Zinc-catalyzed regioselective C-P coupling of p-quinol ethers with secondary phosphine oxides to afford 2-phosphinylphenols

Article abstract of DOI:10.1039/c9ob00129h

The zinc triflate-catalyzed highly regioselective C-P cross coupling reaction of p-quinol ethers with secondary phosphine oxides is reported. The reaction provides a facile alternative method for the synthesis of 2-phosphinylphenols in good to high yields. Mechanistically, zinc triflate may serve as an oxophilic σ-Lewis acid to activate the C-O bond in p-quinol ether first. Then the regioselective attack of the phosphorus nucleophile at the α-carbon position takes place to form the C-P bond and give the product. In addition, α-alkynyl substituted p-quinol ethers also react with secondary phosphine oxides in the same reaction mode to give 6-alkynyl 2-phosphinylphenols in the presence of the zinc catalyst.

Full text of DOI:10.1039/c9ob00129h

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Zinc-Catalyzed Regioselective C–P Couplings of p-Quinol Ethers
with Secondary Phosphine Oxides to Afford 2-Phosphinylphenols
Received 00th January 20xx,
Accepted 00th January 20xx
Ming Zhang,a Xiaoyu Jia,b Haowei Zhu,b Xutong Fang,b Chenyi Ji,b Sizhuo Zhao,b Li-Biao Han,c and
Ruwei Shena,b
*
DOI: 10.1039/x0xx00000x
The zinc triflate-catalyzed highly regioselective C–P cross coupling reaction of p-quinol ethers with secondary phosphine
oxides is reported. The reaction provides a facile alternative method for the synthesis of 2-phosphinylphenols in good to
high yields. Mechanistically, zinc triflate may serve as an oxophilic σ-Lewis acid to activate the C–O bond in p-quinol ether
first. Then the regioselective attack of the phosphorus nucleophile to the α-carbon position takes place to form the C–P
bond and give the product. In addition, α-alkynyl substituted p-quinol ethers also react with secondary phosphine oxides
in a same reaction mode to give 6-alkynyl 2-phosphinylphenols in the presence of the zinc catalyst.
www.rsc.org/
extensively studied for the preparation of some 2-
phosphinylphenols.11 However, the procedure requires the use
of a strong base (LDA or t-BuLi), as the migration of
phosphorus from oxygen to carbon in ortho-lithiated
intermediates is involved. The transition-metal catalyzed Hirao
Introduction
Organophosphorus compounds are of fundamental
importance in organic synthesis, catalysis, biochemistry and
material science.1,
2
Among them, 2-phosphinyl and 2-
reaction of
a
pre-synthesized 2-halophenol with
phosphanyl phenols are highly valuable intermediates, and
many compounds containing such structural units have found
useful applications in the fields such as asymmetric catalysis,3-6
polymerization process,7 supramolecular chemistry8 and
optoelectronic materials (Figure 1a).9 For example, chiral
phosphine-phosphite ligands I and II developed by Schmalz
and Pizzano, have shown outstanding performance on
enantioselective catalytic reactions such as olefin
secondary phosphine oxide provides another useful approach
under mild conditions,12 and some palladium,12c-12g copper12h,
12i
and nickel12j-12l complexes have been reported as modified
catalysts. In addition, the insertion of arynes into P(O)–OH
13
bonds has been reported to afford 2-phosphinylphenols.
However, the method requires an exccess use of the expensive
tetrabutylammonium difluorotriphenylsilicate (TBAT) as the
fluoride source to generate arynes from β-trimethylsilyl
triflates. Thus, new effective and convenient strategies for the
synthesis of these chemicals are still required despite the
usefulness of these methods.14
hydrogenation4b-4d,
hydroformylation4e,
and
5d
4f,
5c
hydrocyanation.5a, 5b Metal complexes IV7a, V7b, 7c and VI7d have
been used as catalysts in olefin polymerization processes, and
phosphinyl functionalized polyether VII has long been known
as a neutral podand capable of forming complexes with
ammonium compounds selectively.8a
p-Quinone monoketals and p-quinol ethers have attracted
increasing interest as valuable synthetic intermediates in
organic synthesis due to their versatile reactivity and easy
availability.15 These compounds can be regarded as synthons
of umpolung phenols capable of accepting nucleophilic attack
to generate functionalized phenols.15a The groups of Kita16 and
others17-19 have demonstrated them as competent building
blocks for selective synthesis of a variety of valuable chemicals
via C–C bond formation. Particularly, Kita16a and Kürti17 have
recently succeeded in the construction of the synthetically
challenging biaryldiol scaffolds via the regioselective couplings
of p-quinone monoketals with electron-rich arenes,
respectively. In contrast to the achievements based on the C–C
bond forming reactions, it is noted that the development of
new reactions of p-quinone monoketals with formation of C–
heteroatom (e.g. P, S, Si, B, etc.) bonds has been somewhat
overlooked.20 Such a strategy is however promising for
selective synthesis of useful organoelemental compounds.
There are several methods available for the synthesis of 2-
phosphinylphenols (Figure 1b). The classical one is the
nucleophilic substitution of a phosphinyl halide by an ortho-
metalated protected phenol.10 This method involves the
generation of aryl Grignard or aryllithium reagents, and is thus
intolerant to many functional groups. The phospho-Fries-
rearrangement of O-phosphorylated phenols has been
a. State Key Laboratory of Materials-Oriented Chemical Engineering, College of
Chemical Engineering, Nanjing Tech University, Nanjing 210009, China. E-mail:
shenrw@njtech.edu.cn
b. College of Oversea Education, Nanjing Tech University, Nanjing 210009, China
c. National Institute of Advanced Industrial Science & Technology (AIST), Tsukuba,
Ibaraki, 305-8565, Japan
† Electronic Supplementary Information (ESI) available. CCDC 1874221 and CCDC
1874220. For ESI and crystallographic data in CIF or other electronic format see
DOI: 10.1039/x0xx00000x
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DOI: 10.1039/C9OB00129H
(a) selected functional molecules derived from 2-phosphinyl or 2-phosphanyl phenols
tBu
Ph
Ph
PPh2
PR2
O
R2
O
O
O
O
P
P
O
O
O
O
P
O
O
Ph2P
O
R1
PPh2
Ph
Ph
O
I
III
tBu
II
O
O
Ph2P
O
Alkyl
Cl
Cl
Alkyl
Ph2P
N
N
PPh2
M
P
M
O
O
NiLn
R1
PPh2
R
O
O
R
O
VII
tBu
tBu
R
V
VI
IV
R2
(b) reported methods for the preparation of 2-phosphinylphenols
OPG
method a
M
OP(O)R1R2
method b
LDA
(phospho-Fries rearrangement)
R1R2P(O)Cl
R
R
OH
O
R1
P
R2
R
method c
method d
OPG
OTf
X
SiMe3
TBAT/R1R2P(O)OH
metal catalyst/R1R2P(O)H
R
R
(Hirao-type C-P coupling)
(c) 2-phsophinylphenols based on the regioselective C-P coupling of cyclohexadienones with secondary phosphine oxides
O
O
R1
(b) This Work
(a) previous communication (ref 22)
OH
O
O
10 mol% Ph3P
MeCN, 100 o
10 mol% Zn(OTf)2
R2
P
H
+
R1
R1
R2
P
H
O
+
DCE, 100 o
C
C
R3
R
P
R3
R3
R2
R
OMe
2
MeO OMe
p-quinone monoketals
p-quinol ethers 1
(R = Me, Et, Ph)
Figure 1 Backgroud of the work: representative functional molecules containing 2-phosphinyl or 2-phosphanylphenolic unit and synthetic methods for 2-phosphinylphenols
In this context and as part of our recent interest in acid catalyst (Figure 1c). Described in this paper are the details
developing new C–P bond forming processes using the stable on this work.
and readily available P(O)H compounds,21 we are aware of the
possibility of developing a selective C–P cross coupling
reaction of quinone monoketals with P(O)H compounds as a
Results and discussion
new route to access phosphorylated phenols. Previously, we
have communicated a triphenylphosphine-mediated C–P cross
coupling reaction of p-quinone monoacetates with
secondary phosphine oxides as a practically useful synthetic
method for 2-phosphinylphenols (Scheme 1c).22 The reaction
takes place with high regioselectivity under mild conditions to
afford a variety of 4-methoxyl-2-phosphinyl phenols in high
yields. However, when we expanded the scope of the method
to include p-quinol ethers as substrates, no reaction was
observed. These results suggest the low reactivity of these
The initial experiments showed that no reaction took place
between 4-methoxy-4-methylcyclohexa-2,5-dien-1-one (1a) an
diphenylphosphine oxide (2a) under the reaction conditions as
we previously developed for p-quinone monoacetates and
secondary phosphine oxides (Table 1, entry 1).22 The reaction
took place slowly and produced the desired product 3aa in the
presence of several organic acids with low selectivity (Table 1,
entries 2-4). It was later found that several Lewis acids
including Zn(OTf)2, Sc(OTf)3, AgOTf and Cu(OTf)2 could also
trigger the reaction to produce 3aa selectively with improved
efficiency (Table 1, entries 5-8). Particularly, when a mixture of
substrates, and the necessity of
a catalyst for the
transformation. As a result, we recently succeeded in the
development of the regioselective C–P coupling reaction of p-
quinol ethers with secondary phosphine oxides using the Lewis
o
1a and 2a was heated in toluene at 100 C in the presence of
10 mol% of Zn(OTf)2, the reaction gave 3aa in 70% yield in 3 h
(Table 1, entry 5).
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Table 1 Optimization on the reaction of 1a and 2a a
5). It is noted that the halide functionalities such as bromine
and iodine atoms incorporated at the C(α) position are
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DOI: 10.1039/C9OB00129H
O
OH
tolerated, and the reactions afforded the corresponding
products 3fa and 3ga in high yields without loss of the reaction
efficiency (Table 2, entries 6 and 7). When the β-methyl quinol
P(O)Ph2
catalyst
+
Ph2P(O)H
conditions
2a
ether 1h was used, the reaction produced
a mixed
Me OMe
Me
regioisomers 3ha and 3ha’ in a combined yield of 93% (Table
2, entry 8). As expected, the reaction selectively gave 3ha as
the major product in which the phosphinyl group was
incorporated into the less sterically hindering position.23
1a
3aa
Entry
Catalyst
Solvent
Tempt (oC) Time (h) Yield (%)
1
2
TPP
Toluene
Toluene
Toluene
100
100
100
100
100
100
100
100
100
100
100
12
12
12
12
3
0
47
52
63
70
49
45
46
40
85
74
75
59
64
29b
HOAc
Table 2 Zn(OTf)2-catalyzed reaction of p-quinol ethers 1 with 2a a
3
PhCO2H
4
CF3CO2H Toluene
O
OH
5
Zn(OTf)2
Sc(OTf)3
AgOTf
Toluene
Toluene
Toluene
Toluene
Toluene
DCE

6
3
P(O)Ph2
10 mol% Zn(OTf)2
R1
R1
Ph2P(O)H
+
7
3

DCE, 100 °C
8
Cu(OTf)2
ZnCl2
3
2a
R2 OMe
9
12
6
R2
10
11
12
13
14
15
Zn(OTf)2
Zn(OTf)2
Zn(OTf)2
Zn(OTf)2
Zn(OTf)2
Zn(OTf)2
1
3
MeCN
6
Product 3, Yield (%)b
Entry
Substrate 1
1,4-Dioxane 100
3
DMSO
DMF
100
100
100
6
O
OH
6
MeOH
6
R
R
P(O)Ph2
3aa, 85%
MeO
1a (R = Me)
aConditions: a mixture of 1a (0.2 mmol) and 2a (0.6 mmol) was treated with 10
mol% of the catalyst at 100 oC in a solvent (2 mL). Isolated yields were given.
bUnidentified byproducts were detected. TPP: triphenylphosphine; DCE:
dichloroethane; DMSO: dimethyl sulfoxide; DMF: N,N-dimethylformamide.
1
2
3
1b (R = Et)
1c (R = Ph)
R
3ba, 76%
3ca, 55%
R
ZnCl2 was also able to promote the reaction, but the reaction
proceeded slowly and gave the product in low yield (Table 1,
entry 9). We noted that the possible P–O coupling product was
not observed in these reactions. We then examined the
solvent effect on the Zn(OTf)2-catalyzed reaction of 1a and 2a
for further improvement. The results showed that DCE was the
optimal solvent, and the reaction produced 3aa in 85% yield in
6 h (Table 1, entry 10). When the reaction was performed in
MeCN and 1,4-dioxane, the product 3aa was obtained in 74%
and 75% yield, respectively (Table 1, entries 11 and 12). The
use of DMSO and DMF gave the product in moderate yields
(Table 1, entries 13 and 14). Nevertheless, the reaction
performed in MeOH gave the product 3aa only in 29% yield,
with the formation of considerable amounts of byproducts
(Table 1, entry 15).
With the optimal conditions in hand, we then explored the
scope of the reaction. Table 2 shows the results on the
reactions of various p-quinol ethers 1 with 2a. 4-ethyl-4-
methoxycyclohexa-2,5-dien-1-one (1b) reacted smoothly with
2a to produce 3ba in 76% yield (Table 2, entry 2). 4-Phenyl-4-
methoxycyclohexa-2,5-dien-1-one (1c) could also be used to
deliver 3ca in 55% yield (Table 2, entry 3). C(α)-substituted p-
quinol ethers were also applicable to the reaction (Table 2,
entries 4-7). For example, α-methyl quinol ether 1d reacted
with 1a to produce the expected product 3da in 75% yield
(Table 2, entry 4). The sterically demanding quinol ether 1e
that bears a tert-butyl group at the C(α)-position gave the
product 3ea in a low yield with less efficiency (Table 2, entry
O
OH
Me
Me
P(O)Ph2
MeO
1d (R = Me)
1e (R = tBu)
1f (R = Br)
1g (R = I)
3da (R = Me), 75%
3ea (R = tBu), 23%c
3fa (R = Br), 90%
3ga (R = I), 82%
4
5
6
7
Me
OH
Me
Me
P(O)Ph2
Me
O
3ha, 58%
+
8d
Me
OH
MeO
1h
P(O)Ph2
Me
3ha', 35%
a
Unless otherwise noted, a mixture of 1 (1 equiv) and 2 (3 equiv) in DCE was
heated at 100 oC for 6 h with 10 mol% of Zn(OTf)2. b Isolated yields were given.
Reaction time: 24 h. d Reaction time: 12 h.
c
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Table 3 The scope of secondary phosphine oxides 2 a
A facile method for introducing different phosphinyl groups
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is highly desirable particularly in view DoOfI:t1h0e.10i3m9/pCo9rOtaBn00c1e29oHf
structurally diverse organophosphorus ligands in catalysis.
Further efforts were thus devoted to applying this reaction to
a variety of other secondary phosphine oxides (Table 3).
Gratifyingly, the present method enables the use of various
electronically different diarylphosphine oxides to produce the
corresponding products in good to high yields (3ab-3ah and
3dh, 70-94%). Functionalities such as methyl, methoxyl,
trifluoromethyl, chlorine and fluorine at the phenyl ring in 2
are tolerated. The reactions generally furnished the products
in 6 h, except that the reaction of di-o-tolylphosphine oxide
required a prolonged reaction time for completion to afford
3ai in 63% yield probably due to the steric effect. Notably, the
thiophene-contained phosphine oxide was also an effective
substrate to produce 3aj in 65% yield. The unsymmetric
secondary phosphine oxides that bear one alkyl group (R1 = Ph,
R2 = methyl, n-butyl or cyclohexyl) also reacted smoothly with
p-quinol ethers to give the desired products 3ak, 3al and 3fm
in high yields. Although dibutylphosphine oxide and
dicyclohexyl phosphine oxide were less reactive, the
corresponding products 3an and 3ao were still obtained in
good yields with prolonged reaction time. The structure of 3ao
was further confirmed by the X-ray crystallographic analysis.24
As for the scope of other P(O)H compounds, it is noted here
that H-phosphonates and H-phosphinates are not suitable
substrates for the present reaction. Indeed, the reaction of
diethyl phosphonate or ethyl phenylphosphinate with 1a gave
a complex mixture of products.25
O
OH
Me
O
R1
P
O
10 mol% Zn(OTf)2
DCE, 100 °C, 6 h
R2
R
R2
P
R1
H
+
Me OMe
1
2
3
Cl
R1
Me
OH
O
P
P
O
OH
Cl
Me
R2
3ah, 77%
3ab (R1 = R2 = Me), 81%
3ac (R1 = R2 = MeO), 84%
3ad (R1 = R2 = F), 80%
Cl
Me
3ae (R1 = R2 = CF3), 71%
3af (R1 = MeO, R2 = H), 94%
3ag (R1 = F, R2 = H), 89%
P
O
Me
OH
Cl
3dh, 70%
Me
Me
O
Me
S
P
P
S
Me
OH
O
OH
3ai, 63%b
3aj, 65%
Me
Me
The versatility of the reaction was demonstrated by a scale-
up experiment. 1.96 g of 3ab (80%) was obtained from the
reaction of 1a and 2b (Eqn. 1). The obtained product 3ab
underwent facile reduction by a combination of HSiCl3 and
Et3N in toluene to afford the 2-phosphanylphenol 4 in 66%
yield (Eqn. 2).
Ph
P
Ph
O
P
O
Me
OH
Me
OH
3ak, 83%
3al, 86%
Br
OH
Me
O
P
O
O
Me
OH
Me
O
2b (3.0 equiv)
P
Ph
OH
P
10 mol% Zn(OTf)2
(1)
Me
DCE, 100 °C
Me
Me OMe
3an, 63%c
Me
3fm, 80%b
Me
1a
(1.000 g, 7.25 mmol)
3ab (1.960 g, 80%)
OH
Me
Me
P
Me
P
HSiCl3/Et3N
toluene, 100 °C
O
3ab
(2)
(1.233 g)
OH
3ao, 60%c
Me
4 (0.846 g, 66%)
a Unless otherwise noted, a mixture of 1 (1 equiv), 2 (3 equiv), Zn(OTf)2 (0.1 equiv)
b
c
in DCE was heated to 100 oC. Isolated yields were given. Reaction time: 24 h.
Furthermore, it is worthy to mention that the cyclization of
2-(1-alkynyl)-2-alken-1-ones with nucleophiles in the presence
of a catalytic amount of Lewis acid is a well-established
strategy for the synthesis of functionalized furan derivatives.26
The reaction was conducted in toluene for 48 h.
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7
1
a) the possible cyclization
6
O
O
O
Ph
2
5
- Zn2+
- MeOH
Ph2P(O)H (2a)
Me
Me
+ Zn2+
4
Me
3
MeO
Ph
Ph
P
Ph
MeO
Zn2+
Ph
P
O
OH
Ph
5a
4-phosphinyl benzofurans
not formed
Ph
b) the observed reaction
O
P(O)Ph2
OH
Me
10 mol% Zn(OTf)2
MeO
toluene, 100 o
C
Ph
5a
+
Me
Ph
Ph2P(O)H
6a, 84%
2a
Scheme 1 The reaction of α-alkynyl p-quinol ether 5a with 2a
The reactions can be regarded as a sequential nucleophilic for phosphorescent organic light-emitting diodes with further
domino attack onto a metal-complexed alkyne, a process modification.29
which is in principle initiated by the nucleophilic attack of the
carbonyl oxygen to the Lewis acid-activated alkyne
Table 4 Zn(OTf)2-catalyzed C-P coupling of 5 and 2 to produce 6 a
P(O)R2
functionality to form the five-membered ring, followed by the
intermolecular nucleophilic attack. Since zinc salts are also
known as mild -Lewis acids to activate C–C triple bonds to
induce cyclization of alkynes with intramolecular
nucleophiles,27, 28 we questioned whether the reaction of α-
alkynyl-substituted p-quinol ether 5a could undergo a similar
domino sequence in the presence of the zinc catalyst to
produce the cyclized 4-phosphinyl benzofuran (Scheme 1a).
However, the following experiment show that such a
process did not occur, and the reaction took place to give the
C(α)–P coupling product, i.e., (2-hydroxy-5-methyl-3-
(phenylethynyl)phenyl)diphenylphosphine oxide (6a), as the
only product. This result suggests that the zinc catalyst in the
reaction functions overwhelmingly as an oxophilic Lewis acid
other than a π-Lewis acid. The structure of 6a was
unambiguously confirmed by an X-ray crystallographic
analysis.24
O
Ar
2
OH
O
P
R2
10 mol% Zn(OTf)2
toluene, 100 °C
R2
H
+
R1
R1 OMe
5
Ar
6
2
P(O)Ph2
OH
Ph
OH
Me
R
O
P
Me
R
R
6b (R = 3-Me), 70%
6c (R = 4-Me), 68%
6d (R = 4-nPr), 65%
6e (R = 3-F), 76%
6g (R = 4-F), 70%
6h (R = 4-Me), 80%
6i (R = 4-OMe), 51%
6j (R = 3-Cl), 67%
Me
P(O)Ph2
We also briefly examined the scope of this transformation.
Table 4 lists some examples of 2-phosphinyl-6-alknyl phenols
prepared by the method. 6a-6f were successfully obtained in
good to high yields from the reactions of α-alkynyl p-quinol
ethers with 2a. Other electronically different diarylphosphine
oxides were also applicable to afford the corresponding
products (6g-6k). Dialkylphosphine oxides showed low
reactivity, yet the reactions still gave the expected products 6l
and 6m in 73% and 57% yields with prolonged reaction time.
Notably, the obtained polyfunctionalized products 6 can serve
as precursors to access 7-phosphinyl benzofurans via
electrophilic cyclization. As exemplified in Eqn.3, the treatment
of 6a with I2 in the presence of NaHCO3 in MeCN afforded the
white crystaline solid 7 in 88% yield. These phosphorylated
heterocyclic compounds may serve as promising host materials
O
OH
Ph
OH
P
Me
Ph
6f, 63%
Me
Me
6k, 24%
Ph
Me
Ph
OH
O
P
HO
Me
P
Me
O
Me
6l, 73%
6m, 57%
Reaction conditions: a mixture of 5 (1 equiv) and 2 (3 equiv) in toluene was heated at
100 oC untill completion with 10 mol% of Zn(OTf)2. Isolated yields were given.
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obtained products are readily reduced to afford 2-
View Article Online
DOI: 10.1039/C9OB00129H
phosphanylphenols, which may be useful building blocks for
P(O)Ph2
OH
P(O)Ph2
O
I2 (3.0 equiv)
the synthesis of useful ligands in transition metal catalysis. In
addition, we also found that α-alkynyl substituted p-quinol
ethers also react with secondary phosphine oxides in a same
reaction mode to give 6-alkynyl 2-phosphinylphenols in the
presence of the zinc catalyst. The zinc catalyst may act as an σ-
Lewis acid in the reaction, and a potential sequential
nucleophilic cyclization process to produce 4-phosphinyl
benzofuran was not observed. The obtaind 2-phosphinyl-6-
alknyl phenols are useful for the synthesis of 7-phosphinyl
benzofurans via electrophilic cyclization. Due to the easy
availability of the starting materials, simple operation of the
procedure and usefulness of the products, we believe that the
method will find applications in related areas.
7
1
NaHCO3 (3.0 equiv)
6
5
(3)
Ph
MeCN, rt, 2 h
88%
2
Me
Me
3
4
I
Ph
7
6a
Finally, a mechanism for the present reaction is proposed
in Scheme 2. The binding of the Zn(II) species as a σ-Lewis acid
to 1a may form an intermediate A to activate the C–O bond.
The SN2’-type substitution via the attack of 2a’ (tautomer of
2a) at the C(α) position of 1a may take place to give an
intermediate B with the formation of the C–P bond and the
loss of one molecule of methanol. Alternatively, the
generation of the cationic intermediate C from A via
heterolytic C–O bond cleavage followed by a regioselective
nucleophilic attack of 2a’ is also a reasonable pathway for the
formation of the intermediate B. The keta-enol
tautomerization of B finally takes place to give the product 3aa.
Experimental
General information
Unless otherwise specified, all reactions were performed
under dry N2 atmosphere. Anhydrous solvents were distilled
prior to use: dioxane and toluene were distilled from sodium
using benzophenone as the indicator; DCM, DMF, MeCN and
DMSO were distilled from CaH2. p-Quinol ethers were
prepared following known procedures by oxidation of the
coresponding phenols with PhI(OAc)2 in MeOH.30 Flash
chromatography was performed on silica gel using petroleum
2a
tautemerization
nucleophilic
attack
Ph
O
O
P
Ph
P(O)Ph2
O
Zn2+
1
ether and EtOAc as eluent. H, 13C and 31P NMR spectra were
2a'
H
1a
recorded on a 400 MHz spectrometer. Chemical shifts (ppm)
were recorded with tetramethylsilane (TMS) as the internal
reference standard. Chemical shifts are expressed in ppm and J
values are given in Hz. HRMS analysis of the products was
performed at the Analytical Center of the State Key Laboratory
of Materials-Oriented Chemical Engineering of Nanjing Tech
University. The X-Ray crystallographic analysis were performed
on a Bruker SMART APEX II CCD diffractometer using a
graphite-monochromated Mo Kα (λ = 0.71073 Å) radiation.
General procedure for the Zn(OTf)2-catalyzed preparation of 2-
phosphinyl phenols 3. An oven-dried Schlenk tube containing a
Teflon-coated stir bar was charged with Zn(OTf)2 (7.2 mg,
10 mol %). The Schlenk tube was sealed and then evacuated
and backfilled with N2 (3 cycles). Then 1 (0.2 mmol) and 2
(0.6 mmol) dissolved in 2 mL of DCE was injected. The Schlenk
tube was sealed and immersed in an oil bath which was
binding
and
activiation
- Zn2+, - MeOH
Me OMe
Me
Zn2+
B
A
- Zn(OMe)+
- H+
Ph
keta-enol
tautemerization
C-O cleavage
O
P
Ph
3aa
O
2a'
H
Me
C
Scheme 2 The proposed mechanism
o
heated to 100 C. After the reaction was complete (monitored
by TLC, 6-48 h), removal of the solvent under vacuum left a
slurry residue, which was purified by flash chromatography on
silica (petroleum ether/ethyl acetate 3/1) to afford the
product 3.
Conclusions
In summary, we have reported a highly regioselective Zn(OTf)2-
catalyzed C–P cross coupling reaction of p-quinol ethers with
secondary phosphine oxides to offer a facile alternative
method for the synthesis of 2-phosphinylphenols in good to
high yields from readily available starting materials.
Particularly interesting is that various types of phosphinyl
groups can be introduced by employing different
secondary phosphine oxides as the coupling partners. The
1
3aa: white solid, mp. 219.3–220.6 °C, 52.5 mg (yield 85%). H
NMR (CDCl3, 400 MHz): δ = 10.96 (s, 1H), 7.72–7.67 (m, 4H),
7.61–7.57 (m, 2H), 7.52–7.48 (m, 4H), 7.22 (d, J = 8.0 Hz, 1H),
6.89 (dd, J1 = 8.4 Hz, J2 = 5.2 Hz, 1H), 6.75 (dd, J1 = 13.2 Hz, J2 =
1.6 Hz, 1H), 2.19 (s, 3H). 13C NMR (CDCl3, 100 MHz): δ = 161.8
(d, JP-C = 12.4 Hz), 135.3 (d, JP-C = 2.3 Hz), 132.4 (d, JP-C = 3.3 Hz),
132.0 (d, JP-C = 9.9 Hz), 131.8 (d, JP-C = 104.4 Hz), 131.5 (d, JP-C
=
9.5 Hz), 128.7 (d, JP-C = 11.8 Hz), 128.1 (d, JP-C = 12.1 Hz), 118.4
6 | J. Name., 2012, 00, 1-3
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Journal Name
ARTICLE
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1
(d, JP-C = 7.9 Hz), 110.4 (d, JP-C = 103.6 Hz), 20.5. 31P NMR (CDCl3, 3ha: white solid, mp. 210.7–212.2 C, 37.3 mg (yVieielwdA5rti8cl%e O).nlinHe
162 MHz): δ = 39.5. This is a known compound.31a
NMR (CDCl3, 400 MHz): δ = 10.88 (s, 1H), 7.72–7.67 (m, 4H),
DOI: 10.1039/C9OB00129H
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1
3ba: White solid, mp. 199.3–201.2 C, 49.0 mg (yield 76%). H 7.60–7.56 (m, 2H), 7.51–7.46 (m, 4H), 6.79 (d, J = 4.8 Hz, 1H),
NMR (CDCl3, 400 MHz): δ = 10.96 (s, 1H), 7.72–7.67 (m, 4H), 6.69 (d, J = 13.2 Hz, 1H), 2.23 (s, 3H) , 2.09 (s, 3H). 31P NMR
7.61–7.57 (m, 2H), 7.52–7.47 (m, 4H), 7.25 (d, J = 7.6 Hz, 1H), (CDCl3, 162 MHz): δ = 39.4. This is a known compound.[14]
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1
6.92 (dd, J1 = 8.8 Hz, J2 = 4.8 Hz, 1H), 6.77 (dd, J1 = 13.6 Hz, J2 = 3ha’: white solid, mp. 205.3–206.1 C, 22.4 mg (yield 35%). H
2.0 Hz, 1H), 2.48 (q, J = 7.6 Hz, 2H), 1.11 (t, J = 7.6 Hz, 3H). 13C NMR (CDCl3, 400 MHz): δ = 12.41 (s, 1H), 7.78–7.73 (m, 4H),
NMR (CDCl3, 100 MHz): δ = 161.9 (d, JP-C = 3.2 Hz), 134.6 (d, JP-C 7.61–7.57 (m, 2H), 7.53–7.49 (m, 4H), 7.25 (d, J = 7.2 Hz, 1H),
= 12.0 Hz), 134.1 (d, JP-C = 2.0 Hz), 132.5 (d, JP-C = 2.8 Hz), 131.0 6.82 (dd, J1 = 8.4 Hz, J2 = 4.8Hz, 1H), 2.10 (s, 3H) , 1.73 (s, 3H).
(d, JP-C = 10.4 Hz), 131.8 (d, JP-C = 103.6 Hz), 130.5 (d, JP-C = 10.2 13C NMR (CDCl3, 100 MHz): δ = 164.5 (d, JP-C = 4.4 Hz), 138.4 (d,
Hz), 128.6 (d, JP-C = 12.3 Hz), 118.5 (d, JP-C = 8.1 Hz), 110.4 (d, JP- JP-C = 8.8 Hz), 136.5 (d, JP-C = 2.4 Hz), 132.4 (d, JP-C = 2.7 Hz),
= 104.3 Hz), 27.8, 15.7. 31P NMR (CDCl3, 162 MHz): δ = 39.6. 132.3 (d, JP-C = 103.9 Hz), 132.0 (d, JP-C = 11.2 Hz), 128.8 (d, JP-C
C
This is a known compound.31b
= 12.3 Hz), 127.8 (d, JP-C = 10.2 Hz), 116.8 (d, JP-C = 8.3 Hz),
o
1
3ca: White solid, mp. 178.8–180.2 C, 40.7 mg (yield 55%). H 108.0 (d, JP-C = 101.4 Hz), 20.6 (d, JP-C = 6.4 Hz), 19.6 (d, JP-C
=
NMR (CDCl3, 400 MHz): δ = 11.26 (s, 1H), 7.77–7.71 (m, 4H), 1.9 Hz). 31P NMR (CDCl3, 162 MHz): δ = 44.0. HRMS (ESI-TOF):
7.66–7.59 (m, 3H), 7.54–7.49 (m, 4H), 7.39–7.36 (m, 4H), 7.31– m/z = 323.1206, calcd for C20H20O2P [MH+] 323.1201.
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1
7.26 (m, 1H), 7.18 (dd, J1 = 14.0 Hz, J2 = 2.4 Hz, 1H), 7.07 (dd, J1 3ab: white solid, mp. 190.0–190.8 C, 54.3 mg (yield 81%). H
= 8.8 Hz, J2 = 4.8 Hz, 1H). 31P NMR (CDCl3, 162 MHz): δ = 39.8. NMR (CDCl3, 400 MHz): δ = 11.03 (s, 1H), 7.59–7.54 (m, 4H),
This is a known compound.31c
7.30–7.28 (m, 4H), 7.19 (d, J = 8.4 Hz, 1H), 6.87 (dd, J1 = 8.4 Hz,
3da: White solid, mp. 161.3–163.1 oC, 48.6 mg (yield 75%). 1H J2 =4.8Hz, 1H), 6.73 (dd, J1 = 13.2 Hz, J2 =1.6 Hz, 1H), 2.42 (s, 6H),
NMR (CDCl3, 400 MHz): δ = 11.08 (s, 1H), 7.71–7.66 (m, 4H), 2.18 (s, 3H). 13C NMR (CDCl3, 100 MHz): δ = 161.7, 143.1, 135.1,
7.59–7.55 (m, 2H), 7.50–7.46 (m, 4H), 7.09 (s, 1H), 6.59 (d, J = 132.1 (d, JP-C = 10.7 Hz), 131.5 (d, JP-C = 10.1 Hz), 129.4 (d, JP-C
14.0 Hz, 1H), 2.23 (s, 3H) , 2.15 (s, 3H). 13C NMR (CDCl3, 100 12.8 Hz), 128.8 (d, JP-C = 106.6 Hz), 128.0 (d, JP-C = 14.5 Hz),
MHz): δ = 159.9 (d, JP-C = 2.4 Hz), 136.3 (d, JP-C = 2.9 Hz), 132.3 118.4 (d, JP-C = 8.1 Hz), 111.0 (d, JP-C = 103.1 Hz), 21.7, 20.5. 31
=
P
(d, JP-C = 13.3 Hz), 132.0 (d, JP-C = 10.5 Hz), 131.9 (d, JP-C = 103.0 NMR (CDCl3, 162 MHz): δ = 39.7. HRMS (ESI-TOF): m/z =
Hz), 128.9 (d, JP-C = 10.1 Hz), 128.6 (d, JP-C = 12.2 Hz), 127.5 (d, 337.1356, calcd for C21H22O2P [MH+] 337.1357.
o
1
JP-C = 13.3 Hz), 127.4 (d, JP-C = 8.3 Hz), 109.5 (d, JP-C = 103.4 Hz), 3ac: white solid, mp. 181.1–181.8 C, 62.0 mg (yield 84%). H
20.5, 15.9 (d, JP-C = 1.0 Hz). 31P NMR (CDCl3, 162 MHz): δ = 39.9. NMR (CDCl3, 400 MHz): δ = 11.05 (s, 1H), 7.63–7.58 (m, 4H),
This is a known compound.31d
7.19 (d, J = 8.0 Hz, 1H), 7.00–6.97 (m, 4H), 6.87 (dd, J1 = 8.4 Hz,
3ea: 16.8 mg (yield 23%). 1H NMR (CDCl3, 400 MHz): δ = 11.19 J2 =4.8Hz, 1H), 6.72 (dd, J1 = 13.6 Hz, J2 =2.0 Hz, 1H), 3.85 (s, 6H),
(s, 1H), 7.71–7.66 (m, 4H), 7.60–7.56 (m, 2H), 7.51–7.46 (m, 2.18 (s, 3H). 13C NMR (CDCl3, 100 MHz): δ = 162.8 (d, JP-C = 3.2
4H), 7.22 (d, J = 1.6 Hz, 1H), 6.59 (dd, J1 = 13.6 Hz, J2 = 1.6 Hz, Hz), 161.5 (d, JP-C = 3.4 Hz), 135.1 (d, JP-C = 2.0 Hz), 134.0 (d, JP-C
1H), 2.17 (s, 3H), 1.41 (s, 9H). 13C NMR (CDCl3, 100 MHz): δ = = 11.8 Hz), 131.6 (d, JP-C = 9.5 Hz), 128.1 (d, JP-C = 12.7 Hz),
161.0, 138.6 (d, JP-C = 7.0 Hz), 132.6, 132.4, 132.1 (d, JP-C =10.2 123.1 (d, JP-C = 110.6 Hz), 118.3 (d, JP-C = 8.0 Hz), 114.2 (d, JP-C
=
H), 131.6, 129.4 (d, JP-C = 10.3 Hz), 128.6 (d, JP-C = 12.4 Hz), 13.6 Hz), 111.5 (d, JP-C = 103.9 Hz), 55.4, 20.5. 31P NMR (CDCl3,
127.1 (d, JP-C = 15.5 Hz), 110.1 (d, JP-C = 102.6 Hz), 35.1, 29.4, 162 MHz): δ = 39.2. HRMS (ESI-TOF): m/z = 369.1266, calcd for
20.9. 31P NMR (CDCl3, 162 MHz): δ = 41.0. HRMS (ESI-TOF): m/z C21H22O4P [MH+] 369.1256.
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1
= 365.1672, calcd for C23H26O2P [MH+] 365.1670.
3ad: white solid, mp. 185.8–186.5 C, 54.9 mg (yield 80%). H
1
3fa: 69.6 mg (yield 90%). H NMR (CDCl3, 400 MHz): δ = 11.77 NMR (CDCl3, 400 MHz): δ = 10.77 (s, 1H), 7.72–7.65 (m, 4H),
(s, 1H), 7.71–7.66 (m, 4H), 7.63–7.59(m, 2H), 7.53–7.49 (m, 5H), 7.25–7.18 (m, 5H), 6.90 (dd, J1 = 8.4 Hz, J2 =4.8Hz, 1H), 6.68 (dd,
6.73 (dd, J1 = 13.2 Hz, J2 = 1.2 Hz, 1H), 2.18 (s, 3H). 13C NMR J1 = 13.6 Hz, J2 =1.6 Hz, 1H), 2.20 (s, 3H). 13C NMR (CDCl3, 100
(CDCl3, 100 MHz): δ = 157.7 (d, JP-C = 4.0 Hz), 138.3 (d, JP-C = 2.3 MHz): δ = 165.4 (dd, JF-C = 252.9 Hz, JP-C = 3.2 Hz), 161.7 (d, JP-C
Hz), 132.7 (d, JP-C = 2.0 Hz), 132.0 (d, JP-C = 9.7 Hz), 131.0 (d, JP-C = 2.8 Hz), 135.7 (d, JP-C = 2.2 Hz), 134.5 (dd, JF-C = 11.7 Hz, JP-C
= 104.9 Hz), 130.9 (d, JP-C = 9.0 Hz), 129.4 (d, JP-C = 12.9 Hz), 9.0 Hz), 131.2 (d, JP-C = 9.8 Hz), 128. 5 (d, J = 12.4 Hz), 127.7 (dd,
128.8 (d, JP-C = 12.3 Hz), 112.2 (d, JP-C = 11.1 Hz), 112.1 (d, JP-C JP-C = 108.0 Hz, JF-C = 3.5 Hz), 118.7 (d, JP-C = 8.8 Hz), 116.3 (dd,
100.6 Hz), 20.2. 31P NMR (CDCl3, 162 MHz): δ = 39.5. HRMS JF-C = 21.6 Hz, JP-C = 13.2 Hz), 110.2 (d, JP-C = 105.5 Hz), 20.6. 31
(ESI-TOF): m/z = 387.0152, calcd for C19H17O2PBr [MH+] NMR (CDCl3, 162 MHz): δ = 37.9. HRMS (ESI-TOF): m/z =
387.0150.
345.0856, calcd for C19H16O2PF2 [MH+] 345.0856.
=
=
P
1
3ga: 69.6 mg (yield 82%). H NMR (CDCl3, 400 MHz): δ = 11.98 3ae: 63.1 mg (yield 71%). 1H NMR (CDCl3, 400 MHz): δ = 10.51
(s, 1H), 7.74–7.65 (m, 5H), 7.62–7.58(m, 2H), 7.52–7.48 (m, 4H), (s, 1H), 7.86–7.76 (m, 8H), 7.27 (d, J = 8.4 Hz, 1H), 6.93 (dd, J1 =
6.76 (dd, J1 = 13.2 Hz, J2 = 0.8Hz, 1H), 2.16 (s, 3H). 13C NMR 8.4 Hz, J2 = 5.2Hz, 1H), 6.75 (dd, J1 = 13.6 Hz, J2 = 1.2 Hz, 1H),
(CDCl3, 100 MHz): δ = 159.9 (d, JP-C = 3.7 Hz), 144.5 (d, JP-C = 2.5 2.22 (s, 3H). Due to the coupling of F-C and P-C, the 13C NMR
Hz), 132.8 (d, JP-C = 2.4 Hz), 132.0 (d, JP-C = 11.0 Hz), 131.9 (d, JP- spectra show complex peaks not easily interprepted. A full list
= 9.0 Hz), 130.9 (d, JP-C = 104.7 Hz), 130.1 (d, JP-C = 13.6 Hz), of the 13C NMR data: 13C NMR (CDCl3, 100 MHz): δ = 161.80,
C
128.8 (d, JP-C = 12.3 Hz), 111.0 (d, JP-C = 100.8 Hz), 87.2 (d, JP-C
=
161.78, 136.31, 136.29, 136.1, 135.1, 134.76, 134.73, 134.44,
9.9 Hz), 20.0. 31P NMR (CDCl3, 162 MHz): δ = 39.4. HRMS (ESI- 134.40, 134.11, 134.08, 132.5, 132.4, 131.1, 130.9, 128.98,
TOF): m/z = 435.0015, calcd for C19H17O2PI [MH+] 435.0011.
128.86, 127.4, 125.90, 125.86, 125.82, 125.79, 125.74, 125.70,
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Journal Name
125.66, 124.7, 122.0, 119.3, 119.03, 118.95, 109.4, 108.3, 20.5. 2.3 Hz), 132.6 (d, JP-C = 8.5 Hz), 132.5 (d, JP-C = 2.7 Hz), 132.3 (d,
View Article Online
31P NMR (CDCl3, 162 MHz): δ = 36.7. HRMS (ESI-TOF): m/z = JP-C = 10.6 Hz), 131.7 (d, JP-C = 9.8 Hz), 12D9O.8I:(1d0,.1J0P3-C9/=C91O0B20.701H29zH),
445.0796, calcd for C21H16F6O2P [MH+] 445.0792.
128.0 (d, JP-C = 12.6 Hz), 125.6 (d, JP-C = 13.2 Hz), 118.5 (d, JP-C =
1
3af: 66.9 mg (yield 94%). H NMR (CDCl3, 400 MHz): δ = 11.03 7.8 Hz), 110.3 (d, JP-C = 101.8 Hz), 21.7 (d, JP-C = 4.8 Hz), 20.6.
(s, 1H), 7.72–7.67 (m, 2H), 7.63–7.56 (m, 3H), 7.51–7.47 (m, 31P NMR (CDCl3, 162 MHz): δ = 46.6. HRMS (ESI-TOF): m/z =
2H), 7.20 (d, J = 8.0 Hz, 1H), 7.34 (dd, J1 = 8.8 Hz, J2 =2.0 Hz, 2H), 337.1356, calcd for C21H22O2P [MH+] 337.1357.
6.88 (dd, J1 = 8.4 Hz, J2 =4.8 Hz, 1H), 6.73 (dd, J1 = 13.6 Hz, J2 3aj: white solid, mp. 188.4–189.8 C. 41.6 mg (yield 65%). H
=1.6 Hz, 1H), 3.86 (s, 3H) , 2.18 (s, 3H). 13C NMR (CDCl3, 100 NMR (CDCl3, 400 MHz): δ = 10.76 (s, 1H), 7.79 (t, J = 4.2 Hz, 2H),
MHz): δ = 162.9 (d, JP-C = 3.2 Hz), 161.7 (d, JP-C = 2.1 Hz), 135.2 7.61–7.58 (m, 2H), 7.24–7.20 (m, 3H), 6.95–6.88 (m, 2H), 2.21
(d, JP-C = 2.3 Hz), 134.0 (d, JP-C = 11.8 Hz), 132.4 (d, JP-C = 3.2 Hz), (s, 3H). 13C NMR (CDCl3, 100 MHz): δ = 160.9 (d, JP-C = 3.5 Hz),
o
1
132.2 (d, J = 104.2 Hz), 132.0 (d, JP-C = 10.0 Hz), 131.7 (d, JP-C
=
137.4 (d, JP-C = 11.3 Hz), 135.8 (d, JP-C = 2.0 Hz), 134.8 (d, JP-C =
10.9 Hz), 128.7 (d, JP-C = 11.6 Hz), 128.1 (d, JP-C = 12.7 Hz), 122.9 6.2 Hz), 133.5 (d, JP-C = 120.3 Hz), 131.1 (d, JP-C = 10.5 Hz), 128.4
(d, JP-C = 111.0 Hz), 118.4 (d, JP-C = 7.9 Hz), 114.3 (d, JP-C = 12.8 (d, JP-C = 14.2 Hz), 128.3 (d, JP-C = 13.1 Hz), 118.3 (d, JP-C = 8.2
Hz), 111.0 (d, JP-C = 103.6 Hz), 55.4, 20.6. 31P NMR (CDCl3, 162 Hz), 111.4 (d, JP-C = 115.5 Hz), 20.4. 31P NMR (CDCl3, 162 MHz):
MHz): δ = 39.3. HRMS (ESI-TOF): m/z = 339.1155, calcd for δ = 23.7. HRMS (ESI-TOF): m/z = 321. 0172, calcd for
C20H20O3P [MH+] 339.1150.
C15H14O2S2P [MH+] 321.0173.
1
1
3ag: 58.0 mg (yield 89%). H NMR (CDCl3, 400 MHz): δ = 10.85 3ak: 40.8 mg (yield 83%). H NMR (CDCl3, 400 MHz): δ = 10.92
(s, 1H), 7.73–7.66 (m, 4H), 7.63–7.59 (m, 1H), 7.53–7.49 (m, (s, 1H), 7.79–7.74 (m, 2H), 7.58–7.48 (m, 3H), 7.19 (d, J = 8.0
2H), 7.24–7.17 (m, 3H), 6.90 (dd, J1 = 9.2 Hz, J2 = 5.2Hz, 1H), Hz, 1H), 6.87–6.81 (m, 2H), 2.22 (s, 3H), 2.09 (d, J = 13.2 Hz,
6.71 (dd, J1 = 13.6 Hz, J2 = 1.6 Hz, 1H), 2.19 (s, 3H). 13C NMR 3H). 13C NMR (CDCl3, 100 MHz): δ = 161.1 (d, JP-C = 2.8 Hz),
(CDCl3, 100 MHz): δ = 165.8 (dd, JF-C = 253.1 Hz, JP-C = 2.9 Hz), 135.2 (d, JP-C = 2.2 Hz) 133.7 (d, JP-C = 102.0 Hz), 132.3 (d, JP-C
=
161.7 (d, JP-C = 2.7 Hz), 135.5 (d, JP-C = 2.2 Hz), 134.6 (dd, JP-C 3.0 Hz), 131.1 (d, JP-C = 10.1 Hz), 130.0 (d, JP-C = 9.8 Hz), 128.9 (d,
=
21.6 Hz, JF-C = 9.1 Hz), 132.6 (d, JP-C = 3.2 Hz), 131.9 (d, JP-C = 9.8 JP-C = 11.7 Hz), 118.4 (d, , JP-C = 7.8 Hz), 112.2 (d, JP-C = 101.3 Hz),
Hz), 131.5 (d, J = 105.8 Hz), 131.3 (d, JP-C = 9.8 Hz), 128.8 (d, JP-C 20.5, 17.0 (d, JP-C = 73.0 Hz). 31P NMR (CDCl3, 162 MHz): δ =
= 12.3 Hz), 128.3 (d, JP-C = 12.4 Hz), 127.8 (d, JP-C = 103.7 Hz), 42.4. HRMS (ESI-TOF): m/z = 247.0885, calcd for C14H16O2P
118.6 (d, JP-C = 8.3 Hz), 116.1 (dd, JF-C = 21.6 Hz, JP-C = 13.2 Hz), [MH+] 247.0888.
1
111.2 (d, JP-C = 104.8 Hz), 20.5. 31P NMR (CDCl3, 162 MHz): δ = 3al: 49.5 mg (yield 86%). H NMR (CDCl3, 400 MHz): δ = 11.06
38.7. HRMS (ESI-TOF): m/z = 327.0956, calcd for C19H17O2PF (s, 1H), 7.81–7.76 (m, 2H), 7.56–7.49 (m, 3H), 7.17 (d, J = 8.4
[MH+] 327.0950.
Hz, 1H), 6.86–6.81 (m, 2H), 2.33–2.25 (m, 2H), 2.23 (s, 3H),
3ah: 58.0 mg (yield 77%). 1H NMR (CDCl3, 400 MHz): δ = 10.62 1.74–1.56 (m, 2H), 1.50–1.41 (m, 2H), 0.91 (t, J = 7.4 Hz, 3H).
(s, 1H), 7.68–7.64 (m, 2H), 7.60–7.52 (m, 4H), 7.49–7.44 (m, 13C NMR (CDCl3, 100 MHz): δ = 161.5, 135.0 (d, JP-C = 2.3 Hz),
2H), 7.26 (d, J = 4.8 Hz, 1H), 6.92 (dd, J1 = 8.4 Hz, J2 =5.2 Hz, 1H), 132.9 (d, JP-C = 97.9 Hz), 132.1 (d, JP-C = 3.1 Hz), 130.3 (d, JP-C
=
6.72 (d, J = 13.6 Hz, 1H), 2.22 (s, 3H). 13C NMR (CDCl3, 100 9.5 Hz), 129.8 (d, JP-C = 10.4 Hz), 128.7 (d, JP-C = 11.6 Hz), 128.3
MHz): δ = 161.8 (d, JP-C = 2.5 Hz), 136.1 (d, JP-C = 2.2 Hz), 135.4 (d, JP-C = 11.2 Hz), 118.2 (d, JP-C = 8.3 Hz), 111.2 (d, JP-C = 97.4
(d, JP-C = 16.4 Hz), 133.6 (d, JP-C = 103.0 Hz), 133.0 (d, J = 3.4 Hz), Hz), 29.7 (d, JP-C = 71.0 Hz), 23.9 (d, JP-C = 14.5 Hz), 23.0 (d, JP-C
=
131.7 (d, JP-C = 10.3 Hz), 131.1 (d, JP-C = 10.2 Hz), 130.3 (d, JP-C
=
3.7 Hz), 20.5, 13.6. 31P NMR (CDCl3, 162 MHz): δ = 44.9. HRMS
13.6 Hz), 130.0 (d, JP-C = 10.7 Hz), 128.7 (d, JP-C = 12.8 Hz), 118.9 (ESI-TOF): m/z = 289.1361, calcd for C17H22O2P [MH+] 289.1357.
(d, JP-C = 8.8 Hz), 109.1 (d, JP-C = 104.7 Hz), 20.6. 31P NMR (CDCl3, 3fm: 63.2 mg (yield 80%). 1H NMR (CDCl3, 400 MHz): δ = 11.98
162 MHz): δ = 37.2. HRMS (ESI-TOF): m/z = 377.0265, calcd for (s, 1H), 7.84–7.79 (m, 2H), 7.56–7.49(m, 3H), 7.44 (d, J = 2.0 Hz,
C19H16O2PCl2 [MH+] 377.0265.
1H), 6.87 (dd, J1 = 12.0 Hz, J2 = 1.6 Hz, 1H), 2.32–2.25 (m, 1H),
3dh: 54.8 mg (yield 70%). 1H NMR (CDCl3, 400 MHz): δ = 10.76 2.23 (s, 3H), 1.84–1.64 (m, 6H), 1.35–1.23 (m, 4H). 13C NMR
(s, 1H), 7.68–7.64 (m, 2H), 7.58–7.51 (m, 4H), 7.47–7.43 (m, (CDCl3, 100 MHz): δ = 157.8 (d, JP-C = 3.2 Hz), 137.8 (d, JP-C = 2.0
2H), 7.14 (s, 1H), 6.55 (d, J = 13.2 Hz, 1H), 2.23 (s, 3H) , 2.18 (s, Hz), 132.2 (d, JP-C = 2.8 Hz), 130.7 (d, JP-C = 8.6 Hz), 130.5 (d, JP-C
3H). 13C NMR (CDCl3, 100 MHz): δ = 160.1 (d, JP-C = 3.1 Hz), = 94.7 Hz), 129.5 (d, JP-C = 13.2 Hz), 128.95 (d, JP-C = 9.4 Hz),
137.0 (d, JP-C = 3.2 Hz), 135.4 (d, JP-C = 16.2 Hz), 133.9 (d, JP-C
103.1 Hz), 132.9 (d, JP-C = 2.9 Hz), 131.7 (d, JP-C = 11.8 Hz), 130.3 = 10.0 Hz), 37.1 (d, JP-C = 72.6 Hz), 26.1 (d, JP-C = 4.2 Hz), 26.0 (d,
(d, JP-C = 13.3 Hz), 130.0 (d, JP-C = 10.5 Hz), 128.5 (d, JP-C JP-C = 5.2 Hz), 25.5 (d, JP-C = 1.4 Hz), 24.2 (d, JP-C = 3.1 Hz), 23.7
=
128.89 (d, JP-C = 11.4 Hz), 112.1 (d, JP-C = 91.2 Hz), 111.9 (d, JP-C
=
10.2Hz), 128.1 (d, JP-C = 13.3 Hz), 127.9 (d, JP-C = 9.3 Hz), 108.1 (d, JP-C = 3.1 Hz), 20.2. 31P NMR (CDCl3, 162 MHz): δ = 47.4.
(d, JP-C = 105.7 Hz), 20.6, 16.0 (d, JP-C = 1.4 Hz). 31P NMR (CDCl3, HRMS (ESI-TOF): m/z = 393.0612, calcd for C19H23O2PBr [MH+]
162 MHz): δ = 37.7. HRMS (ESI-TOF): m/z = 391.0426, calcd for 393.0619.
C20H18O2PCl2 [MH+] 391.0421.
3an: 33.6 mg (yield 63%). 1H NMR (CDCl3, 400 MHz): δ = 11.08
o
1
3ai: white solid, mp. 198.2–199.0 C, 42.5 mg (yield 63%). H (s, 1H), 7.19 (d, J = 8.4 Hz, 1H), 6.82 (dd, J1 = 8.8 Hz, J2 =4.4Hz,
NMR (CDCl3, 400 MHz): δ = 11.10 (s, 1H), 7.49–7.45 (m, 2H), 1H), 6.75 (dd, J1 = 12.4 Hz, J2 =1.6 Hz, 1H), 2.27 (s, 3H), 2.01–
7.36–7.33 (m, 2H), 7.25–7.16 (m, 3H), 7.13–7.07 (m, 2H), 6.92 1.84 (m, 4H), 1.72–1.63 (m, 4H), 1.43–1.38 (m, 4H), 0.90 (t, J =
(dd, J1 = 8.4 Hz, J2 =4.8Hz, 1H), 6.43 (dd, J1 = 13.6 Hz, J2 =1.6 Hz, 7.2 Hz, 6H). 13C NMR (CDCl3, 100 MHz): δ = 162.0 (d, JP-C = 2.0
1H), 2.57 (s, 6H), 2.15 (s, 3H). 13C NMR (CDCl3, 100 MHz): δ = Hz), 134.9 (d, JP-C = 2.1 Hz), 128.7 (d, JP-C = 10.0 Hz), 128.3 (d, JP-
162.2 (d, JP-C = 2.8 Hz), 143.4 (d, JP-C = 8.4 Hz), 135.4 (d, JP-C
=
= 11.8 Hz), 118.1 (d, JP-C = 7.2 Hz), 110.5 (d, JP-C = 92.0 Hz),
C
8 | J. Name., 2012, 00, 1-3
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30.3 (d, JP-C = 67.4 Hz), 23.9 (d, JP-C = 14.9 Hz), 23.1 (d, JP-C = 4.1 (CDCl3, 162 MHz): δ = 39.1. HRMS (ESI-TOF): m/z = 409.1350,
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+
Hz), 20.5, 13.6. 31P NMR (CDCl3, 162 MHz): δ = 56.0. HRMS calcd for C27H22O2P [MH ] 409.1357. The structure of this
(ESI-TOF): m/z = 269.1671, calcd for C15H26O2P [MH+] 269.1670. compound was further confirmed by an X-ray crystallographic
3ao: 38.2 mg (yield 60%). 1H NMR (CDCl3, 400 MHz): δ = 11.33 analysis.
DOI: 10.1039/C9OB00129H
(s, 1H), 7.19 (d, J = 8.4 Hz, 1H), 6.81 (dd, J1 = 8.4 Hz, J2 = 4.0Hz, 6b: 59.2 mg (yield 70%). 1H NMR (CDCl3, 400 MHz): δ = 11.43 (s,
1H), 6.73 (dd, J1 = 10.8 Hz, J2 =1.2 Hz, 1H), 2.28 (s, 3H), 2.06– 1H), 7.73–7.67 (m, 4H), 7.61–7.57 (m, 2H), 7.51–7.47 (m, 4H),
2.01 (m, 4H), 1.87–1.69 (m, 8H), 1.42–1.20 (m, 10H). 13C NMR 7.44–7.35 (m, 3H), 7.21 (t, J=7.6 Hz, 1H), 7.12 (d, J= 7.6 Hz, 1H),
(CDCl3, 100 MHz): δ = 163.1, 134.7 (d, JP-C = 1.9 Hz), 129.2 (d, JP- 6.78 (dd, J1 = 13.6 Hz, J2 = 1.6 Hz, 1H), 2.33 (s, 3H), 2.19 (s, 3H).
= 10.0 Hz), 127.6 (d, JP-C = 10.9 Hz), 118.1 (d, JP-C = 7.2 Hz), 13C NMR (CDCl3, 100 MHz): δ = 161.8 (d, JP-C = 3.7 Hz), 138.2 (d,
C
107.9 (d, JP-C = 85.9 Hz), 35.7 (d, JP-C = 65.6 Hz), 26.3 (d, JP-C
=
JP-C = 2.5 Hz), 137.8, 132.6 (d, JP-C = 3.4 Hz), 132.2, 132.0 (d, JP-C
14.9 Hz), 26.1 (d, JP-C = 11.8 Hz), 25.7, 25.2 (d, JP-C = 2.9 Hz), = 9.9 Hz), 131.3 (d, JP-C = 96.5 Hz), 129.1, 128.68, 128.66 (d, JP-C
24.0 (d, JP-C = 3.1 Hz), 20.6. 31P NMR (CDCl3, 162 MHz): δ = 60.5. = 12.4 Hz), 128.1, 128.0, 123.0, 113.3 (d, JP-C = 9.4 Hz), 111.3 (d,
HRMS (ESI-TOF): m/z = 321.1986, calcd for C19H30O2P [MH+] JP-C = 102.2 Hz), 94.6, 84.2 (d, JP-C = 2.7 Hz), 21.1, 20.3. 31P NMR
321.1983.
Synthetic
(CDCl3, 162 MHz): δ = 39.0. HRMS (ESI-TOF): m/z = 423.1516,
2-(di-p-tolylphosphanyl)-4- calcd for C28H24O2P [MH+] 423.1514.
procedure
for
methylphenol (4): To a solution of 3ab (1.233 g, 4.0 mmol) and 6c: white solid, mp 181.4–182.8 °C, 57.0 mg(yield 68%). 1H
triethylamine (2.8 mL, 20 mmol) in toluene (20 mL) was added NMR (CDCl3, 400 MHz): δ = 11.40 (s, 1H), 7.73–7.67 (m, 4H),
trichlorosilane (1.9 mL, 20 mmol) dropwise at 0 oC. The 7.61–7.57 (m, 2H), 7.51–7.44 (m, 7H), 7.13 (d, J = 8.0 Hz, 2H),
mixture was then stirred at 100 ºC for 48 h. After the mixture 6.77 (dd, J1 = 13.6 Hz, J2 = 1.6 Hz, 1H), 2.34 (s, 3H), 2.18 (s, 3H).
o
was cooled to 0 C, 1 N NaOH (aq) (20 mL) was slowly added, 13C NMR (CDCl3, 100 MHz): δ = 161.8 (d, JP-C = 2.9 Hz), 138.4,
and the mixture was warmed to room temperature, and then 138.2 (d, JP-C = 3.0 Hz), 132.6 (d, JP-C = 3.5 Hz), 132.0 (d, JP-C
stirred at 60 ºC for 30 min. The mixture was cooled to room 10.6 Hz), 131.8 (d, JP-C = 9.4 Hz), 131.5, 130.9, 129.0, 128.7 (d,
temperature, and filtered through a pad of celite eluted with JP-C = 12.4 Hz), 128.0 (d, JP-C = 12.4 Hz), 120.1, 113.4 (d, JP-C
=
=
ethyl acetate. The organic layer was separated, dried over 9.5 Hz), 111.3 (d, JP-C = 102.5 Hz), 94.6, 83.9 (d, JP-C = 1.8 Hz),
MgSO4, filtered, and concentrated on a rotary evaporator. The 21.5, 20.3. 31P NMR (CDCl3, 162 MHz): δ = 39.0. HRMS (ESI-
residue was subjected to flash column chromatography on TOF): m/z = 423.1514, calcd for C28H24O2P [MH+] 423.1514.
o
1
silica gel (petroleum ether/ethyl acetate 30/1–10/1) to give 4 6d: white solid, mp 154.6–155.5 C, 58.6 mg (yield 65%). H
1
(0.846 g, 66%). H NMR (CDCl3, 400 MHz): δ = 7.25–7.15 (m, NMR (CDCl3, 400 MHz): δ = 11.37 (s, 1H), 7.73–7.68 (m, 4H),
8H), 7.08 (dd, J1 = 8.4 Hz, J2 =1.6 Hz, 1H), 6.82–6.79 (m, 2H), 7.61–7.57 (m, 2H), 7.52–7.44 (m, 7H), 7.14 (d, J = 8.4 Hz, 2H),
5.99 (s, 1H), 2.35 (s, 6H), 2.17 (s, 3H). 13C NMR (CDCl3, 100 6.77 (dd, J1 = 13.2 Hz, J2 = 1.2 Hz, 1H), 2.58 (t, J = 7.4 Hz, 2H),
MHz): δ = 156.9 (d, JP-C = 16.8 Hz), 139.0, 134.7 (d, JP-C = 5.9 Hz), 2.19 (s, 3H), 1.68–1.58 (m, 2H), 0.93 (t, J= 7.4 Hz, 3H). 13C NMR
133.4 (d, JP-C = 19.2 Hz), 132.2, 131.6 (d, JP-C = 3.8 Hz), 130.1 (d, (CDCl3, 100 MHz): δ = 161.7 (d, JP-C = 3.2 Hz), 143.1, 138.2 (d, JP-
JP-C = 2.4 Hz), 129.5 (d, JP-C = 7.2 Hz), 120.9 (d, JP-C = 6.0 Hz), C = 1.9 Hz), 132.5 (d, JP-C = 2.3 Hz), 132.0 (d, JP-C = 9.7 Hz), 131.8
115.4 (d, JP-C = 1.6 Hz), 21.4, 20.6. 31P NMR (CDCl3, 162 MHz): δ (d, JP-C = 9.6 Hz), 131.7, 131.3 (d, JP-C = 95.7 Hz), 128.7 (d, JP-C
= -29.6. HRMS (ESI-TOF): m/z = 321.1416, calcd for C21H22OP 12.4 Hz), 128.4, 128.0 (d, JP-C = 12.5 Hz), 120.3, 113.4 (d, JP-C
=
=
[MH+] 321.1408.
9.5 Hz), 111.2 (d, JP-C = 101.6 Hz), 94.7, 83.9 (d, JP-C = 1.8 Hz),
General procedure for the Zn(OTf)2-catalyzed preparation of 2- 37.9, 24.3, 20.3, 13.7. 31P NMR (CDCl3, 162 MHz): δ = 38.9.
phosphinyl phenols 6. An oven-dried Schlenk tube containing a HRMS (ESI-TOF): m/z = 451.1826, calcd for C30H28O2P [MH+]
Teflon-coated stir bar was charged with Zn(OTf)2 (7.2 mg, 451.1827.
10 mol %). The Schlenk tube was sealed and then evacuated 6e: 64.5 mg (yield 76%). 1H NMR (CDCl3, 400 MHz): δ = 11.58 (s,
and backfilled with N2 (3 cycles). Then 5 (0.2 mmol) and 2 1H), 7.73–7.68 (m, 4H), 7.62–7.58 (m, 2H), 7.53–7.48 (m, 4H),
(0.6 mmol) dissolved in 2 mL of toluene was injected. The 7.44 (s, 1H), 7.35–7.24 (m, 3H), 7.04–6.99 (m, 1H), 6.79 (dd, J1
Schlenk tube was sealed and immersed in an oil bath which = 13.6 Hz, J2 = 1.6 Hz, 1H), 2.20 (s, 3H). Due to the coupling of
was heated to 100 oC. After the reaction was complete (6-48 h, F-C and P-C, the 13C NMR spectra show complex peaks not
monitored by TLC), removal of the solvent under vacuum left a easily interprepted. Typical signals belong to the alkyne unit: δ
slurry residue, which was purified by flash chromatography on = 92.98 (d, JF-C = 2.7 Hz), 85.66 (d, JP-C = 2.4 Hz). Signals belong
silica (petroleum ether/ethyl acetate 10/1 to 4/1) to afford the to the methyl group: δ = 20.3. A full list of the 13C NMR data:
product 6.
13C NMR (CDCl3, 100 MHz): δ = 163.5, 162.2, 162.1, 161.1,
o
1
6a: white solid, mp 201.5–202.4 C, 69.7 mg (yield 84%). H 138.33, 138.31, 132.67, 132.65, 132.3, 132.2, 132.1, 132.0,
NMR (CDCl3, 400 MHz): δ = 11.47 (s, 1H), 7.73–7.68 (m, 4H), 131.9, 130.8, 129.8, 129.7, 128.8, 128.7, 128.2, 128.0, 127.60,
7.61–7.55 (m, 4H), 7.52–7.48 (m, 4H), 7.45 (s, 1H), 7.34–7.32 127.58, 125.1, 125.0, 118.5, 118.3, 115.7, 115.4, 112.9, 112.8,
(m, 3H), 6.78 (d, J = 12.0 Hz, 1H), 2.19 (s, 3H). 13C NMR (CDCl3, 111.9, 110.8, 92.99, 92.96, 85.67, 85.65, 20.3. 31P NMR (CDCl3,
100 MHz): δ = 161.9 (d, JP-C = 2.8 Hz), 138.2 (d, JP-C = 2.5 Hz), 162 MHz): δ = 39.3. HRMS (ESI-TOF): m/z = 427.1261, calcd for
132.6 (d, JP-C = 3.1 Hz), 132.0 (d, JP-C = 10.1 Hz), 131.9 (d, JP-C
=
C27H21O2PF [MH+] 427.1263.
1
9.6 Hz), 131.7, 130.9, 128.7 (d, JP-C = 12.4 Hz), 128.23, 128.21, 6f: white solid, mp 238.0–239.0 °C, 53.6 mg (yield 63%). H
128.1 (d, JP-C = 12.6 Hz), 123.2, 113.2 (d, JP-C = 9.5 Hz), 111.3 (d, NMR (CDCl3, 400 MHz): δ = 11.43 (s, 1H), 7.73–7.68 (m, 4H),
JP-C = 103.1 Hz), 94.4, 84.6 (d, JP-C = 2.5 Hz), 20.3. 31P NMR 7.61–7.48 (m, 9H), 7.34–7.31 (m, 3H), 6.81 (dd, J1 = 13.2 Hz, J2
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1
= 2.0 Hz, 1H), 2.49 (q, J= 7.6 Hz, 2H), 1.13 (t, J= 7.6, 3H). 13C 6k: 21.0 mg (yield 24%). H NMR (CDCl3, 400 MHz): δ = 8.32–
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NMR (CDCl3, 100 MHz): δ = 162.0 (d, JP-C = 3.0 Hz), 137.0 (d, JP-C 8.27 (m, 2H), 7.43–7.31 (m, 9H), 7.28–7D.2O3I:(1m0.,1023H9/)C, 97O.1B500(1t2,9JH=
= 3.1 Hz), 134.5 (d, JP-C = 12.2 Hz), 132.6 (d, JP-C = 2.8 Hz), 131.9 6.4 Hz, 2H), 6.94 (dd, J1 = 8.4 Hz, J2 = 2.0 Hz, 1H), 2.39 (s, 6H),
(d, JP-C = 11.0 Hz), 131.6, 131.3 (d, JP-C = 104.6 Hz), 131.0 (d, JP-C 2.24 (s, 3H). 13C NMR (CDCl3, 100 MHz): δ = 149.7 (d, JP-C = 8.0
= 10.2 Hz), 128.7 (d, JP-C = 12.4 Hz), 128.23, 128.19, 123.12, Hz), 141.8 (d, JP-C = 11.1 Hz), 133.9 (d, JP-C = 10.0 Hz), 133.5,
113.2 (d, JP-C = 9.5 Hz), 111.3 (d, JP-C = 102.1 Hz), 94.3, 84.7 (d, 133.3, 132.5 (d, JP-C = 2.8 Hz), 131.5 (d, JP-C = 13.2 Hz), 130.2,
JP-C = 2.4 Hz), 27.6, 15.5. 31P NMR (CDCl3, 162 MHz): δ = 39.1. 129.7 (d, JP-C = 132.7 Hz), 128.3, 125.6 (d, JP-C = 12.9 Hz), 123.2,
HRMS (ESI-TOF): m/z = 423.1516, calcd for C28H24O2P [MH+] 119.2 (d, JP-C = 5.1 Hz), 114.8 (d, JP-C = 6.8 Hz), 93.6, 85.6, 21.2
423.1514.
(d, JP-C = 4.3 Hz), 20.4. 31P NMR (CDCl3, 162 MHz): δ = 30.0.
1
6g: white solid, mp 199.3–200.5 °C, 61.8 mg (yield 70%). H HRMS (ESI-TOF): m/z = 437.1676, calcd for C29H26O2P [MH+]
NMR (CDCl3, 400 MHz): δ = 11.07 (s, 1H), 7.73–7.67 (m, 4H), 437.1670.
7.56-7.54 (m, 2H), 7.47 (s, 1H), 7.34–7.32 (m, 3H), 7.23–7.18 6l: 53.8 mg (yield 73%). 1H NMR (CDCl3, 400 MHz): δ = 11.33 (s,
(m, 4H), 6.77 (dd, J1 = 13.6 Hz, J2 = 1.6 Hz, 1H), 2.21 (s, 3H). Due 1H), 7.58–7.55 (m, 2H), 7.43 (s, 1H), 7.34–7.32 (m, 3H), 6.83
to the coupling of F-C and P-C, the 13C NMR spectra show (dd, J1 = 12.4 Hz, J2 = 1.6 Hz, 1H), 2.28 (s, 3H) , 2.04–1.85 (m,
complex peaks not easily interprepted. Typical signals belong 4H), 1.73–1.63 (m, 2H), 1.52–1.36 (m, 6H), 0.89 (t, J= 7.2 Hz,
to the alkyne unit: δ = 94.75, 84.27 (d, JP-C = 3.0 Hz). Signals 6H). 13C NMR (CDCl3, 100 MHz): δ = 161.7 (d, JP-C = 2.4 Hz),
belong to the methyl group: δ = 20.3. A full list of the 13C NMR 137.8 (d, JP-C = 2.7 Hz), 131.7, 129.7 (d, JP-C = 9.8 Hz), 128.31,
data: 13C NMR (CDCl3, 100 MHz): δ = 166.70, 166.68, 161.49, 128.27, 128.22, 123.1, 112.6 (d, JP-C = 8.5 Hz), 111.4 (d, JP-C
=
161.45, 138.46, 138.43, 134.65, 134.56, 134.53, 134.44, 131.79, 90.5 Hz), 94.4, 84.6 (d, JP-C = 1.2 Hz), 30.1 (d, JP-C = 67.9 Hz),
131.70, 131.65, 128.47, 128.36, 128.23, 127.81, 127.79, 126.73, 23.9 (d, JP-C = 13.8 Hz), 23.1 (d, JP-C = 4.3 Hz), 20.3, 13.6.31P
126.70, 123.00, 116.42, 116.28, 116.21, 116.07, 113.45, 113.36, NMR (CDCl3, 162 MHz): δ = 55.3. HRMS (ESI-TOF): m/z =
111.74, 110.70, 94.7, 84.28, 84.25, 20.3. 31P NMR (CDCl3, 162 369.1987, calcd for C23H30O2P [MH+] 369.1983.
MHz): δ = 36.9. HRMS (ESI-TOF): m/z = 445.1171, calcd for 6m: 48.1 mg (yield 57%). 1H NMR (CDCl3, 400 MHz): δ = 12.03
C27H20O2PF2 [MH+] 445.1169.
(s, 1H), 7.57–7.55 (m, 2H),7.43 (s, 1H), 7.34–7.31 (m, 3H), 6.74
1
6h: white solid, mp 211.1–212.3 °C, 69.8 mg (yield 80%). H (dd, J1 = 10.8 Hz, J2 = 1.6Hz, 1H), 2.29 (s, 3H), 2.07–2.02 (m, 4H),
NMR (CDCl3, 400 MHz): δ = 11.65 (s, 1H), 7.60–7.54 (m, 6H), 1.87–1.69 (m, 8H), 1.43–1.20 (m, 10H). 13C NMR (CDCl3, 100
7.42 (d, J= 2.0 Hz, 1H), 7.33–7.25 (m, 7H), 6.76 (dd, J1 = 13.2 Hz, MHz): δ = 163.4, 137.8 (d, JP-C = 2.2 Hz), 131.7, 129.6 (d, JP-C
=
J2 = 1.6 Hz, 1H), 2.41 (s, 6H), 2.17 (s, 3H). 13C NMR (CDCl3, 100 8.8 Hz), 128.14, 128.12, 127.4 (d, JP-C = 10.5 Hz), 123.3, 112.9
MHz): δ = 161.9 (d, JP-C = 2.7 Hz), 143.1 (d, JP-C = 2.5 Hz), 138.0 (d, JP-C = 9.0 Hz), 108.4 (d, JP-C = 84.0 Hz), 94.1, 85.0 (d, JP-C = 2.2
(d, JP-C = 2.7 Hz), 132.0 (d, JP-C = 10.6 Hz), 131.9 (d, JP-C = 9.5 Hz), Hz), 35.6 (d, JP-C = 65.8 Hz), 26.16 (d, JP-C = 3.3 Hz), 26.15 (d, JP-C
131.6, 129.4 (d, JP-C = 13.8 Hz), 128.3 (d, JP-C = 107.2 Hz), 128.1, = 28.3 Hz), 25.6, 25.1 (d, JP-C = 2.9 Hz), 24.0 (d, JP-C = 3.4 Hz),
127.8 (d, JP-C = 12.6 Hz), 123.2, 113.0 (d, JP-C = 9.4 Hz), 111.8 (d, 20.3. 31P NMR (CDCl3, 162 MHz): δ = 60.9. HRMS (ESI-TOF): m/z
JP-C = 102.7 Hz), 94.2, 84.8 (d, JP-C = 2.5 Hz), 21.6, 20.3. 31P NMR = 421.2291, calcd for C27H34O2P [MH+] 421.2296.
(CDCl3, 162 MHz): δ = 39.4. HRMS (ESI-TOF): m/z = 437.1675, Synthetic procedure for (3-Iodo-5-methyl-2-phenylbenzofuran-7-
calcd for C29H26O2P [MH+] 437.1670.
yl)diphenyl phosphine oxide (7): An oven-dried Schlenk tube
6i: 47.9 mg (yield 51%). 1H NMR (CDCl3, 400 MHz): δ = 11.69 (s, containing a Teflon-coated stir bar was charged with 6a
1H), 7.64–7.54 (m, 6H), 7.42 (d, J= 1.6 Hz, 1H), 7.35-7.31 (m, (81.7mg, 0.2 mmol) NaHCO3 (50.4, 0.6 mmol) and MeCN (2
3H), 7.00–6.97 (m, 4H), 6.74 (dd, J1 = 13.6 Hz, J2 = 1.6 Hz, 1H), mL). After stirring at rt for 30 min, I2 (151.8 mg, 0.6 mmol ) was
3.85 (s, 6H), 2.18 (s, 3H). 13C NMR (CDCl3, 100 MHz): δ = 162.9 added. After the reaction was complete (monitored by TLC, 2
(d, JP-C = 3.1 Hz), 161.9 (d, JP-C = 2.7 Hz), 137.9 (d, JP-C = 1.8 Hz), h), the reaction was quenched with aq. Na2S2O3. The mixture
133.9 (d, JP-C = 11.6 Hz), 132.0 (d, JP-C = 9.6 Hz), 131.6, 128.2, was extracted with EtOAc. The combined organic layers were
127.8 (d, JP-C = 12.5 Hz), 122.2, 114.2 (d, JP-C = 12.8 Hz), 113.0 (d, dried over MgSO4, filtered and concentrated. The residue was
JP-C = 9.6 Hz), 112.2 (d, JP-C = 103.0 Hz), 94.1, 84.9 (d, JP-C = 2.9 purified with silica gel column chromatography (PE/EtOAc 3/1
Hz), 55.3, 20.3. 31P NMR (CDCl3, 162 MHz): δ = 39.0. HRMS to 1/1) to afford compound 7 as a white solid (93.6 mg, 88%).
o
1
(ESI-TOF): m/z = 469.1566, calcd for C29H26O4P [MH+] 469.1569. mp. 240.4–241.0 C. H NMR (CDCl3, 400 MHz): 7.87–7.77 (m,
6j: 63.5 mg (yield 67%). 1H NMR (CDCl3, 400 MHz): δ = 10.68 (s, 5H), 7.68–7.64 (m, 2H), 7.58–7.53 (m, 2H), 7.48–7.44 (m, 5H),
1H), 7.70–7.66 (m, 2H), 7.59–7.54 (m, 6H), 7.49–7.43 (m, 3H), 7.37–7.33 (m, 3H), 2.53 (s, 3H). 13C NMR (CDCl3, 100 MHz): δ =
7.34–7.32 (m, 3H), 6.84 (dd, J1 = 13.6 Hz, J2 = 1.6 Hz, 1H), 2.23 153.5, 151.5 (d, JP-C = 3.0 Hz), 133.4 (d, JP-C = 100.1 Hz), 133.8,
(s, 3H). 13C NMR (CDCl3, 100 MHz): δ = 161.1 (d, JP-C = 4.2 Hz), 133.0, 132.0 (d, JP-C = 3.3 Hz), 131.9 (d, JP-C = 10.2 Hz), 131.6 (d,
138.7 (d, JP-C = 2.8 Hz), 135.3 (d, JP-C = 16.4 Hz), 133.2 (d, JP-C
=
JP-C = 4.6 Hz), 129.3, 128.6, 128.4 (d, JP-C = 7.3 Hz), 127.2, 126.3
103.8 Hz), 133.0 (d, JP-C = 1.9 Hz), 131.8 (d, JP-C = 9.7 Hz), 131.62, (d, JP-C = 2.3 Hz), 115.6 (d, JP-C = 101.4 Hz), 60.6, 21.2. 31P NMR
131.60 (d, JP-C = 11.0 Hz), 131.6, 130.2 (d, JP-C = 13.2 Hz), 129.9 (CDCl3, 162 MHz): δ = 23.3; HRMS (ESI-TOF): m/z = 535.0327,
(d, JP-C = 10.5 Hz), 128.7 (d, JP-C = 13.3 Hz), 128.4, 128.2, 122.8, calcd for C27H21O2PI [MH+]535.0324.
113.4 (d, JP-C = 9.7 Hz), 110.5 (d, JP-C = 104.2 Hz), 95.0, 84.0 (d,
JP-C = 2.7 Hz), 20.3. 31P NMR (CDCl3, 162 MHz): δ = 35.7. HRMS
(ESI-TOF): m/z = 477.0571, calcd for C27H20Cl2O2P [MH+]
Conflicts of interest
477.0578.
There are no conflicts to declare.
10 | J. Name., 2012, 00, 1-3
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6
7
(a) N. Takahiro, M. Yuko and H. Tamio, Org. Lett., 2011, 13,
Acknowledgements
View Article Online
3674; (b) M. Hatano and K. Ishihara, Chem. Rec., 2008, 8,
DOI: 10.1039/C9OB00129H
143.
Financial support from the National Natural Science
Foundation of China (21302095), Jiangsu Provincial NSFC
(BK20130924), Training Program of Innovation and
Entrepreneurship for Undergraduates (2018DC313) and
Nanjing Tech University is acknowledged.
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This journal is © The Royal Society of Chemistry 20xx
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I. Weidner, J.-M. Neudörfl, J. Lex and H.-G. Schmalz, Adv.
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Table of contents
View Article Online
DOI: 10.1039/C9OB00129H
A highly regioselective C–P coupling reaction of p-quinol ethers with secondary phosphine oxides is
developed as a new synthetic method for 2-phosphinylphenols by using Zn(OTf)2 as the catalyst.
selective
OH
O
P
R3
O
C() P coupling
R2
O

cat. Zn(OTf)2
R1
R2
P
R3
H
R1
+
- MeOH

R
OMe
R
36 examples (yield: 24%-94%)
R = Me, Et, Ph
R1 = Me, tBu, Ph, halide, alkynyl
R2, R3 = Ar or Alkyl