procedure II and
purified by column chromatography on silica gel and eluted with petroleum ether: ethyl acetate = 2:1 (v:v) to afford a
colorless oil in 45% yield (24.1 mg). 1H NMR (400 M, CDCl3) δ 7.75-7.70 (m, 2H), 7.48-7.44 (m, 1H), 7.40-7.36 (m,
2H), 4.02-3.90 (m, 4H), 1.60-1.52 (m, 4H), 1.35-1.26 (m, 4H), 0.84-0.79 (m, 6H); 13C{1H} NMR (100 MHz, CDCl3) δ
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132.1 (d, JC-P = 2.9 Hz), 131.5 (d, JC-P = 9.6 Hz), 128.2 (d, JC-P = 15.0 Hz), 128.1 (d, JC-P = 186.9 Hz), 65.6 (d, JC-P
5.6 Hz), 32.2 (d, JC-P = 6.4 Hz), 18.5, 13.4; 31P NMR (162 MHz, CDCl3) δ 18.7.
=
benzyldiphenylphosphine oxide (4a)27. The title compound was prepared according to the general procedure III and
purified by column chromatography on silica gel and eluted with petroleum ether: ethyl acetate: dichloromethane =
1
2:2:1 (v:v:v) to afford a white solid in 94% yield (55.0 mg). H NMR (400 MHz, CDCl3) δ 7.65-7.60 (m, 4H),
7.46-7.42 (m, 2H), 7.39-7.34 (m, 4H), 7.13-7.10 (m, 3H), 7.05-7.02 (m, 2H), 3.59 (d, J = 13.6 Hz, 2H); 13C{1H} NMR
(100 MHz, CDCl3) δ 132.2 (d, JC-P = 97.4 Hz), 131.7 (d, JC-P = 2.1 Hz), 131.1 (d, JC-P = 9.1 Hz), 130.1 (d, JC-P = 5.2
Hz), 128.4 (d, JC-P =11.6 Hz), 128.3 (d, JC-P = 2.4 Hz), 126.7 (d, JC-P = 2.8 Hz), 38.1 (d, JC-P = 66.1 Hz); 31P NMR (162
MHz, CDCl3) δ 29.7.
(4-methylbenzyl)diphenylphosphine oxide (4b)27. The title compound was prepared according to the general
procedure III and purified by column chromatography on silica gel and eluted with petroleum ether: ethyl acetate:
1
dichloromethane = 2:2:1 (v:v:v) to afford a white solid in 92% yield (56.6 mg). H NMR (400 MHz, CDCl3) δ
7.65-7.60 (m, 4H), 7.46-7.42 (m, 2H), 7.39-7.35 (m, 4H), 6.92 (s, 4H), 3.55 (d, J = 13.6 Hz, 2H), 2.19 (d, J = 2.0 Hz,
13
3H); C{1H} NMR (100 MHz, CDCl3) δ 136.3 (d, JC-P = 3.1 Hz), 132.4(d, JC-P = 98.0 Hz), 131.7 (d, JC-P = 2.5 Hz),
131.1 (d, JC-P = 9.1 Hz), 129.9 (d, JC-P = 5.2 Hz), 129.1 (d, JC-P = 2.3 Hz), 128.4 (d, JC-P = 11.6 Hz), 127.8 (d, JC-P = 7.9
Hz), 37.6 (d, JC-P = 66.6 Hz), 21.0; 31P NMR (162 MHz, CDCl3) δ 29.6.
(3-methylbenzyl)diphenylphosphine oxide (4c)27. The title compound was prepared according to the general
procedure III and purified by column chromatography on silica gel and eluted with petroleum ether: ethyl acetate:
1
dichloromethane = 2:2:1 (v:v:v) to afford a white solid in 91% yield (55.7 mg). H NMR (400 MHz, CDCl3) δ
7.64-7.59 (m, 4H), 7.44-7.41 (m, 2H), 7.37-7.34 (m, 4H), 6.98 (dd, J1 = J2 = 7.6 Hz, 1H), 6.90 (d, J = 7.2 Hz, 1H), 6.84
(s, 1H), 6.78 (d, J = 7.6 Hz, 1H), 3.54 (d, J = 13.6 Hz, 2H), 2.14 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ 137.9 (d,
JC-P = 1.5 Hz), 132.3(d, JC-P = 98.9 Hz), 131.7 (d, JC-P = 1.5 Hz), 131.1 (d, JC-P = 9.0 Hz), 130.9 (d, JC-P = 4.9 Hz),
130.8 (d, JC-P = 7.8 Hz), 128.4 (d, JC-P = 11.5 Hz), 128.1 (d, JC-P = 1.2 Hz), 127.5 (d, JC-P = 2.1 Hz), 127.0 (d, JC-P = 4.9
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Hz), 38.0 (d, JC-P = 66.8 Hz), 21.2; 31P NMR (162 MHz, CDCl3) δ 29.6.
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(2-methylbenzyl)diphenylphosphine oxide (4d)27. The title compound was prepared according to the general
4
5
procedure III and purified by column chromatography on silica gel and eluted with petroleum ether: ethyl acetate:
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dichloromethane = 2:2:1 (v:v:v) to afford a white solid in 87% yield (53.2 mg). H NMR (400 MHz, CDCl3) δ
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9
7.62-7.57 (m, 4H), 7.46-7.42 (m, 2H), 7.38-7.33 (m, 4H), 7.02-7.00 (m, 2H), 6.93-6.86 (m, 2H), 3.59 (d, J = 14.0 Hz,
2H), 2.06 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ 137.4 (d, JC-P = 5.2 Hz), 132.4(d, JC-P = 98.0 Hz), 131.8 (d, JC-P
= 2.7 Hz), 131.1 (d, JC-P = 9.0 Hz), 130.6 (d, JC-P = 4.7 Hz), 130.4 (d, JC-P = 2.6 Hz), 129.6 (d, JC-P =8.1 Hz), 128.4 (d,
JC-P = 11.6 Hz), 126.9 (d, JC-P = 3.1 Hz), 125.7 (d, JC-P = 2.8 Hz), 35.2 (d, JC-P = 66.2 Hz), 20.0 (d, JC-P = 0.9 Hz); 31P
NMR (162 MHz, CDCl3) δ 29.7.
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(4-(tert-butyl)benzyl)diphenylphosphine oxide (4e)27. The title compound was prepared according to the general
procedure III and purified by column chromatography on silica gel and eluted with petroleum ether: ethyl acetate:
o
1
dichloromethane = 2:2:1 (v:v:v) to afford a white solid in 91% yield (63.3 mg), m.p. 247.9-248.8 C. H NMR (400
MHz, CDCl3) δ 7.73-7.67 (m, 4H), 7.51-7.48 (m, 2H), 7.44-7.40 (m, 4H), 7.20 (d, J = 8.0 Hz, 2H), 7.04 (dd, J1= 8.4
Hz, J2= 2.4 Hz, 2H), 3.63 (d, J = 13.2 Hz, 2H), 1.25 (s, 9H); 13C{1H} NMR (100 MHz, CDCl3) δ 149.5 (d, JC-P = 3.1
Hz), 132.4 (d, JC-P = 98.1 Hz), 131.7 (d, JC-P = 2.7 Hz), 131.1 (d, JC-P = 8.9 Hz), 129.7 (d, JC-P = 5.3 Hz), 128.4 (d, JC-P
= 11.5 Hz), 127.8 (d, JC-P = 8.0 Hz), 125.3 (d, JC-P = 2.6 Hz), 37.4 (d, JC-P = 66.5 Hz), 34.3, 31.2; 31P NMR (162 MHz,
CDCl3) δ 29.5.
(4-methoxybenzyl) diphenylphosphine oxide (4f)27. The title compound was prepared according to the general
procedure III and purified by column chromatography on silica gel and eluted with petroleum ether: ethyl acetate:
1
dichloromethane = 2:2:1 (v:v:v) to afford a white solid in 96% yield (61.9 mg). H NMR (400 MHz, CDCl3) δ
7.64-7.59 (m, 4H), 7.45-7.40 (m, 2H), 7.38-7.33 (m, 4H), 6.96-6.93 (m, 2H), 6.65 (d, J = 8.4 Hz, 2H), 3.66 (s, 3H),
3.52 (d, J = 13.2 Hz, 2H); 13C{1H} NMR (100 MHz, CDCl3) δ 158.5 (d, JC-P = 2.8 Hz), 132.4(d, JC-P = 97.9 Hz), 131.7
(d, JC-P = 2.6 Hz), 131.13 (d, JC-P = 8.8 Hz) , 131.05 (d, JC-P = 3.4 Hz), 128.4 (d, JC-P = 11.5 Hz), 122.9 (d, JC-P = 8.0
Hz), 113.8 (d, JC-P = 2.5 Hz) , 55.1, 37.0 (d, JC-P = 67.1 Hz); 31P NMR (162 MHz, CDCl3) δ 29.4.
([1,1'-biphenyl]-4-ylmethyl)diphenylphosphine oxide (4g)13c. The title compound was prepared according to the
general procedure III and purified by column chromatography on silica gel and eluted with petroleum ether: ethyl
acetate: dichloromethane = 2:2:1 (v:v:v) to afford a white solid in 81% yield (59.5 mg). 1H NMR (400 MHz, CDCl3) δ
7.75-7.70 (m, 4H), 7.55-7.51 (m, 4H), 7.48-7.39 (m, 8H), 7.33-7.30 (m, 1H), 7.17 (dd, J = 8.0, 2.0 Hz, 2H), 3.70 (d, J
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= 13.6 Hz, 2H); 13C{1H} NMR (100 MHz, CDCl3) δ 140.6, 139.6 (d, JC-P = 3.0 Hz), 132.2 (d, JC-P = 98.8 Hz), 131.9 (d,
JC-P = 2.5 Hz), 131.2 (d, JC-P = 9.2 Hz), 130.5 (d, JC-P = 5.2 Hz), 130.1 (d, JC-P = 8.0 Hz), 128.7, 128.5 (d, JC-P = 11.7
Hz), 127.2, 127.1 (d, JC-P = 2.5 Hz), 126.9, 37.7 (d, JC-P = 66.1 Hz); 31P NMR (162 MHz, CDCl3) δ 29.6.
(naphthalen-1-ylmethyl)diphenylphosphine oxide (4h)13a. The title compound was prepared according to the
general procedure III and purified by column chromatography on silica gel and eluted with petroleum ether: ethyl
acetate: dichloromethane = 2:2:1 (v:v:v) to afford a white solid in 93% yield (63.7 mg). 1H NMR (400 MHz, CDCl3) δ
7.85 (d, J = 8.4 Hz, 1H), 7.71-7.69 (m, 1H), 7.64-7.59 (m, 5H), 7.42-7.38 (m, 2H), 7.35-7.29 (m, 6H), 7.20-7.15 (m,
2H), 4.05 (d, J = 13.6 Hz, 2H); 13C{1H} NMR (100 MHz, CDCl3) δ 133.7 (d, JC-P = 2.0 Hz), 132.4 (d, JC-P = 4.3 Hz),
132.3 (d, JC-P = 97.5 Hz), 131.8 (d, JC-P = 2.5 Hz), 131.2 (d, JC-P = 8.9 Hz), 128.6 (d, JC-P = 6.2 Hz), 128.5, 128.4 (d,
JC-P = 11.6 Hz), 127.7 (d, JC-P = 9.5 Hz), 127.6, 125.9, 125.5, 125.1 (d, JC-P = 3.1 Hz), 124.2, 34.8 (d, JC-P = 66.5 Hz);
31P NMR (162 MHz, CDCl3) δ 29.7.
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(naphthalen-2-ylmethyl)diphenylphosphine oxide (4i)27. The title compound was prepared according to the
general procedure III and purified by column chromatography on silica gel and eluted with petroleum ether: ethyl
acetate: dichloromethane = 2:2:1 (v:v:v) to afford a white solid in 95% yield (64.9 mg). 1H NMR (400 MHz, CDCl3) δ
7.66-7.56 (m, 7H), 7.48 (s, 1H), 7.42-7.38 (m, 2H), 7.35-7.30 (m, 6H), 7.17-7.13 (m, 1H), 3.72 (d, J = 13.6 Hz, 2H);
13C{1H} NMR (100 MHz, CDCl3) δ 133.2 (d, JC-P = 2.5 Hz), 132.2 (d, JC-P = 98.3 Hz), 132.1 (d, JC-P = 1.8 Hz), 131.8
(d, JC-P = 2.5 Hz), 131.1 (d, JC-P = 9.1 Hz), 128.9 (d, JC-P = 6.6 Hz), 128.7 (d, JC-P =8.3 Hz), 128.4 (d, JC-P = 11.6 Hz),
128.1 (d, JC-P = 4.1 Hz), 127.9 (d, JC-P = 1.5 Hz), 127.54, 127.47, 125.9, 125.6, 38.2 (d, JC-P = 66.0 Hz); 31P NMR (162
MHz, CDCl3) δ 29.4.
(4-fluorobenzyl)diphenylphosphine oxide (4j)27. The title compound was prepared according to the general
procedure III and purified by column chromatography on silica gel and eluted with petroleum ether: ethyl acetate:
1
dichloromethane = 2:2:1 (v:v:v) to afford a white solid in 45% yield (27.9 mg). H NMR (400 MHz, CDCl3) δ
7.66-7.59 (m, 4H), 7.47-7.43 (m, 2H), 7.40-7.36 (m, 4H), 7.02-6.98 (m, 2H), 6.80 (dd, J1 = J2 = 8.4 Hz, 2H), 3.55 (d, J
13
= 13.2 Hz, 2H); C{1H} NMR (100 MHz, CDCl3) δ 161.8 (dd, JC-F = 240.7 Hz, JC-P = 3.0 Hz), 132.1 (d, JC-P = 99.3
Hz), 131.9 (d, JC-P = 2.5 Hz), 131.5 (dd, JC-F = 7.8 Hz, JC-P = 4.9 Hz), 131.1 (d, JC-P = 9.1 Hz), 128.5 (d, JC-P = 11.6
Hz), 126.8 (dd, JC-P = 8.1 Hz, JC-F = 3.1 Hz), 115.2 (dd, JC-F = 21.3, JC-P = 2.3 Hz), 37.1 (d, JC-P = 66.3 Hz); 31P NMR
(162 MHz, CDCl3) δ 29.5 (d, JP-F = 4.4 Hz).
(4-chlorobenzyl)diphenylphosphine oxide (4k)27. The title compound was prepared according to the general
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procedure III and purified by column chromatography on silica gel and eluted with petroleum ether: ethyl acetate:
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dichloromethane = 2:2:1 (v:v:v) to afford a white solid in 61% yield (39.9 mg). H NMR (400 MHz, CDCl3) δ
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7.65-7.58 (m, 4H), 7.48-7.42 (m, 2H), 7.40-7.35 (m, 4H), 7.08 (d, J = 8.4 Hz, 2H), 7.00-6.93 (m, 2H), 3.54 (d, J = 13.6
Hz, 2H); 13C{1H} NMR (100 MHz, CDCl3) δ 132.8 (d, JC-P = 3.5 Hz), 131.95 (d, JC-P = 98.7 Hz), 131.92 (d, JC-P = 2.5
Hz), 131.3 (d, JC-P = 5.1 Hz), 131.1 (d, JC-P = 9.2 Hz), 129.7 (d, JC-P = 8.0 Hz), 128.6 (d, JC-P = 11.6 Hz), 128.5 (d, JC-P
= 2.0 Hz), 37.4 (d, JC-P = 65.8 Hz); 31P NMR (162 MHz, CDCl3) δ 29.2.
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(4-bromobenzyl)diphenylphosphine oxide (4l)28. The title compound was prepared according to the general
procedure III and purified by column chromatography on silica gel and eluted with petroleum ether: ethyl acetate:
1
dichloromethane = 2:2:1 (v:v:v) to afford a white solid in 36% yield (27.0 mg). H NMR (400 MHz, CDCl3) δ
7.64-7.59 (m, 4H), 7.47-7.43 (m, 2H), 7.40-7.36 (m, 4H), 7.23 (d, J = 8.4 Hz, 2H), 6.91 (dd, J1 = 1.6 Hz, J2 = 8.4 Hz,
2H), 3.53 (d, J = 13.6 Hz, 2H); 13C{1H} NMR (100 MHz, CDCl3) δ 132.0 (d, JC-P = 2.7 Hz),131.9 (d, JC-P = 99.0 Hz),
131.7 (d, JC-P = 5.1 Hz), 131.4 (d, JC-P = 2.4 Hz), 131.1 (d, JC-P = 9.3 Hz), 130.2 (d, JC-P = 7.9 Hz), 128.6 (d, JC-P = 11.6
Hz), 121.0 (d, JC-P = 3.6 Hz), 37.5 (d, JC-P = 65.7 Hz); 31P NMR (162 MHz, CDCl3) δ 29.0.
4-((diphenylphosphoryl)methyl)benzonitrile (4m)27. The title compound was prepared according to the general
procedure III and purified by column chromatography on silica gel and eluted with petroleum ether: ethyl acetate:
1
dichloromethane = 2:2:1 (v:v:v) to afford a white solid in 87% yield (55.4 mg). H NMR (400 MHz, CDCl3): δ
7.64-7.59 (m, 4H), 7.50-7.46 (m, 2H), 7.42-7.38 (m, 6H), 7.15 (dd, J1= 8.0 Hz, J2= 1.6 Hz, 2H), 3.63 (d, J = 13.6 Hz,
2H); 13C{1H} NMR (100 MHz, CDCl3) δ 137.1 (d, JC-P = 7.9 Hz), 132.1 (d, JC-P = 2.4 Hz), 132.0 (d, JC-P = 2.2 Hz),
131.5 (d, JC-P = 99.7 Hz), 130.9 (d, JC-P = 9.3 Hz), 130.8 (d, JC-P = 5.0 Hz), 128.7 (d, JC-P = 11.8 Hz), 118.7, 110.7 (d,
JC-P = 3.1 Hz), 38.4 (d, JC-P = 63.9 Hz); 31P NMR (162 MHz, CDCl3) δ 29.0.
diphenyl(4-(trifluoromethyl)benzyl)phosphine oxide (4n)27. The title compound was prepared according to the
general procedure III and purified by column chromatography on silica gel and eluted with petroleum ether: ethyl
acetate: dichloromethane = 2:2:1 (v:v:v) to afford a white solid in 91% yield (65.8 mg). 1H NMR (400 MHz, CDCl3) δ
7.65-7.60 (m, 4H), 7.47-7.43 (m, 2H), 7.40-7.35 (m, 6H), 7.15 (d, J = 7.2 Hz, 2H), 3.62 (d, J = 13.6 Hz, 2H); 13C{1H}
NMR (100 MHz, CDCl3) δ 135.5 (d, JC-P = 8.3 Hz), 132.0 (d, JC-P = 2.6 Hz), 131.8 (d, JC-P = 99.5 Hz), 131.0 (d, JC-P
9.2 Hz), 130.3 (d, JC-P = 5.1 Hz), 129.6-128.5 (m, 1C), 128.6 (d, JC-P = 11.7 Hz), 125.3-125.1 (m, 1C), 124.1 (q, JC-P
270.2 Hz), 38.0 (d, JC-P = 64.9 Hz); 31P NMR (162 MHz, CDCl3) δ 29.2 (d, JP-F = 1.8 Hz).
=
=
(benzofuran-2-ylmethyl)diphenylphosphine oxide (4o)29. The title compound was prepared according to the
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general procedure III and purified by column chromatography on silica gel and eluted with petroleum ether: ethyl
acetate: dichloromethane = 2:2:1 (v:v:v) to afford a white solid in 93% yield (62.1 mg). 1H NMR (400 MHz, CDCl3) δ
7.78-7.73 (m, 4H), 7.54-7.51 (m, 2H), 7.47-7.41 (m, 5H), 7.30 (d, J = 1.9 Hz, 1H), 7.19-7.12 (m, 2H), 6.54 (d, J = 2.8
Hz, 1H), 3.88 (d, J = 14.0 Hz, 2H); 13C{1H} NMR (100 MHz, CDCl3) δ 154.6 (d, JC-P = 1.0 Hz), 148.6 (d, JC-P = 7.8
Hz), 132.1 (d, JC-P = 2.8 Hz), 131.8 (d, JC-P = 100.5 Hz), 131.1 (d, JC-P = 9.5 Hz), 128.582 (d, JC-P = 2.2 Hz), 128.581
(d, JC-P = 11.9 Hz), 123.7, 122.6, 120.6, 110.8, 106.0 (d, JC-P = 6.1 Hz), 31.8 (d, JC-P = 67.7 Hz); 31P NMR (162 MHz,
CDCl3) δ 27.8.
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(benzo[b]thiophen-2-ylmethyl)diphenylphosphine oxid (4p). The title compound was prepared according to the
general procedure III and purified by column chromatography on silica gel and eluted with petroleum ether: ethyl
acetate: dichloromethane = 2:2:1 (v:v:v) to afford a white solid in 70% yield (48.7 mg) , m.p. 254.2-255.9 oC. 1H NMR
(400 MHz, CDCl3) δ 7.79-7.74 (m, 4H), 7.68 (d, J = 7.6 Hz, 1H), 7.62 (d, J = 7.4 Hz, 1H), 7.56-7.52 (m, 2H),
7.49-7.45 (m, 4H), 7.29-7.21 (m, 3H), 3.94 (d, J = 13.2 Hz, 2H); 13C{1H} NMR (100 MHz, CDCl3) δ 139.8, 139.7 (d,
JC-P = 2.5 Hz), 133.1 (d, JC-P = 8.5 Hz), 132.1 (d, JC-P = 2.5 Hz), 131.7 (d, JC-P = 99.0 Hz), 131.1 (d, JC-P = 9.1 Hz),
128.7 (d, JC-P = 11.7 Hz), 124.5 (d, JC-P = 7.6 Hz), 124.1, 123.9, 123.1, 121.9, 33.3 (d, JC-P = 67.4 Hz); 31P NMR (162
MHz, CDCl3) δ 28.4. HRMS (ESI, positive mode): C21H18OPS for [M+H]+, calculated 349.0810, found 349.0803.
diphenyl(quinolin-6-ylmethyl)phosphine oxide (4q). The title compound was prepared according to the general
procedure III and purified by column chromatography on silica gel and eluted with petroleum ether: ethyl acetate:
o
1
dichloromethane = 1:2:2 (v:v:v) to afford a white solid in 91% yield (62.2 mg), m.p. 229.7-230.3 C. H NMR (400
MHz, CDCl3) δ 8.85 (d, J = 3.2 Hz, 1H), 8.02 (d, J = 8.4 Hz, 1H), 7.90 (d, J = 8.8 Hz, 1H), 7.74-7.69 (m, 4H), 7.66 (s,
1H), 7.54-7.50 (m, 2H), 7.47-7.42 (m, 4H), 7.39-7.33 (m, 2H), 3.84 (d, J = 14.0 Hz, 2H); 13C{1H} NMR (100 MHz,
CDCl3) δ 150.2, 147.2 (d, JC-P = 2.1 Hz), 135.8, 132.0 (d, JC-P = 98.8 Hz), 131.9 (d, JC-P = 2.6 Hz), 131.7 (d, JC-P = 4.3
Hz), 131.1 (d, JC-P = 9.1 Hz), 129.7 (d, JC-P = 8.3 Hz), 129.3 (d, JC-P = 1.6 Hz), 128.8 (d, JC-P = 6.2 Hz), 128.5 (d, JC-P
=
31
11.7 Hz), 128.0 (d, JC-P = 2.7 Hz), 121.2, 38.1 (d, JC-P = 65.2 Hz); P NMR (162 MHz, CDCl3) δ 29.2. HRMS (ESI,
positive mode): C22H19NOP for [M+H]+, calculated 344.1199, found 344.1168.
benzyldi-p-tolylphosphine oxide (4r)27. The title compound was prepared according to the general procedure III
and purified by column chromatography on silica gel and eluted with petroleum ether: ethyl acetate: dichloromethane =
1
2:2:1 (v:v:v) to afford a white solid in 80% yield (51.2 mg). H NMR (400 MHz, CDCl3) δ 7.50-7.45 (m, 4H),
7.15-7.08 (m, 7H), 7.03-7.01 (m, 2H), 3.53 (d, J = 13.6 Hz, 2H), 2.28 (s, 6H); 13C{1H} NMR (100 MHz, CDCl3) δ
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142.0 (d, JC-P =2.7 Hz), 132.0 (d, JC-P = 10.4 Hz), 131.3 (d, JC-P = 7.9 Hz), 131.0 (d, JC-P = 9.4 Hz), 130.1 (d, JC-P = 5.2
Hz), 129.1 (d, JC-P = 12.0 Hz), 129.0 (d, JC-P = 100.9 Hz), 128.2 (d, JC-P = 2.3 Hz), 126.6 (d, JC-P = 2.9 Hz), 38.1 (d,
JC-P = 66.3 Hz), 21.5 (d, JC-P = 0.9 Hz); 31P NMR (162 MHz, CDCl3) δ 30.0.
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benzyl(butyl)(phenyl)phosphine oxide (4s)27. The title compound was prepared according to the general procedure
III and purified by column chromatography on silica gel and eluted with petroleum ether: ethyl acetate:
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dichloromethane = 2:2:1 (v:v:v) to afford a white solid in 69% yield (37.4 mg). H NMR (400 MHz, CDCl3) δ
7.53-7.48 (m, 2H), 7.45-7.41 (m, 1H), 7.38-7.33 (m, 2H), 7.18-7.12 (m, 3H), 7.02-7.00 (m, 2H), 3.30-3.17 (m, 2H),
1.964-1.74 (m, 2H), 1.57-1.47 (m, 1H), 1.38-1.23 (m, 3H), 0.77 (t, J = 7.2 Hz, 3H); 13C{1H} NMR (100 MHz, CDCl3)
δ 131.74 (d, JC-P = 7.4 Hz), 131.71 (d, JC-P = 92.5 Hz), 131.5 (d, JC-P = 2.7 Hz), 130.7 (d, JC-P = 8.6 Hz), 129.7 (d, JC-P
= 4.9 Hz), 128.4 (d, JC-P = 2.7 Hz), 128.3 (d, JC-P = 11.0 Hz), 126.7 (d, JC-P = 2.9 Hz), 38.9 (d, JC-P = 62.0 Hz), 27.9 (d,
JC-P = 69.1 Hz), 24.0 (d, JC-P = 14.5 Hz), 23.2 (d, JC-P = 4.0 Hz), 13.5; 31P NMR (162 MHz, CDCl3) δ 38.2.
ethyl benzyl(phenyl)phosphinate (4t)27. The title compound was prepared according to the general procedure III
and purified by column chromatography on silica gel and eluted with petroleum ether: ethyl acetate: dichloromethane =
1
2:2:1 (v:v:v) to afford a white solid in 38% yield (19.8 mg). H NMR (400 MHz, CDCl3) δ 7.62-7.57 (m, 2H),
7.52-7.48 (m, 1H), 7.41-7.37 (m, 2H), 7.23-7.17 (m, 3H), 7.10-7.07 (m, 2H), 4.12-4.02 (m, 1H), 3.93-3.83 (m, 1H),
3.29 (d, J = 18.0 Hz, 2H), 1.27 (t, J = 7.2 Hz, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ 132.1 (d, JC-P = 2.7 Hz), 131.8
(d, JC-P = 9.4 Hz), 131.3 (d, JC-P = 7.5 Hz), 130.0 (d, JC-P = 124.8 Hz), 129.8 (d, JC-P = 5.7 Hz), 128.17 (d, JC-P = 5.4
Hz), 128.15 (d, JC-P = 10.0 Hz), 126.5 (d, JC-P = 3.4 Hz), 60.8 (d, JC-P = 6.5 Hz), 38.0 (d, JC-P = 94.7 Hz), 16.3 (d, JC-P
6.5 Hz); 31P NMR (162 MHz, CDCl3) δ 39.9.
=
AUTHOR INFORMATION
Corresponding Author
*E-mail: chentieqiao@hnu.edu.cn
Notes
The authors declare no competing financial interest.
SUPPORTING INFORMATION
The Supporting Information including optimization of the reactions and copies of 1H, 13C and 31P NMR spectroscopies. This
material is available free of charge via the Internet at http://pubs.acs.org.
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ACKNOWLEDGMENT
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Partial financial support from the HNNSFC (No. 219MS005) and the NSFC (No. 21871070) is gratefully acknowledged.
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(14) One referee was interested in the reactivity difference between thioesters and esters. We did the comparison by
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