Hydroxyphosphinylation reaction of 3-cyclopropylideneprop-2-en-1-ones via C-P σ-bond cleavage

Article abstract of DOI:10.1021/jo400610q

An unexpected hydroxyphosphinylation of 3-cyclopropylideneprop-2-en-1-ones with phosphines has been observed. This method provides a unique regio- and stereoselective synthesis of highly functionalized 1-dialkylphinyl-3-oxo-(1Z)- alkenyl cyclopropanols with important potentials. The reaction displays an unusual mechanistic feature - a highly selective cleavage of C-P σ bonds in phosphines.

Full text of DOI:10.1021/jo400610q

Article
pubs.acs.org/joc
Hydroxyphosphinylation Reaction of 3‑Cyclopropylideneprop-2-en-
1-ones via C−P σ‑Bond Cleavage
Maozhong Miao,† Jian Cao,† Xian Huang,†,‡,§ and Luling Wu*,†
†Department of Chemistry, Zhejiang University, Hangzhou 310028, People’s Republic of China
‡State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences,
Shanghai 200032, People’s Republic of China
S
* Supporting Information
ABSTRACT: An unexpected hydroxyphosphinylation of 3-cyclo-
propylideneprop-2-en-1-ones with phosphines has been observed.
This method provides a unique regio- and stereoselective synthesis
of highly functionalized 1-dialkylphinyl-3-oxo-(1Z)-alkenyl cyclo-
propanols with important potentials. The reaction displays an
unusual mechanistic featurea highly selective cleavage of C−P σ
bonds in phosphines.
synthetic access to vinylbicyclo[(n+2).1.0]alkanols with ex-
cellent regio- and diastereoselectivity4 (Scheme 1, eq 2).
However, to best of our knowledge, reports on the addition
reactions of allenes with the introduction of the hydroxyl group
and organophosphorus group at the same time are limited.
Meanwhile, the 3-cyclopropylideneprop-2-en-1-ones,5 which
contain the highly strained cyclopropyl ring and carboxyl group
adjacent to the two ends of cumulated CC bonds, are a kind
of highly activated analogue of allenes. In the presence of the
carboxyl group adjacent to the allene group, the substrates have
great potential to react with organophosphorus compounds.
Thus, we turned our effort toward such a “phosphorus-
hydroxylation” reaction of 3-cyclopropylideneprop-2-en-1-ones
(Scheme 1, eq 3).
On the other hand, the selective cleavage of an unactivated
element−carbon bond has always been an attractive topic in
organic synthesis.6 Several reactions involving the cleavage of
C−P bonds have been well reported.7 In particular, the C−P
bond cleavage in tertiary phosphines has attracted considerable
interest because they are important ligands for transition metals
and are versatile intermediates in organic synthesis.8 Much
progress on C−P activation with transition metals in tertiary
phosphines has been achieved in the past few decades:9 For
example, Chan and co-workers have reported a catalytic user-
friendly phosphination using triarylphosphines (Scheme 2, eq
1);9a Jackson and co-workers have established the preparation
of diphenyl-substituted phosphines using alkali metals in silica
gel (M-SG) (Scheme 2, eq 2).9b However, very few examples of
direct cleavage of C−P σ bonds that form phosphorus-
containing compounds10 without metals have been reported
because of the relatively strong C−P σ bond.11 Herein we
disclose our recent unexpected observations on the hydrox-
yphosphinylation reaction of 3-cyclopropylideneprop-2-en-1-
INTRODUCTION
■
The addition reactions of a carbon−carbon multiple bond
constitute highly synthetically versatile processes. Two identical
or different functionalities, which can undergo a multitude of
further synthetic transformations, are added to the unsaturated
moiety in a single step.1 In the past few decades, much
attention has been paid to the halohydroxylation reaction of
allenes because it is a powerful method for introducing the
halogen and hydroxyl groups to form β-halogen-substituted
alcohols.2 Previously, Ma3 has reported that attaching a
heteroatom such as sulfur or phosphorus adjacent to allenes
would be an effective solution and a series of corresponding 2-
halogen-substituted allylic alcohols could be regio- and
stereoselectively synthesized via the halohydroxylation of the
substituted allenes (Scheme 1, eq 1). In this case, we have
presented a comprehensive study of the halohydroxylation
reaction of vinylidenecyclopropanes that provides direct
Scheme 1. Reported Halohydroxylation Reactions and Our
Concept of the “Phosphorus-Hydroxylation” Reaction
Received: April 1, 2013
© XXXX American Chemical Society
A
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reaction are summarized in Table 1. The yield was improved to
74% when 7.5 equiv of H2O was used; a higher loading of H2O
failed to give a higher yield (Table 1, entries 2 and 3). A 1.5
equiv amount of triphenylphosphine is necessary (Table 1,
entries 2, 4, and 5). The reaction could also be conducted in
DCM and CH3CN, affording 3a in good yields (Table 1,
entries 6 and 7); however, the reaction performed poorly in
nonpolar toluene (Table 1, entry 8); CH3OH turned out to be
totally ineffective, probably due to the nucleophilic solvent
leading to other reactions (Table 1, entry 9). The yield of 3a
dropped at a higher temperature (Table 1, entries 10 and 11).
Moreover, using pure oxygen instead of air led to a faster
reaction, albeit with a lower yield of 3a (Table 1, entry 12).
When the reaction was conducted under an N2 atmosphere,
only a trace amount of 3a was formed (Table 1, entry 13),
indicating that the oxygen in the air must play an important role
in this reaction. Finally, the best conditions are defined as
follows: reaction in acetone at 0 °C using 1.5 equiv of
triphenylphosphine (2a) and 7.5 equiv of H2O in open air
(Table 1, entry 2).
Scheme 2. Reported C−P Cleavage Reactions and Our
Observations on Metal-Free C−P Cleavage Reactions
ones for introducing the hydroxyl group and phosphorus group
via C−P bond cleavage (Scheme 2, eq 3).
RESULTS AND DISCUSSION
■
Initially, the reaction of 1a with 1.5 equiv of triphenylphosphine
(2a) in the presence of 2.5 equiv of H2O in acetone in open air
afforded the unknown product 3a (Table 1, entry 1). Through
Scope of the Hydroxyphosphinylation Reaction. With
the optimized conditions in hand, the scope of the reaction of a
variety of compounds 1 with triphenylphosphine (2a) was
examined. The results summarized in Table 2 show that
Table 1. Optimization of the Reaction Conditions for the
a
Formation of 3a
Table 2. Scope of the Reaction of Various Compounds 1
a
with Triphenylphosphine 2a for the Formation of 3
amt of PPh3
(equiv)
amt of H2O
(equiv)
yield of 3a
b
entry
solvent
(%)
b
entry
R1, R2 for 1
yield of 3 (%)
1
2
3
4
5
6
7
1.5
1.5
1.5
1.0
2.0
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
2.5
7.5
10
acetone
acetone
acetone
acetone
acetone
DCM
60
74
74
1
4-MeC6H4, Ph (1a)
Ph, Ph (1b)
74 (3a)
69 (3b)
87 (3c)
90 (3d)
73 (3e)
56 (3f)
43 (3g)
57 (3h)
72 (3i)
90 (3j)
94 (3k)
79 (3l)
2
c
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
46
3
4-FC6H4, Ph (1c)
4-BrC6H4, Ph (1d)
4-MeOC6H4, Ph (1e)
2-furyl, Ph (1f)
73
69
72
29
4
5
CH3CN
toluene
CH3OH
acetone
acetone
acetone
acetone
6
d
8
7
2-thienyl, Ph (1g)
4-ClC6H4, 2-MeOC6H4 (1h)
Ph, 3-MeC6H4 (1i)
Ph, 4-MeOC6H4 (1j)
Ph, 4-FC6H4 (1k)
Ph, 2-naphthyl (1l)
e
9
0
8
f
10
52
9
g
11
complex
62
10
11
12
h
12
i
13
trace
a
a
The reaction was carried out using 1a (0.15 mmol) in 5 mL of
Unless otherwise specified, the reaction was carried out using 1 (0.15
b
c
solvent in open air. Isolated yields. 17% of 1a was recovered.
mmol) in presence of 1.5 equiv of PPh3 and 7.5 equiv of H2O in 5 mL
d
e
f
b
Reaction time 36 h. Unknown products were formed. The reaction
of acetone in an air atmosphere at 0 °C. Isolated yields.
g
was conducted at room temperature. The reaction was conducted
under reflux. The reaction was conducted under an oxygen
atmosphere for 4 h. The reaction was conducted under a nitrogen
h
i
different products 3 could be obtained smoothly in moderate to
high yields. When R2 is a phenyl group, various useful
substituted phenyl (Table 2, entries 1−5) were well tolerated at
the R1 position, with the more electron-deficient 1c,d affording
3c,d in higher yields (Table 2, entries 3 and 4); the
heteroaromatic substituted 1f,g also gave the products in
moderate yields (Table 2, entries 6 and 7). Moreover, electron-
donating groups or electron-withdrawing groups on the
aromatic rings and β-naphthyl were well tolerated at the R2
position (Table 2, entries 9−12).
atmosphere.
spectroscopic (1H and 13C NMR, MS) and X-ray diffraction
analysis (Figure S1, Supporting Information), we identified that
the product 3a contains a vinylcyclopropanol unit with a
phosphoryl group attached to the CC bond, showing an
exclusive Z selectivity; thus, the reaction showed an unexpected
aryl−P bond cleavage with unique regio- and stereoselectivity.
Optimization of the Hydroxyphosphinylation Reac-
tion. Efforts were then made to optimize the reaction
conditions to improve the yield of 3a. Typical results of the
Subsequently, we investigated the scope and limitations of
phosphines with substrate 1b (Table 3). The reaction may be
conducted with arylphosphines substituted with electron-
B
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Table 3. Scope of the Reaction of 1b with Phosphines 2 for
the Formation of 3
Scheme 4. Electronic Effects on the Selectivity of C−P Bond
Cleavage in the Hydroxyphosphinylation Reaction
a
b
entry
R (2)
yield of 3 (%)
1
2
3
4
5
6
7
8
9
4-MeOC6H4 (2b)
3,5-(MeO)2C6H4 (2c)
4-FC6H4 (2d)
80 (3m)
78 (3n)
c
50 (3o)
c
4-ClC6H4 (2e)
4-MeC6H4 (2f)
3-MeC6H4 (2g)
2-MeC6H4 (2h)
n-Bu (2i)
48 (3p)
64 (3q)
69 (3r)
NR
complex
74 (3s)
Scheme 5. Reaction of Isobutyl Ketone 1m with
Triphenylphosphine 2a
2-naphthyl (2j)
a
Unless otherwise specified, the reaction was carried out using 1b
(0.15 mmol) in presence of 1.5 equiv of PR3 and 7.5 equiv of H2O in 5
mL of acetone in an air atmosphere at 0 °C. Isolated yields. The
b
c
reaction was conducted at 0 °C and then at room temperature for 10
h.
donating and electron-withdrawing groups and tri-β-naphthyl-
phosphine (Table 3 entries 1−6 and 9). With R being 4-
halophenyl, the reaction proceeded at 0 °C and then at room
temperature for 10 h to give products 3o,p in moderate yields
(Table 3, entries 3 and 4). When R is a 2-methylphenyl group,
no reaction was observed (Table 3, entry 7). Moreover, the
reaction gave a complex mixture when applying tri-n-
butylphosphine (2i) (Table 3, entry 8).
In order to find out whether different C−P bonds may be
selectively cleaved, the reaction of 1b with alkyldiaryl-
substituted phosphines was also tested. With R′ being n-
butyl, ethyl, or the cyclopropanyl group, the reaction proceeded
smoothly to give the corresponding products 3t−v in good
yields via highly selective cleavage of the phenyl−P bond
(Scheme 3).
unambiguously established by single-crystal X-ray diffraction
analysis (Figure 1), indicating that the product 7m may be
Scheme 3. Highly Selective Hydroxyphosphinylation
Reaction of 1b with Akyldiphenylphosphines 2k−m
Figure 1. ORTEP representation of 7m.
The electronic effect on the selectivity of C−P bond cleavage
in this hydroxyphosphinylation reaction was also studied. The
reaction of phenylbis(4-chlorophenyl)phosphine (2n) with 1b
gave 3w in 56% yield by selective cleavage of the 4-
chlorophenyl−phosphorus bond (Scheme 4). In addition, the
reaction of (4-methoxyphenyl)diphenylphosphine (2o) with 1b
afforded 3x via highly selective phenyl−phosphorus bond
cleavage in 75% yield together with 5% of product 3b, cleaving
the 4-methoxyphenyl−phosphorus bond (Scheme 4).
Mechanistic Study. The reaction of isobutyl ketone 1m in
the presence of 1.5 equiv of triphenylphosphine (2a) in acetone
at 0 °C gave the 1,2-oxaphospholene 7m in 76% yield with high
stereoselectivity (Scheme 5). The structure of this product was
formed from the key intermediate 1,2-oxaphospholene 5m via
the CC bond rearrangement in the presence of a highly
strained CC bond. In addition, we reasoned that the
presence of high strain in the CC bond is also important to
the hydroxyphosphinylation reaction.
Finally, we carried out the reaction of 1a with triphenyl-
phosphine (2a) in the presence of H218O (Scheme 6) and
observed the following. (1) The aryl group cleaved from
triphenylphosphine was transformed to phenol, which was
confirmed by comparison with the standard MS data of phenol,
and the yield was calculated with an interior standard.
Moreover, 3,5-dimethoxyphenol was isolated in 78% yield
when the substrate 1b was treated with tris(3,5-
C
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would afford 1,2-oxaphospholene 7 (path B). When R1 = aryl,
the cycloaddition reaction of resonance form B with O2
produces the five-membered cyclic oxyphosphorane C.
Subsequent intramolecular [1,2]-phenyl group migration
cleaving the O−O linkage affords zwitterion D.13 In this step,
triarylphosphine with electron-withdrawing groups on the
aromatic ring may have a better migratory aptitude than
electron-donating groups due to its stabilization effect on the
positively charged phosphorus center in D, which was
nucleophilically attacked by H218O at the phosphorus atom to
give the intermediate E. Finally, the intermediate E eliminates
the phenol to furnish the final product 3 (path A).
Diverse Transformations of Vinylcyclopropanol. The
vinylcyclopropanol is a common motif in numerous natural
products and valuable intermediates for further elaboration.14
For example, the vinylcyclopropanol 3e was converted to
phosphoryl-substituted 5H-benzo[7]annulen-7(6H)-one 8 in
84% yield via intramolecular radical cyclization15 (Scheme 7).
The structure of 8 was unambiguously established by single-
crystal X-ray diffraction analysis (Figure S2, Supporting
Information). The functionalized (Z)-ene-1,4-dione 9 can be
easily prepared in 80% yield with excellent stereoselectivity via
the Au(I)-catalyzed rearrangement16 of vinylcyclopropanol 3e.
Furthermore, a two-step strategy4 was developed for the
synthesis of the unsymmetrical divinyl ketone 10 in 82% yield
(Scheme 8).
Scheme 6. Mechanistic Study
dimethoxyphenyl)phosphine (2c) (Scheme 6, eq 2); (2)
3a-18O was formed in 71% yield with 76.8% of 18O in the
oxygen atom of the phosphoryl group as identified by MS
analysis. In addition, there is no incorporation of 18O in the
hydroxy group of 3a and phenol.
On the basis of the above observation, we proposed a
plausible mechanism for this reaction (Scheme 7): the reaction
Scheme 7. Plausible Mechanism
CONCLUSION
■
In conclusion, we have observed a unique carbon−phosphorus
bond cleavage in the hydroxyphosphinylation reaction of 3-
cyclopropylideneprop-2-en-1-ones with phosphines, which
provides an efficient entry to highly functionalized 1-
dialkylphosphinyl-3-oxo-(1Z)-alkenyl cyclopropanols with
high stereoselectivity. The product can be easily transformed
to 5H-benzo[7]annulen-7(6H)-one, (Z)-ene-1,4-dione, and
unsymmetrical divinyl ketone. Due to the easy availability of
starting materials and simple and convenient operation, this
reaction facilitates an easy introduction of the phosphorus
functionality to produce cyclopropanols. In addition, a plausible
reaction mechanism was proposed on the basis of a mechanistic
study. Further studies including the scope and synthetic utility
of the method are underway.
starts with an attack of triphenylphosphine at the central allenic
carbon atom to form zwitterion A and the resonance form B.12
B is probably favored due to the release of strain. When R1 =
alkyl, intramolecular nucleophilic attack of the carbonyl oxygen
at the phosphonium atom of intermediate A affords the 1,2-
oxaphospholene 5. Subsequent CC bond rearrangement
EXPERIMENTAL PROCEDURES
■
1
General Methods. Melting points are uncorrected. H, 13C, and
31P NMR spectra were recorded at 400, 100, and 162 MHz,
respectively. The chemical shifts of 31P NMR was taken with reference
Scheme 8. Diverse Transformations of Vinylcyclopropanol 3e
D
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1
to 85% H3PO4 in D2O and those of H and 13C with reference to
(M+, 5.41), 201 (100); TOF HRMS (EI) calcd for C30H24O3PF (M+):
482.1447, found 482.1445.
TMS, the residual protonated DMSO, or CHCl3 in the corresponding
deuterated solvent. Chemical shifts are expressed in ppm, and J values
are given in Hz. Organic solvents used were dried by standard
methods when necessary. THF, toluene, and CH3OH were distilled
from sodium−benzophenone, and DCM and CH3CN were distilled
from CaH2; unless otherwise specified, acetone containing 1.12 mmol
(20 mg) of H2O/5 mL was used. Commercially available reagents
were used without further purification. Petroleum ether refers to the
fraction with a boiling point in the range 60−90 °C. All reactions were
monitored by TLC with GF 254 silica gel coated plates. Flash column
chromatography was carried out using 300−400 mesh silica gel.
Procedure for Synthesis of 3a−x: Typical Procedure for (Z)-
3-(Diphenylphosphoryl)-3-(1-hydroxycyclopropyl)-2-phenyl-
1-p-tolylprop-2-en-1-one (3a). To a stirred solution of 1a (39 mg,
0.150 mmol) in acetone (5 mL with 20 mg of H2O) was added 1.5
equiv of triphenylphosphine (2a) (59 mg) in open air at 0 °C. After it
was stirred for 10 h (monitored by TLC), the resulting mixture was
concentrated under reduced pressure. The residue was subjected to
flash column chromatography (petroleum ether/ethyl acetate 2/1 v/v)
to give the desired product 3a (53 mg, 0.111 mmol, 74%) as a white
solid: mp 186−187 °C (petroleum ether/ethyl acetate); 1H NMR
(400 MHz, DMSO-d6, 80 °C) δ 7.73−7.82 (m, 4H), 7.57 (d, J = 6.8
Hz, 2H), 7.30−7.52 (m, 11H), 7.06 (d, J = 8.0 Hz, 2H), 5.29 (bs, 1H),
2.28 (s, 3H), 0.40−0.49 (m, 2H), 0−0.08 (m, 2H); 13C NMR (100
(Z)-1-(4-Bromophenyl)-3-(diphenylphosphoryl)-3-(1-hydroxycy-
clopropyl)-2-phenylprop-2-en-1-one (3d). The reaction of 1d (49
mg, 0.151 mmol) and triphenylphosphine (2a; 59 mg, 1.5 equiv) at 0
°C afforded 3d (74 mg, 0.136 mmol, 90%) as a white solid (eluent:
petroleum ether/ethyl acetate 2/1): mp 188−189 °C (petroleum
ether/ethyl acetate); 1H NMR (400 MHz, DMSO-d6, 80 °C) δ 7.71−
7.85 (m, 4H), 7.30−7.65 (m, 15H), 5.28 (s, 1H), 0.36−0.50 (m, 2H),
−0.01 to 0.11 (m, 2H); 13C NMR (100 MHz, DMSO-d6, 80 °C) δ
193.0 (d, 3JC−P = 5.9 Hz), 155.3 (d, 2JC−P = 10.5 Hz), 135.5 (d, 1JC−P
=
3
1
91.2 Hz), 134.8 (d, JC−P = 17.1 Hz), 134.7, 132.2 (d, JC−P = 101.6
2
Hz), 131.9 (d, JC−P = 10.6 Hz), 131.4, 130.7, 130.6, 128.6, 128.3,
3
2
128.0, 127.8, 127.6 (d, JC−P = 12.7 Hz), 52.6 (d, JC−P = 11.8 Hz),
15.8 (d, JC−P = 5.1 Hz); 31P NMR (162 MHz, DMSO-d6, 25 °C) δ
3
29.13; IR (neat) 3260, 1659, 1580, 1486, 1257, 1235, 1181, 1115, 878,
745, 725, 693 cm−1; MS (70 eV, EI) m/z (%) 542 (M(79Br)+, 4.32),
544 (M(81Br)+, 7.08), 201 (100); TOF HRMS (EI) calcd for
C30H24O3P79Br (M+): 542.0646, found 542.0639.
(Z)-3-(Diphenylphosphoryl)-3-(1-hydroxycyclopropyl)-1-(4-me-
thoxyphenyl)-2-phenylprop-2-en-1-one (3e). The reaction of 1e (41
mg, 0.149 mmol) and triphenylphosphine (2a; 59 mg, 1.5 equiv) at 0
°C afforded 3e (54 mg, 0.109 mmol, 73%) as a white solid (eluent:
petroleum ether/ethyl acetate 2/1): mp 205−206 °C (petroleum
ether/ethyl acetate); 1H NMR (400 MHz, DMSO-d6, 80 °C) δ 7.71−
7.82 (m, 4H), 7.57 (d, J = 7.6 Hz, 2H), 7.29−7.54 (m, 11H), 6.76 (d, J
= 8.8 Hz, 2H), 5.35 (s, 1H), 3.77 (s, 3H), 0.40−0.50 (m, 2H), 0.01−
0.06 (m, 2H); 13C NMR (100 MHz, DMSO-d6, 80 °C) δ 192.4 (d,
MHz, DMSO-d6, 80 °C) δ 193.5 (d, 3JC−P = 6.2 Hz), 155.8 (d, 2JC−P
=
3
1
11.3 Hz), 142.7, 135.4 (d, JC−P = 15.0 Hz), 134.8 (d, JC−P = 91.9
1
2
Hz), 133.1, 132.3 (d, JC−P = 100.9 Hz), 131.9 (d, JC−P = 9.2 Hz),
4
131.3 (d, JC−P = 2.3 Hz), 129.0, 128.4, 128.3, 128.0, 127.8, 127.5 (d,
2
3
3JC−P = 6.1 Hz), 162.6, 155.7 (d, JC−P = 10.9 Hz), 135.5 (d, JC−P
=
3JC−P = 11.9 Hz), 52.8 (d, JC−P = 10.2 Hz), 20.6, 15.8 (d, JC−P = 5.3
2
3
1
1
14.8 Hz), 134.6 (d, JC−P = 92.9 Hz), 132.2 (d, JC−P = 100.5 Hz),
131.9 (d, JC−P = 10.3 Hz), 131.33 (d, JC−P = 2.9 Hz), 131.26, 128.6,
Hz); 31P NMR (162 MHz, DMSO-d6, 25 °C) δ 29.32; IR (neat) 3268,
1653, 1598, 1437, 1260, 1177, 1115, 746, 724, 692 cm−1; MS (70 eV,
EI) m/z (%) 478 (M+, 13.91), 201 (100); TOF HRMS (EI) calcd for
C31H27O3P (M+) 478.1698, found 478.1702.
2
4
3
128.5, 128.2, 128.7, 127.5 (d, JC−P = 11.3 Hz), 112.9, 55.1, 53.1 (d,
2JC−P = 10.8 Hz), 15.8 (d, JC−P = 5.1 Hz); 31P NMR (162 MHz,
3
DMSO-d6, 25 °C) δ 29.87; IR (neat) 3247, 1647, 1595, 1568, 1438,
1254, 1173, 1115, 1027, 832, 747, 694 cm−1; MS (70 eV, EI) m/z (%)
494 (M+, 6.98), 135 (100), 201 (92.61); TOF HRMS (EI) calcd for
C31H27O4P (M+) 494.1647, found 494.1639.
The following compounds were prepared according to this
procedure.
(Z)-3-(Diphenylphosphoryl)-3-(1-hydroxycyclopropyl)-1,2-diphe-
nylprop-2-en-1-one (3b). The reaction of 1b (37 mg, 0.150 mmol)
and triphenylphosphine (2a; 59 mg, 1.5 equiv) at 0 °C afforded 3b (48
mg, 0.103 mmol, 69%) as a white solid (eluent: petroleum ether/ethyl
(Z)-3-(Diphenylphosphoryl)-1-(furan-2-yl)-3-(1-hydroxycyclo-
propyl)-2-phenylprop-2-en-1-one (3f). The reaction of 1f (35 mg,
0.148 mmol) and triphenylphosphine (2a; 59 mg, 1.5 equiv) at 0 °C
afforded 3f (38 mg, 0.084 mmol, 56%) as a white solid (eluent:
petroleum ether/ethyl acetate 2/1): mp 197−198 °C (petroleum
ether/ethyl acetate); 1H NMR (400 MHz, DMSO-d6, 80 °C) δ 7.70−
7.83 (m, 4H), 7.31−7.69 (m, 12H), 6.72 (s, 1H), 6.40 (s, 1H), 5.39 (s,
1H), 0.39−0.49 (m, 2H), −0.04 to 0.06 (m, 2H); 13C NMR (100
1
acetate 2/1): mp 185−186 °C (petroleum ether/ethyl acetate); H
NMR (400 MHz, DMSO-d6, 80 °C) δ 7.71−7.82 (m, 4H), 7.54−7.64
(m, 4H), 7.31−7.52 (m, 10H), 7.27 (t, J = 7.6 Hz, 2H), 5.28 (s, 1H),
0.40−0.48 (m, 2H), 0.01−0.09 (m, 2H); 13C NMR (100 MHz,
DMSO-d6, 80 °C): δ 193.9 (d, 3JC−P = 6.3 Hz), 155.7 (d, 2JC−P = 10.9
3
1
Hz), 135.5, 135.2 (d, JC−P = 14.4 Hz), 135.0 (d, JC−P = 93.1 Hz),
MHz, DMSO-d6, 80 °C) δ 181.6 (d, 3JC−P = 6.3 Hz), 153.9 (d, 2JC−P
11.7 Hz), 151.4, 146.7, 135.8 (d, JC−P = 91.9 Hz), 135.2 (d, JC−P
=
=
132.24 (d, 1JC−P = 100.7 Hz), 132.19, 132.0 (d, 2JC−P = 9.2 Hz), 131.3
1
3
4
3
(d, JC−P = 2.5 Hz), 128.9, 128.5, 128.3, 127.9, 127.6 (d, JC−P = 12.5
1
2
Hz), 127.4, 52.8 (d, JC−P = 11.5 Hz), 15.8 (d, JC−P = 5.5 Hz); 31P
NMR (162 MHz, DMSO-d6, 25 °C) δ 29.37; IR (neat) 3412, 1653,
1597, 1435, 1264, 1227, 1158, 1114, 722, 690 cm−1; MS (70 eV, EI)
m/z (%) 464 (M+, 7.05), 201 (100); TOF HRMS (EI) calcd for
C30H25O3P (M+) 464.1541, found 464.1544.
2
3
14.4 Hz), 132.1 (d, JC−P = 100.9 Hz), 131.8 (d, JC−P = 10.0 Hz),
4
2
131.4 (d, JC−P = 2.4 Hz), 128.6, 128.4, 127.8, 127.5 (d, JC−P = 12.0
2
3
Hz), 118.9, 111.8, 53.2 (d, JC−P = 9.5 Hz), 15.8 (d, JC−P = 5.1 Hz);
31P NMR (162 MHz, DMSO-d6, 25 °C) δ 30.52; IR (neat) 3418,
1638, 1561, 1486, 1456, 1228, 1156, 1116, 773, 698 cm−1; MS (70 eV,
EI) m/z (%) 454 (M+, 13.12), 201 (100); TOF HRMS (EI) calcd for
C28H23O4P (M+) 454.1334, found 454.1341.
(Z)-3-(Diphenylphosphoryl)-1-(4-fluorophenyl)-3-(1-hydroxycy-
clopropyl)-2-phenylprop-2-en-1-one (3c). The reaction of 1c (40 mg,
0.152 mmol) and triphenylphosphine (2a; 59 mg, 1.5 equiv) at 0 °C
afforded 3c (63 mg, 0.131 mmol, 87%) as a white solid (eluent:
petroleum ether/ethyl acetate 2/1): mp 184−185 °C (petroleum
ether/ethyl acetate); 1H NMR (400 MHz, DMSO-d6, 80 °C) δ 7.72−
7.83 (m, 4H), 7.63−7.76 (m, 2H), 7.58 (d, J = 7.2 Hz, 2H), 7.30−7.54
(m, 9H), 7.06 (t, J = 8.8 Hz, 2H), 5.32 (s, 1H), 0.40−0.49 (m, 2H),
0.01−0.10 (m, 2H); 13C NMR (100 MHz, DMSO-d6, 80 °C) δ 192.5
(d, 3JC−P = 6.4 Hz), 164.3 (d, 1JC−F = 250.5 Hz), 155.3 (d, 2JC−P = 11.0
Hz), 135.3 (d, 1JC−P = 91.6 Hz), 135.0 (d, 3JC−P = 14.4 Hz), 132.3 (d,
(Z)-3-(Diphenylphosphoryl)-3-(1-hydroxycyclopropyl)-2-phenyl-
1-(thien-2-yl)prop-2-en-1-one (3g). The reaction of 1g (38 mg, 0.151
mmol) and triphenylphosphine (2a; 59 mg, 1.5 equiv) at 0 °C
afforded 3g (31 mg, 0.066 mmol, 43%) as white solid (eluent:
petroleum ether/ethyl acetate 2/1): mp 199−200 °C (petroleum
ether/ethyl acetate); 1H NMR (400 MHz, DMSO-d6, 80 °C) δ 7.70−
7.84 (m, 5H), 7.59 (d, J = 5.2 Hz, 2H), 7.34−7.54 (m, 9H), 7.25 (s,
1H), 6.92 (s, 1H), 5.42 (s, 1H), 0.40−0.50 (m, 2H), −0.04 to 0.08 (m,
2H); 13C NMR (100 MHz, DMSO-d6, 80 °C) δ 186.4 (d, 3JC−P = 6.2
1
2
4JC−F = 2.1 Hz), 132.2 (d, JC−P = 102.1 Hz), 132.0 (d, JC−P = 10.1
Hz), 131.7 (d, 3JC−F = 9.1 Hz), 131.4 (d, 4JC−P = 2.2 Hz), 128.6, 128.3,
128.0, 127.6 (d, 3JC−P = 12.5 Hz), 114.6 (d, 2JC−F = 22.0 Hz), 52.8 (d,
2
3
Hz), 154.5 (d, JC−P = 11.0 Hz), 142.9, 135.57 (d, JC−P = 14.8 Hz),
135.56 (d, 1JC−P = 90.5 Hz), 134.3, 134.2, 132.0 (d, 1JC−P = 101.3 Hz),
131.9 (d, 2JC−P = 9.7 Hz), 131.4, 128.7, 128.4, 127.9, 127.4 (d, 3JC−P
12.0 Hz), 127.3, 53.2 (d, 2JC−P = 9.7 Hz), 15.9 (d, 3JC−P = 5.2 Hz); 31
=
P
2JC−P = 10.5 Hz), 15.8 (d, JC−P = 5.6 Hz); 31P NMR (162 MHz,
3
NMR (162 MHz, DMSO-d6, 25 °C) δ 30.09; IR (neat) 3409, 1627,
DMSO-d6, 25 °C) δ 29.40; IR (neat) 3373, 1662, 1595, 1438, 1263,
1228, 1157, 1118, 827, 727, 695 cm−1; MS (70 eV, EI) m/z (%) 482
1435, 1275, 1227, 1156, 1115, 835, 724, 693 cm−1; MS (70 eV, EI) m/
E
dx.doi.org/10.1021/jo400610q | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Article
3
3
z (%) 470 (M+, 5.50), 201 (100); TOF HRMS (EI) calcd for
C28H23O3PS (M+) 470.1106, found 470.1103.
131.4, 130.7 (d, JC−F = 8.1 Hz), 128.9, 127.6 (d, JC−P = 12.9 Hz),
2
2
127.5, 114.9(d, JC−F = 22.2 Hz), 52.7 (d, JC−P = 10.1 Hz), 15.8 (d,
3JC−P = 4.4 Hz); 31P NMR (162 MHz, DMSO-d6, 25 °C) δ 29.18; IR
(Z)-1-(4-Chlorophenyl)-3-(diphenylphosphoryl)-3-(1-hydroxycy-
clopropyl)-2-(2-methoxyphenyl)prop-2-en-1-one (3h). The reaction
of 1h (47 mg, 0.152 mmol) and triphenylphosphine (2a; 59 mg, 1.5
equiv) at 0 °C afforded 3h (45 mg, 0.085 mmol, 57%) as a white solid
(eluent: petroleum ether/ethyl acetate 2/1): mp 167−168 °C
(neat) 3203, 1735, 1660, 1594, 1504, 1437, 1229, 1179, 1110, 732, 686
cm−1; MS (70 eV, EI) m/z (%) 482 (M+, 4.30), 201 (100); TOF
HRMS (EI) calcd for C30H24O3PF (M+) 482.1447, found 482.1448.
(Z)-3-(Diphenylphosphoryl)-3-(1-hydroxycyclopropyl)-2-(naph-
thalen-2-yl)-1-phenylprop-2-en-1-one (2l). The reaction of 1l (44
mg, 0.149 mmol) and triphenylphosphine (2a; 59 mg, 1.5 equiv) at 0
°C afforded 3l (61 mg, 0.119 mmol, 79%) as a white solid (eluent:
petroleum ether/ethyl acetate 2/1): mp 127−128 °C (petroleum
1
(petroleum ether/ethyl acetate); H NMR (400 MHz, DMSO-d6, 80
°C) δ 7.75−7.85 (m, 4H), 7.66 (d, J = 7.2 Hz, 1H), 7.53 (d, J = 8.4
Hz, 2H), 7.38−7.49 (m, 6H), 7.33 (t, J = 8.4 Hz, 1H), 7.27 (d, J = 8.4
Hz, 2H), 7.02 (t, J = 7.6 Hz, 1H), 6.96 (d, J = 8.0 Hz, 1H), 5.26 (s,
1H), 3.64 (s, 3H), 0.40−0.47 (m, 2H), 0.10−0.18 (m, 2H); 13C NMR
1
ether/ethyl acetate); H NMR (400 MHz, DMSO-d6, 80 °C) δ 8.03
3
(100 MHz, DMSO-d6, 80 °C) δ 192.5 (d, JC−P = 5.6 Hz), 155.9,
(s, 1H), 7.75−7.95 (m, 8H), 7.65 (d, J = 8.0 Hz, 2H), 7.33−7.55 (m,
9H), 7.25 (t, J = 7.2 Hz, 2H), 5.38 (s, 1H), 0.40−0.47 (m, 2H), 0.03−
0.10 (m, 2H); 13C NMR (100 MHz, DMSO-d6, 80 °C) δ 193.8 (d,
2
1
151.4 (d, JC−P = 10.7 Hz), 139.0 (d, JC2−P = 90.7 Hz), 136.9, 134.6,
1
132.3 (d, JC−P = 101.4 Hz), 132.0 (d, JC−P = 10.0 Hz), 131.2 (d,
4JC−P = 2.5 Hz), 130.9, 130.5, 130.2, 127.5 (d, 3JC−P = 12.4 Hz), 127.2,
3JC−P = 5.6 Hz), 155.7 (d, JC−P = 10.9 Hz), 135.5, 135.4 (d, JC−P
=
2
1
3
2
91.3 Hz), 132.7 (d, 3JC−P = 14.8 Hz), 132.4, 132.20, 132.18 (d, 1JC−P
=
124.9 (d, JC−P = 14.3 Hz), 120.3, 111.8, 55.4, 54.0 (d, JC−P = 10.1
Hz), 15.3 (d, 3JC−P = 5.7 Hz); 31P NMR (162 MHz, DMSO-d6, 25 °C)
δ 32.66; IR (neat) 3316, 1670, 1587, 1482, 1435, 1256, 1230, 1149,
1116, 1094, 1004, 829, 766, 725, 693 cm−1; MS (70 eV, EI) m/z (%)
528 (M(35Cl)+, 7.99), 530 (M(37Cl)+, 3.80), 201 (100); TOF HRMS
(EI) calcd for C31H26O4P35Cl (M+) 528.1257, found 528.1254.
(Z)-3-(Diphenylphosphoryl)-3-(1-hydroxycyclopropyl)-1-phenyl-
2-m-tolylprop-2-en-1-one (3i). The reaction of 1i (39 mg, 0.150
mmol) and triphenylphosphine (2a; 59 mg, 1.5 equiv) at 0 °C
afforded 3i (52 mg, 0.109 mmol, 72%) as white solid (eluent:
petroleum ether/ethyl acetate 2/1): mp 161−162 °C (petroleum
ether/ethyl acetate); 1H NMR (400 MHz, DMSO-d6, 80 °C) δ 7.70−
7.84 (m, 4H), 7.61 (d, J = 8.0 Hz, 2H), 7.33−7.51 (m, 9H), 7.21−7.31
(m, 3H), 7.15 (d, J = 7.6 Hz, 1H), 5.28 (s, 1H), 2.29 (s, 3H), 0.41−
0.49 (m, 2H), 0.01−0.10 (m, 2H); 13C NMR (100 MHz, DMSO-d6,
80 °C) δ 193.9 (d, 3JC−P = 5.9 Hz), 155.8 (d, 2JC−P = 10.6 Hz), 137.2,
2
4
100.5 Hz), 132.1, 132.0 (d, JC−P = 10.5 Hz), 131.4 (d, JC−P = 2.0
3
Hz), 128.9, 128.0, 127.6 (d, JC−P = 12.5 Hz), 127.4, 127.1, 126.6,
126.2, 126.1, 52.9 (d, JC−P = 11.0 Hz), 15.8 (d, JC−P = 5.5 Hz); 31P
NMR (162 MHz, DMSO-d6, 25 °C) δ 29.48; IR (neat) 3299, 1658,
1591, 1437, 1245, 1172, 1117, 1100, 1001, 731, 684 cm−1; MS (70 eV,
EI) m/z (%) 514 (M+, 3.97), 201 (100); TOF HRMS (EI) calcd for
C34H27O3P (M+) 514.1698, found 514.1695.
2
3
(Z)-3-(Bis(4-methoxyphenyl)phosphoryl)-3-(1-hydroxycycloprop-
yl)-1,2-diphenylprop-2-en-1-one (3m). The reaction of 1b (37 mg,
0.150 mmol) and tris(4-methoxyphenyl)phosphine (2b; 79 mg, 1.5
equiv) at 0 °C afforded 3m (63 mg, 0.120 mmol, 80%) as a white solid
(eluent: petroleum ether/ethyl acetate 1/1): mp 194−195 °C
1
(petroleum ether/ethyl acetate); H NMR (400 MHz, DMSO-d6, 80
°C) δ 7.58−7.70 (m, 4H), 7.50−7.57 (m, 4H), 7.30−7.44 (m, 4H),
7.25 (t, J = 7.4 Hz, 2H), 6.92 (d, J = 6.8 Hz, 4H), 5.41 (s, 1H), 3.77 (s,
6H), 0.45−0.51 (m, 2H), −0.02 to 0.06 (m, 2H); 13C NMR (100
3
1
135.5, 135.1 (d, JC−P = 14.8 Hz), 134.8 (d, JC−P = 92.2 Hz), 132.23
1
2
MHz, DMSO-d6, 80 °C) δ 194.1 (d, 3JC−P = 6.0 Hz), 161.8 (d, 4JC−P
=
(d, JC−P = 100.5 Hz), 132.15, 131.9 (d, JC−P = 10.1 Hz), 131.3 (d,
4JC−P = 2.4 Hz), 129.2, 128.9, 128.6, 127.7, 127.5 (d, 3JC−P = 11.7 Hz),
127.4, 125.5, 52.8 (d, 2JC−P = 10.3 Hz), 20.5, 15.8 (d, 3JC−P = 5.5 Hz);
31P NMR (162 MHz, DMSO-d6, 25 °C) δ 32.66; IR (neat) 3365,
2.8 Hz), 154.4 (d, 2JC−P = 10.8 Hz), 136.1 (d, 1JC−P = 92.7 Hz), 135.2
3
2
(d, JC−P = 14.9 Hz), 135.0, 133.9 (d, JC−P = 10.9 Hz), 132.2, 129.0,
128.5, 128.3, 127.9, 127.3, 123.1 (d, 1JC−P = 107.2 Hz), 113.4 (d, 3JC−P
2
3
1662, 1595, 1439, 1262, 1228, 1157, 1117, 928, 729, 691 cm−1; MS
(70 eV, EI) m/z (%) 478 (M+, 4.89), 201 (100); TOF HRMS (EI)
calcd for C31H27O3P (M+) 478.1698, found 478.1704.
= 12.7 Hz), 54.9, 53.3 (d, JC−P = 10.3 Hz), 15.5 (d, JC−P = 5.5 Hz);
31P NMR (162 MHz, DMSO-d6, 25 °C) δ 29.85; IR (neat) 3276,
1655, 1595, 1569, 1501, 1294, 1256, 1096, 1022, 825, 800, 704, 672
cm−1; MS (70 eV, EI) m/z (%) 524 (M+, 4.18), 261 (100); TOF
HRMS (EI) calcd for C32H29O5P (M+) 524.1753, found 524.1757.
(Z)-3-(Bis(3,5-dimethoxyphenyl)phosphoryl)-3-(1-hydroxycyclo-
propyl)-1,2-diphenylprop-2-en-1-one (3n). The reaction of 1b (37
mg, 0.15 mmol) and tris(3,5-dimethoxyphenyl)phosphine (2c; 99 mg,
1.5 equiv) at 0 °C afforded 3,5-dimethoxyphenol (18 mg, 0.117 mmol,
78%) as an yellow oil (eluent: petroleum ether/ethyl acetate 6/1) and
3n (68 mg, 0.116 mmol, 78%) as a white solid (eluent: petroleum
ether/ethyl acetate 1/2): mp 157−158 °C (petroleum ether/ethyl
(Z)-3-(Diphenylphosphoryl)-3-(1-hydroxycyclopropyl)-2-(4-me-
thoxyphenyl)-1-phenylprop-2-en-1-one (3j). The reaction of 1j (41
mg, 0.149 mmol) and triphenylphosphine (2a; 59 mg, 1.5 equiv) at 0
°C afforded 3j (67 mg, 0.136 mmol, 90%) as white solid (eluent:
petroleum ether/ethyl acetate 2/1): mp 180−181 °C (petroleum
ether/ethyl acetate); 1H NMR (400 MHz, DMSO-d6, 80 °C) δ 7.70−
7.80 (m, 4H), 7.57 (d, J = 7.2 Hz, 2H), 7.35−7.54 (m, 9H), 7.2−7.30
(m, 2H), 6.93 (d, J = 8.0 Hz, 2H), 5.29 (s, 1H), 3.75 (s, 3H), 0.45−
0.55 (m, 2H), 0.04−0.12 (m, 2H); 13C NMR (100 MHz, DMSO-d6,
80 °C) δ 194.0 (d, 3JC−P = 6.2 Hz), 159.7, 155.4 (d, 2JC−P = 12.3 Hz),
1
acetate); H NMR (400 MHz, DMSO-d6, 80 °C) δ 7.50−7.65 (m,
1
135.6, 133.7 (d, 1JC−P = 93.0 Hz), 132.3 (d, JC−P = 100.3 Hz), 132.1,
4H), 7.18−7.45 (m, 6H), 6.85−7.02 (m, 4H), 6.54 (s, 2H), 5.45 (s,
1H), 3.75 (s, 12H), 0.40−0.60 (m, 2H), −0.03 to 0.16 (m, 2H); 13C
NMR (100 MHz, DMSO-d6, 80 °C) δ 193.8 (d, 3JC−P = 4.9 Hz), 159.9
(d, 3JC−P = 17.7 Hz), 155.3 (d, 2JC−P = 12.1 Hz), 135.2 (d, 3JC−P = 15.2
2
4
131.9 (d, JC−P = 11.1 Hz), 131.3 (d, JC−P = 1.8 Hz), 130.0, 128.9,
3
3
127.5 (d, JC−P = 12.5 Hz), 127.4, 127.2 (d, JC−P = 15.3 Hz), 113.6,
54.8, 52.9 (d, JC−P = 11.4 Hz), 16.0 (d, JC−P = 5.4 Hz); 31P NMR
(162 MHz, DMSO-d6, 25 °C) δ 29.64; IR (neat) 3432, 1661, 1596,
1510, 1438, 1256, 1226, 1159, 1118, 1024, 825, 741, 687 cm−1; MS
(70 eV, EI) m/z (%) 494 (M+, 6.14), 201 (100); TOF HRMS (EI)
calcd for C31H27O4P (M+) 494.1647, found 494.1650.
2
3
1
1
Hz), 134.9, 134.8 (d, JC−P = 92.9 Hz), 133.5 (d, JC−P = 99.9 Hz),
2
132.3, 128.8, 128.6, 128.3, 127.9, 127.3, 110.2 (d, JC−P = 11.5 Hz),
103.6, 55.1, 53.1 (d, JC−P = 10.8 Hz), 15.7 (d, JC−P = 5.3 Hz); 31P
NMR (162 MHz, DMSO-d6, 25 °C) δ 29.65; IR (neat) 1652, 1589,
1451, 1418, 1290, 1205, 1158, 1064, 874, 708, 629 cm−1; MS (70 eV,
EI) m/z (%) 584 (M+, 6.49), 321 (100); TOF HRMS (EI) calcd for
C34H33O7P (M+) 584.1964, found 584.1962.
2
3
(Z)-3-(Diphenylphosphoryl)-2-(4-fluorophenyl)-3-(1-hydroxycy-
clopropyl)-1-phenylprop-2-en-1-one (3k). The reaction of 1k (40
mg, 0.152 mmol) and triphenylphosphine (2a; 59 mg, 1.5 equiv) at 0
°C afforded 3k (68 mg, 0.141 mmol, 94%) as a white solid (eluent:
petroleum ether/ethyl acetate 2/1): mp 195−196 °C (petroleum
ether/ethyl acetate); 1H NMR (400 MHz, DMSO-d6, 80 °C) δ 7.71−
7.83 (m, 4H), 7.56−7.67 (m, 4H), 7.36−7.54 (m, 7H), 7.24−7.33 (m,
2H), 7.18 (t, J = 8.6 Hz, 2H), 5.30 (s, 1H), 0.40−0.55 (m, 2H), 0.02−
0.13 (m, 2H); 13C NMR (100 MHz, DMSO-d6, 80 °C) δ 193.8 (d,
3,5-Dimethoxyphenol:17 1H NMR (400 MHz, CDCl3) δ 6.06−6.09
(m, 1H), 6.03 (d, J = 2.4 Hz, 2H), 5.51 (s, 1H), 3.74 (s, 6H); 13C
NMR (100 MHz, CDCl3) δ 161.6, 157.4, 94.3, 93.1, 55.3; IR (neat)
3387, 1597, 1550, 1459, 1342, 1195, 1143, 1057, 820, 680 cm−1; MS
(70 eV, EI) m/z (%) 154 (M+, 100), 125 (81.22).
(Z)-3-(Bis(4-fluorophenyl)phosphoryl)-3-(1-hydroxycyclopropyl)-
1,2-diphenylprop-2-en-1-one (3o). The reaction of 1b (37 mg, 0.150
mmol) and tris(4-fluorophenyl)phosphine (2d; 71 mg, 1.5 equiv) at 0
°C and then room temperature for 10 h afforded 3o (38 mg, 0.076
1
2
3JC−P = 4.9 Hz), 162.1 (d, JC−F = 250.5 Hz), 154.8 (d, JC−P = 11.8
1
1
Hz), 135.43, 135.37 (d, JC−P = 91.6 Hz), 132.3, 132.18 (d, JC−P
102.0 Hz), 131.9 (d, JC−P = 10.5 Hz), 131.5 (d, JC−F = 3.3 Hz),
=
2
4
F
dx.doi.org/10.1021/jo400610q | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Article
mmol, 50%) as a white solid (eluent: petroleum ether/ethyl acetate 2/
mmol) and tris(2-naphthylphenyl)phosphine (2j; 93 mg, 1.5 equiv) at
0 °C afforded 3s (63 mg, 0.112 mmol, 74%) as a white solid (eluent:
petroleum ether/ethyl acetate 2/1): mp 175−176 °C (petroleum
1
1): mp 200−201 °C (petroleum ether/ethyl acetate); H NMR (400
MHz, DMSO-d6, 80 °C) δ 7.72−7.89 (m, 4H), 7.51−7.65 (m, 4H),
7.10−7.50 (m, 10H), 5.39 (s, 1H), 0.40−0.52 (m, 2H), −0.02 to 0.13
1
ether/ethyl acetate); H NMR (400 MHz, DMSO-d6, 80 °C) δ 8.41
(m, 2H); 13C NMR (100 MHz, DMSO-d6, 80 °C) δ 194.0 (d, 3JC−P
=
(d, J = 12.8 Hz, 2H), 7.80−8.02 (m, 8H), 7.41−7.71 (m, 8H), 7.30−
7.46 (m, 3H), 7.16 (s, 1H), 7.04 (s, 2H), 5.48 (s, 1H), 0.40−0.59 (m,
2H), 0.05−0.21 (m, 2H); 13C NMR (100 MHz, DMSO-d6, 80 °C) δ
5.7 Hz), 164.0 (dd, 4JC−P = 2.6 Hz, 1JC−F = 249.8 Hz,), 155.9 (d, 2JC−P
1
2
= 11.6 Hz), 135.3, 135.1, 134.8 (d, JC−P = 89.7 Hz), 114.9 (dd, JC−P
3
3
2
= 11.6 Hz, JC−F = 8.7 Hz), 132.4, 128.9, 128.7, 127.9, 127.5, 134.9
194.0 (d, JC−P = 5.6 Hz), 155.8 (d, JC−P = 11.9 Hz), 135.221 (d,
(dd, 3JC−P = 13.5 Hz, 2JC−F = 21.3 Hz), 52.8 (d, 2JC−P = 11.9 Hz), 15.9
(d, 3JC−P = 5.2 Hz); 31P NMR (162 MHz, DMSO-d6, 25 °C) δ 24.31;
IR (neat) 3412, 1656, 1579, 1482, 1389, 1259, 1227, 1160, 1087, 821,
755, 705 cm−1; MS (70 eV, EI) m/z (%) 500 (M+, 4.70), 237 (100);
TOF HRMS (EI) calcd for C30H23O3F2P (M+) 500.1353, found
500.1354.
3JC−P = 14.2 Hz), 135.217 (d, JC−P = 93.0 Hz), (135.0, 134.0, 133.9,
overlap), 133.9, 132.0, 131.5 (d, JC−P = 12.6 Hz), 129.6 (d, JC−P
1
2
1
=
3
3
100.2 Hz), 128.6, 128.4 (d, JC−P = 15.8 Hz), 127.9 (d, JC−P = 14.1
Hz), (127.2, 127.2, 127.1, 127.1, overlap), 126.3, 53.1 (d, 2JC−P = 11.2
Hz), 15.9 (d, 3JC−P = 4.6 Hz); 31P NMR (162 MHz, DMSO-d6, 25 °C)
δ 29.83; IR (neat) 3056, 1658, 1592, 1448, 1260, 1227, 1155, 1088,
858, 819, 747, 705, 659 cm−1; MS (70 eV, EI) m/z (%) 564 (M+,
12.66), 301 (100); TOF HRMS (EI) calcd for C38H29O3P (M+)
564.1854, found 564.1857.
(Z)-3-(Bis(4-chlorophenyl)phosphoryl)-3-(1-hydroxycyclopropyl)-
1,2-diphenylprop-2-en-1-one (3p). The reaction of 1b (37 mg, 0.150
mmol) abs tris(4-chlorophenyl)phosphine (2e; 82 mg, 1.5 equiv) at 0
°C 10 h and then room temperature for 10 h afforded 3p (38 mg,
0.071 mmol, 48%) as a white solid (eluent: chloroform/ethyl acetate
8/1): mp 185−186 °C (petroleum ether/ethyl acetate); 1H NMR
(400 MHz, DMSO-d6, 80 °C) δ 7.68−7.81 (m, 4H), 7.53−7.64 (m,
4H), 7.42−7.51 (m, 5H), 7.34−7.41 (m, 5H), 5.40 (s, 1H), 0.42−0.50
(m, 2H), 0.04−0.12 (m, 2H); 13C NMR (100 MHz, DMSO-d6, 80
°C) δ 193.9 (d, 3JC−P = 6.1 Hz), 156.3 (d, 2JC−P = 11.5 Hz), 137.0 (d,
(Z)-3-(Butyl(phenyl)phosphoryl)-3-(1-hydroxycyclopropyl)-1,2-di-
phenylprop-2-en-1-one (3t). The reaction of 1b (37 mg, 0.150 mmol)
and n-butyldiphenylphosphine (2k; 54 mg, 1.5 equiv) at 0 °C afforded
3t (49 mg, 0.110 mmol, 73%) as a white solid (eluent: petroleum
ether/ethyl acetate 2/1): mp 85−86 °C (petroleum ether/ethyl
1
acetate); H NMR (400 MHz, DMSO-d6, 80 °C) δ 7.70−7.90 (m,
4H), 7.20−7.60 (m, 11H), 5.49 (s, 1H), 2.25−2.47 (m, 2H), 1.65 (m,
1H), 1.30−1.54 (m, 3H), 0.75−1.00 (m, 3H), 0.35−0.60 (m, 2H),
−0.10 to 0.10 (m, 1H), −0.30 to −0.16 (m, 1H); 13C NMR (100
3
1
4JC−P = 2.5 Hz), 135.2, 134.9 (d, JC−P = 15.7 Hz), 134.5 (d, JC−P
=
2
1
92.3 Hz), 133.8 (d, JC−P = 11.8 Hz), 132.4, 130.9 (d, JC−P = 102.9
MHz, DMSO-d6, 80 °C) δ 194.0 (d, 3JC−P = 5.7 Hz), 155.1 (d, 2JC−P
=
Hz), 128.9, 128.7, 128.3, 128.0, 127.9 (d, 3JC−P = 13.0 Hz), 127.5, 52.7
9.0 Hz), 136.6, 135.5 (d, 3JC−P = 14.3 Hz), 135.4 (d, 1JC−P = 83.7 Hz),
(d, JC−P = 10.1 Hz), 15.9 (d, JC−P = 5.6 Hz); 31P NMR (162 MHz,
DMSO-d6, 25 °C) δ 29.67; IR (neat) 3412, 1656, 1579, 1482, 1389,
1259, 1227, 1160, 1087, 821, 755, 705 cm−1; MS (70 eV, EI) m/z (%)
2
3
1
2
134.3 (d, JC−P = 92.8 Hz), 131.8, 130.84, 130.8 (d, JC−P = 8.8 Hz),
3
128.6, 128.3, 128.2, 127.8, 127.7 (d, JC−P = 11.3 Hz), 127.6, 51.8 (d,
2JC−P = 10.8 Hz), 27.8 (d, 1JC−P = 69.2 Hz), 22.9 (d, 2JC−P = 15.8 Hz),
532 (M(35,35Cl) +, 3.34), 534 (M(35,37Cl) , 2.53), 536 (M(37,37Cl)+,
+
0.79), 105 (100); TOF HRMS (EI) calcd for C30H23O3P35Cl2 (M+)
532.0762, found 532.0765.
22.8 (d, 3JC−P = 4.4 Hz), 15.9 (d, 3JC−P = 7.5 Hz), 15.8 (d, 3JC−P = 2.8
Hz), 13.0; 31P NMR (162 MHz, DMSO-d6, 25 °C) δ 33.57; IR (neat)
3210, 1666, 1594, 1489, 1255, 1224, 1153, 1110, 876, 747, 695, 648
cm−1; MS (70 eV, EI) m/z (%) 444 (M+, 3.51), 181 (36.81), 105
(100); TOF HRMS (EI) calcd for C28H29O3P (M+) 444.1854, found
444.1843.
(Z)-3-(Di-p-tolylphosphoryl)-3-(1-hydroxycyclopropyl)-1,2-diphe-
nylprop-2-en-1-one (3q). The reaction of 1b (37 mg, 0.150 mmol)
and tris(4-methylphenyl)phosphine (2f; 68 mg, 1.5 equiv) at 0 °C
afforded 3q (47 mg, 0.096 mmol, 64%) as a white solid (eluent:
petroleum ether/ethyl acetate 2/1): mp 181−182 °C (petroleum
ether/ethyl acetate); 1H NMR (400 MHz, DMSO-d6, 80 °C) δ 7.47−
7.70 (m, 8H), 7.29−7.45 (m, 4H), 7.10−7.29 (m, 6H), 5.35 (s, 1H),
2.28 (s, 6H), 0.40−0.54 (m, 2H), −0.03 to 0.10 (m, 2H); 13C NMR
(Z)-3-(Ethyl(phenyl)phosphoryl)-3-(1-hydroxycyclopropyl)-1,2-di-
phenylprop-2-en-1-one (3u). The reaction of 1b (37 mg, 0.150
mmol) and ethyldiphenylphosphine (2l; 48 mg, 1.5 equiv) at 0 °C
afforded 3u (51 mg, 0.123 mmol, 82%) as a white solid (eluent:
petroleum ether/ethyl acetate 2/1): mp 175−176 °C (petroleum
ether/ethyl acetate); 1H NMR (400 MHz, DMSO-d6, 80 °C) δ 7.70−
7.90 (m, 4H), 7.20−7.60 (m, 11H), 5.51 (s, 1H), 2.25−2.47 (m, 2H),
1.00−1.23 (m, 3H), 0.30−0.60 (m, 2H), −0.10 to 0.10 (m, 1H),
−0.30 to −0.17 (m, 1H); 13C NMR (100 MHz, DMSO-d6, 80 °C) δ
194.1 (d, 3JC−P = 4.9 Hz), 155.5 (d, 2JC−P = 10.5 Hz), 136.6, 135.5 (d,
3
(100 MHz, DMSO-d6, 80 °C) δ 193.9 (d, JC−P = 6.1 Hz), 154.9 (d,
2JC−P = 10.9 Hz), 141.5 (d, 4JC−P = 1.9 Hz), 135.7 (d, 1JC−P = 92.0 Hz),
3
2
135.2 (d, JC−P = 14.2 Hz), 135.0, 132.1, 132.0 (d, JC−P = 11.3 Hz),
128.9, 128.8 (d, 1JC−P = 102.2 Hz), 128.5, 128.3, 128.2 (d, 3JC−P = 13.1
Hz), 127.9, 127.2, 53.1 (d, 2JC−P = 10.3 Hz), 20.5, 15.6 (d, 3JC−P = 5.4
Hz); 31P NMR (162 MHz, DMSO-d6, 25 °C) δ 30.11; IR (neat) 3354,
1658, 1599, 1446, 1392, 1259, 1232, 1148, 1118, 1097, 808, 707, 662
cm−1; MS (70 eV, EI) m/z (%) 492 (M+, 3.92), 229 (100); TOF
HRMS (EI) calcd for C32H29O3P (M+) 492.1854, found 492.1855.
(Z)-3-(Dim-tolylphosphoryl)-3-(1-hydroxycyclopropyl)-1,2-diphe-
nylprop-2-en-1-one (3r). The reaction of 1b (37 mg, 0.15o mmol),
tris(3-methylphenyl)phosphine (2g; 68 mg, 1.5 equiv) at 0 °C
afforded 3r (51 mg, 0.104 mmol, 69%) as a white solid (eluent:
petroleum ether/ethyl acetate 2/1): mp 155−156 °C (petroleum
ether/ethyl acetate); 1H NMR (400 MHz, DMSO-d6, 80 °C) δ 7.45−
7.65 (m, 8H), 7.15−7.44 (m, 10H), 5.40 (s, 1H), 2.27 (s, 6H), 0.40−
0.55 (m, 2H), −0.04 to 0.10 (m, 2H); 13C NMR (100 MHz, DMSO-
1
1
3JC−P = 12.3 Hz), 135.1 (d, JC−P = 83.6 Hz), 134.0 (d, JC−P = 94.3
2
Hz), 131.7, 130.86, 130.81 (d, JC−P = 9.4 Hz), 128.6, 128.3, 128.2,
127.8, 127.7 (d, 3JC−P = 8.9 Hz), 127.6, 51.7 (d, 2JC−P = 11.9 Hz), 20.9
(d, 1JC−P = 70.7 Hz), 15.9 (d, 3JC−P = 6.2 Hz), 15.7, 4.8 (d, 2JC−P = 3.8
Hz); 31P NMR (162 MHz, DMSO-d6, 25 °C) δ 34.88; IR (neat) 3158,
1665, 1595, 1444, 1254, 1225, 1148, 1108, 1028, 877, 727, 693, 646
cm−1; MS (70 eV, EI) m/z (%) 416 (M+, 8.67), 153 (65.84), 105
(100); TOF HRMS (EI) calcd for C26H25O3P (M+) 416.1541, found
416.1548.
(Z)-3-(Cyclopropyl(phenyl)phosphoryl)-3-(1-hydroxycyclopropyl)-
1,2-diphenylprop-2-en-1-one (3v). The reaction of 1b (37 mg, 0.150
mmol) and cyclopropyldiphenylphosphine (2m; 51 mg, 1.5 equiv) at 0
°C afforded 3v (45 mg, 0.105 mmol, 70%) as a white solid (eluent:
petroleum ether/ethyl acetate 2/1): mp 162−163 °C (petroleum
ether/ethyl acetate); 1H NMR (400 MHz, DMSO-d6, 80 °C) δ 7.73−
7.96 (m, 4H), 7.20−7.65 (m, 11H), 5.46 (bs, 1H), 1.69−1.87 (m,
1H), 0.75−0.95 (m, 3H), 0.60−0.74 (m, 1H), 0.45−0.57 (m, 2H),
0.04−0.14 (m, 1H), −0.20--0.03 (m, 1H); 13C NMR (100 MHz,
3
2
d6, 80 °C) δ 193.8 (d, JC−P = 5.8 Hz), 155.1 (d, JC−P = 11.3 Hz),
3
1
137.0 (d, JC−P = 11.3 Hz), 135.4 (d, JC−P = 91.6 Hz), 135.21 (d,
3JC−P = 12.5 Hz), 135.15, 132.3 (d, 2JC−P = 10.3 Hz), 132.1 (d, 3JC−P
=
1
2
15.4 Hz), 132.0, 131.9 (d, JC−P = 100.8 Hz), 129.2 (d, JC−P = 10.7
Hz), 128.8, 128.5, 128.3, 127.9, 127.4 (d, 3JC−P = 12.8 Hz), 127.3, 53.1
(d, JC−P = 10.8 Hz), 20.5, 15.8 (d, JC−P = 4.8 Hz); 31P NMR (162
MHz, DMSO-d6, 25 °C) δ 30.28; IR (neat) 3368, 1662, 1595, 1448,
1392, 1259, 1227, 1150, 1114, 872, 707, 653 cm−1; MS (70 eV, EI) m/
z (%) 492 (M+, 4.45), 229 (100); TOF HRMS (EI) calcd for
C32H29O3P (M+) 492.1854, found 492.1850.
2
3
2
DMSO-d6, 80 °C) δ 194.3 (d, 3JC−P = 6.0 Hz), 154.3 (d, JC−P = 11.2
1
3
Hz), 136.3, 135.6 (d, JC−P = 90.4 Hz), 135.2 (d, JC−P = 13.8 Hz),
1
2
134.0 (d, JC−P = 98.7 Hz), 131.9, 130.8, 130.6 (d, JC−P = 10.1 Hz),
128.7, 128.31, 128.26, 127.8, 127.7 (d, 3JC−P = 8.9 Hz), 127.6, 51.7 (d,
2JC−P = 12.6 Hz), 16.1 (d, 3JC−P = 6.0 Hz), 15.3 (d, 3JC−P = 4.0 Hz), 5.9
(Z)-3-(Dinaphthalen-2-ylphosphoryl)-3-(1-hydroxycyclopropyl)-
1,2-diphenylprop-2- en-1-one (3s). The reaction of 1b (37 mg, 0.150
G
dx.doi.org/10.1021/jo400610q | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Article
(d, 1JC−P = 101.8 Hz), 2.5 (d, 2JC−P = 4.4 Hz), 2.4 (d, 2JC−P = 2.3 Hz);
31P NMR (162 MHz, DMSO-d6, 25 °C) δ 32.46; IR (neat) 3276,
96.77(8), C(7)−P(1)−O(1) = 176.80(7), C(18)−P(1)−C(19) =
119.84(9), C(18)−P(1)−O(1) = 85.34(7), C(19)−P(1)−O(1) =
85.94(7), C(30)−O(1)−P(1) = 114.82(10).
1669, 1443, 1254, 1253, 1152, 1109, 1027, 897, 724, 692 cm−1; MS
(70 eV, EI) m/z (%) 428 (M+, 7.84), 323 (100), 165 (65.47); TOF
HRMS (EI) calcd for C27H25O3P (M+) 428.1541, found 428.1536.
(Z)-3-((4-Chlorophenyl)(phenyl)phosphoryl)-3-(1-hydroxycyclo-
propyl)-1,2-diphenylprop-2-en-1-one (3w). The reaction of 1b (37
mg, 0.150 mmol) and bis(4-chlorophenyl)phenylphosphine (2n; 74
mg, 1.5 equiv) at 0 °C and then room temperature for 10 h afforded
3w (42 mg, 0.084 mmol, 56%) as s white solid and 3o (13 mg, 0.024
mmol, 16%) as a white solid (eluent: petroleum ether/ethyl acetate 2/
3a-18O. In an atmosphere of dry air, H2O (27 mg, 1.5 mmol, 10
equiv) was added to a solution of 1a (39 mg, 0.150 mmol) in 5 mL of
dry DCM at room temperature. Then PPh3 (79 mg, 0.3 mmol, 2
equiv) was added to the mixture. After it was stirred for 10 h
(monitored by TLC), the reaction was followed by GC-MS. Filtration,
evaporation, and flash chromatography on silica gel (petroleum ether/
ethyl acetate 2/1 v/v) afforded 3a-18O (51 mg, 0.106 mmol, 71%) as a
white solid: 1H NMR (400 MHz, DMSO-d6, 80 °C) δ 7.73−7.82 (m,
4H), 7.57 (d, J = 6.8 Hz, 2H), 7.30−7.52 (m, 11H), 7.06 (d, J = 8.0
Hz, 2H), 5.30 (bs, 1H), 2.28 (s, 3H), 0.40−0.53 (m, 2H), −0.50 to
0.11 (m, 2H); 13C NMR (100 MHz, DMSO-d6, 80 °C) δ 193.5 (d,
1
1). 3w: mp 193−194 °C (petroleum ether/ethyl acetate); H NMR
(400 MHz, DMSO-d6, 80 °C) δ 7.65−7.88 (m, 4H), 7.20−7.65 (m,
15H), 5.34 (s, 1H), 0.35−0.55 (m, 2H), −0.01−0.14 (m, 2H); 13C
NMR (100 MHz, DMSO-d6, 80 °C) δ 193.9 (d, 3JC−P = 4.5 Hz), 156.0
2
3
3JC−P = 5.0 Hz), 155.8 (d, JC−P = 11.3 Hz), 142.7, 135.4 (d, JC−P
=
2
(d, 2JC−P = 11.2 Hz), 136.8 (d, 4JC−P = 2.0 Hz), 153.3, 135.0 (d, JC−P
1
1
14.9 Hz), 134.7 (d, JC−P = 92.6 Hz), 133.1, 132.3 (d, JC−P = 100.5
1
3
Hz), 131.9 (d, 2JC−P = 9.7 Hz), 131.3 (d, 4JC−P = 3.0 Hz), 129.0, 128.4,
= 14.1 Hz), 134.7 (d, JC−P = 93.4 Hz), 133.9 (d, JC−P = 10.6 Hz),
132.3, 132.0 (d, 1JC−P = 100.3 Hz), 131.8 (d, JC−P = 10.4 Hz), 131.5,
3
3
2
128.3, 128.0, 127.8, 127.5 (d, JC−P = 12.4 Hz), 52.9 (d, JC−P = 11.0
131.1 (d, 1JC−P = 101.1 Hz), 128.9, 128.6, 128.3, 127.9, 127.7 (d, 2JC−P
= 12.4 Hz), 127.5, 52.7 (d, 2JC−P = 10.2 Hz), 15.9 (d, 3JC−P = 4.7 Hz),
Hz), 20.6, 15.8 (d, JC−P = 7.6 Hz); 31P NMR (162 MHz, DMSO-d6,
3
25 °C) δ 29.86.
15.8 (d, JC−P = 5.2 Hz); 31P NMR (162 MHz, DMSO-d6, 25 °C) δ
3
Synthetic Applications. 8-(Diphenylphosphoryl)-9-(4-methox-
ybenzoyl)-5H-benzo[7]annulen-7(6H)-one (8). To a stirred solution
of 3e (49 mg, 0.10 mmol) in CH3CN (2 mL) was added 2.0 equiv of
CAN (110 mg) at 30 °C. After it was stirred for 10 min (monitored by
TLC), the resulting mixture was concentrated under reduced pressure.
The residue was subjected to flash column chromatography
(petroleum ether/ethyl acetate 4/1 v/v) to give the product 8 (41
mg, 0.083 mmol, 84%) as a white solid: mp 222−224 °C (petroleum
28.74; IR (neat) 3400, 1654, 1579, 1481, 1385, 1261, 1226, 1158,
1116, 1091, 823, 746, 711 cm−1; MS (70 eV, EI) m/z (%) 498
(M(35Cl)+, 6.66), 500(M(37Cl)+, 3.09), 235 (100); TOF HRMS (EI)
calcd for C30H24O3P35Cl (M+) 498.1152, found 498.1159.
(Z)-3-(1-hydroxycyclopropyl)-3-((4-methoxyphenyl)(phenyl)-
phosphoryl)-1,2-diphenylprop-2-en-1-one (3x). The reaction of 1b
(37 mg, 0.150 mmol) and bis(4-methoxyphenyl)phenylphosphine
(2o; 66 mg, 1.5 equiv) at 0 °C afforded 3x (56 mg, 0.113 mmol, 75%)
and 3b (3 mg, 0.06 mmol, 5%) as a white solid (eluent: petroleum
ether/ethyl acetate 2/1). 3x: mp 187−188 °C (petroleum ether/ethyl
1
ether/chloroform); H NMR (400 MHz, DMSO-d6, 80 °C) δ 7.69−
7.80 (m, 4H), 7.66 (d, J = 8.4 Hz, 2H), 7.56−7.63 (m, 2H), 7.48−7.56
(m, 4H), 7.44 (d, J = 7.6 Hz, 1H), 7.32 (t, J = 7.2 Hz, 1H), 7.22 (t, J =
7.6 Hz, 1H), 7.05 (d, J = 8.0 Hz, 1H), 6.92 (d, J = 8.4 Hz, 2H), 3.81 (s,
3H), 3.23 (m, 2H), 2.59 (t, J = 5.6 Hz, 2H); 13C NMR (100 MHz,
1
acetate); H NMR (400 MHz, DMSO-d6, 80 °C) δ 7.75−7.86 (m,
2H), 7.53−7.65 (m, 6H), 7.30−7.52 (m, 7H), 7.26 (t, J = 7.6 Hz, 2H),
6.89 (d, J = 7.6 Hz, 2H), 5.34 (s, 1H), 3.76 (s, 3H), 0.40−0.52 (m,
2H), −0.03−0.10 (m, 2H); 13C NMR (100 MHz, DMSO-d6, 80 °C) δ
194.0 (d, 3JC−P = 5.8 Hz), 161.8, 155.0 (d, 2JC−P = 11.4 Hz), 135.6 (d,
1JC−P = 92.9 Hz), 135.21, 135.17 (d, 3JC−P = 13.7 Hz), 134.0 (d, 2JC−P
2
3
DMSO-d6, 80 °C) δ 203.4 (d, JC−P = 8.1 Hz), 192.1 (d, JC−P = 6.4
4
1
Hz), 162.9, 155.7 (d, JC−P = 3.5 Hz), 139.3, 137.7 (d, JC−P = 83.4
Hz), 133.2 (d, 2JC−P = 13.4 Hz), 131.9 (d, 1JC−P = 105.3 Hz), 131.6 (d,
4JC−P = 1.8 Hz), 131.5 (d, 2JC−P = 10.3 Hz), 130.8, 130.0, 129.5, 128.9,
1
3
127.9 (d, JC−P = 12.6 Hz), 127.3, 127.2, 113.5, 55.2, 49.7, 28.4; 31P
3
= 11.1 Hz), 132.5 (d, JC−P = 100.7 Hz), 132.2, 131.8 (d, JC−P = 9.8
2
Hz), 131.3, 128.9, 128.5, 128.3, 127.9, 127.6 (d, JC−P = 12.6 Hz),
NMR (162 MHz, DMSO-d6, 25 °C) δ 25.1; IR (neat) 3058, 1682,
1598, 1575, 1510, 1438, 1316, 1261, 1238, 1188, 1166, 1117, 1025,
973 cm−1; MS (70 eV, EI) m/z (%) 492 (M+, 12.53), 135 (100). TOF
HRMS (EI) calcd for C31H25O4P (M+) 492.1490, found 492.1495.
(Z)-3-(Diphenylphosphoryl)-1-(4-methoxyphenyl)-2-phenylhex-
2-ene-1,4-dione (9). To a stirred solution of 3e (49 mg, 0.10 mmol) in
toluene (2 mL) was added 5% of AuPPh3Cl (2 mg) and AgOTf (1
mg) at 120 °C. After it was stirred for 1 h (monitored by TLC), the
resulting mixture was concentrated under reduced pressure. The
residue was subjected to flash column chromatography (petroleum
ether/ethyl acetate 4/1 v/v) to give the product 9 (39 mg, 0.079
1
3
127.3, 122.8 (d, JC−P = 106.5 Hz), 113.3 (d, JC−P = 13.8 Hz), 54.9,
53.1 (d, 2JC−P = 11.0 Hz), 15.8 (d, 3JC−P = 5.0 Hz), 15.5 (d, 3JC−P = 5.5
Hz); 31P NMR (162 MHz, DMSO-d6, 25 °C) δ 29.62; IR (neat) 3393,
1655, 1596, 1572, 1500, 1295, 1258, 1220, 1157, 1116, 1019, 838, 705,
650 cm−1; MS (70 eV, EI) m/z (%) 494 (M+, 1.11), 232 (100); TOF
HRMS (EI) calcd for C31H27O4P (M+) 494.1647, found 494.1642.
Mechanistic Studies. 7m. To a stirred solution of 1m (34 mg,
0.15 mmol) in acetone (5 mL with 20 mg of H2O) was added 1.5
equiv of triphenylphosphine (2a; 59 mg, 1.5 equiv) in an air
atmosphere at 0 °C. After it was stirred for 10 h, the resulting mixture
was concentrated under reduced pressure. The residue was recrystal-
lized (petroleum ether/dichloromethane 15/1) to give the product 7m
(56 mg, 0.115 mmol, 76%) as a white solid: mp 173−174 °C
(petroleum ether/ethyl acetate); 1H NMR (400 MHz, CDCl3) δ
7.34−7.44 (m, 11H), 7.20−7.30 (m, 9H), 4.18 (d, J = 8.8 Hz, 1H),
2.34−2.46 (m, 1H), 0.67 (d, J = 6.4 Hz, 6H), 0.48−0.59 (m, 1H),
1
mmol, 80%) as an oil: H NMR (400 MHz, CDCl3, 25 °C) δ 7.78−
7.87 (m, 4H), 7.72 (d, J = 8.4 Hz, 2H), 7.45−7.55 (m, 4H), 7.37−7.44
(m, 4H), 7.31−7.36 (m, 3H), 6.63 (d, J = 8.8 Hz, 2H), 3.75 (s, 3H),
1.79 (q, J = 6.8 Hz, 2H), 0.45 (t, J = 6.8 Hz, 3H); 13C NMR (100
MHz, CDCl3, 25 °C) δ 206.8 (d, 2JC−P = 8.9 Hz), 192.2 (d, 3JC−P = 6.1
4
1
Hz), 163.4, 156.3 (d, JC−P = 3.0 Hz), 138.6 (d, JC−P = 78.9 Hz),
−0.2−0.05 (m, 4H); 13C NMR (100 MHz, CDCl3) δ 159.3 (d, 2JC−P
22.9 Hz), 151.5 (d, 4JC−P = 3.1 Hz), 143.8 (d, 1JC−P = 102.9 Hz), 136.7
=
135.1 (d, 3JC−P = 14.7 Hz), 132.3 (d, 2JC−P = 10.3 Hz), 131.9 (d, 4JC−P
1
= 2.5 Hz), 131.7, 131.2 (d, JC−P = 108.8 Hz), 130.1, 129.0, 128.9,
2
3
128.21 (d, JC−P = 11.8 Hz), 128.20, 113.3, 55.3, 37.8, 7.5; 31P NMR
3
(d, JC−P = 21.0 Hz), 131.7 (d, JC−P = 8.1 Hz), 130.0, 128.0, 127.6,
127.5, 126.9 (d, 2JC−P = 12.4 Hz), 126.6 (d, JC−P = 121.9 Hz), 111.5,
1
(162 MHz, CDCl3, 25 °C) δ 21.6; IR (neat) 3057, 1664, 1596,1510,
1438, 1315, 1257, 1219, 1192, 1164, 1115, 1024, 908 cm−1; MS (70
eV, EI) m/z (%) 494 (M+, 8.17), 135 (100). TOF HRMS (EI) calcd
for C31H27O4P (M+) 494.1647, found 494.1656.
(Z)-3-(Diphenylphosphoryl)-1-(4-methoxyphenyl)-2-phenylhexa-
2,5-diene-1,4-dione (10). To a stirred solution of 3e (49 mg, 0.10
mmol) in CH3CN (2 mL) was added 1 equiv of NBS (18 mg) at 30
°C. After it was stirred for 30 min, to the resulting mixture was added 3
equiv of Et3N (0.042 mL) by syringe and the temperature was raised
to 80 °C. After the mixture was stirred for 3 h (monitored by TLC),
10 mL of chloroform was added to quench the reaction; after that, the
mixture was extracted with three 3 mL portions of H2O (in order to
25.3, 23.2, 14.8 (d, JC−P = 20.6 Hz), 10.9 (d, JC−P = 6.6 Hz); 31P
NMR (162 MHz, CDCl3, 25 °C) δ −46.50; IR (neat) 2955, 1610,
1572, 1432, 1383, 1217, 1189, 1079, 1058, 805, 724, 692 cm−1; MS
(70 eV, EI) m/z (%) 488 (M+, 11.8), 262 (100); TOF HRMS (EI)
calcd for C34H33OP (M+) 488.2269, found 488.2262.
2
3
Selected bond lengths (Å) and angles (deg) for 7m: P(1)−C(6) =
1.8213(18), P(1)−C(7) = 1.9046(17), P(1)−C(18) = 1.8319(19),
P(1)−C(19) = 1.8393(18), P(1)−O(1) = 1.8578(12), O(1)−C(30) =
1.336(2); C(6)−P(1)−C(7) = 95.49(8), C(6)−P(1)−C(18) =
121.55(9), C(6)−P(1)−C(19) = 116.66(8), C(6)−P(1)−O(1) =
84.77(7), C(7)−P(1)−C(18) = 91.82(8), C(7)−P(1)−C(19) =
H
dx.doi.org/10.1021/jo400610q | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Article
get rid of pyrrolidine-2,5-dione). The organic layers were dried over
anhydrous MgSO4. After filtration and removal of the solvent in vacuo,
the residues were purified with flash silica chromatography (petroleum
ether/ethyl acetate 4/1 v/v) to give the product 10 (40 mg, 0.081
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1
mmol, 82%) as an oil: H NMR (400 MHz, CDCl3, 25 °C) δ 7.75−
7.84 (m, 4H), 7.72 (d, J = 8.0 Hz, 2H), 7.43−7.52 (m, 4H), 7.35−7.42
(m, 4H), 7.27−7.32 (m, 3H), 6.64 (d, J = 8.4 Hz, 2H), 5.95 (d, J =
1
2
16.8 Hz, 1H), 5.80 (dd, J = 17.6 Hz, J = 10.0 Hz, 1H), 5.39 (d, J =
10.4 Hz, 1H), 3.76 (s, 3H); 13C NMR (100 MHz, CDCl3, 25 °C) δ
195.3 (d, 2JC−P = 10.3 Hz), 192.1 (d, 3JC−P = 6.0 Hz), 163.4, 158.9 (d,
4
1
4JC−P = 3.8 Hz), 135.84 (d, JC−P = 1.8 Hz), 135.80 (d, JC−P = 80.8
Hz), 135.1 (d, 3JC−P = 14.0 Hz), 132.3 (d, 2JC−P = 10.7 Hz), 131.9 (d,
4JC−P = 2.5 Hz), 131.7, 131.2 (d, JC−P = 107.3 Hz), 130.6, 130.1,
1
128.9, 128.8, 128.5, 128.2 (d, 3JC−P = 13.1 Hz), 113.4, 55.3; 31P NMR
(162 MHz, CDCl3, 25 °C) δ 22.7; IR (neat) 3057, 1664, 1597, 1510,
1487, 1438, 1398, 1316, 1251, 1193, 1164, 1116, 1022, 925 cm−1; MS
(70 eV, EI) m/z (%) 492 (M+, 42.18), 135 (100). TOF HRMS (EI)
calcd for C31H25O4P (M+) 492.1490, found 492.1494.
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Vols. 1−15.
ASSOCIATED CONTENT
■
S
* Supporting Information
Figures giving 1H and 13C NMR spectra for compounds 3, 7m,
and 8−10 and figures and CIF files giving structures and X-ray
crystallographic data for 3a, 7m, and 8. This material is
available free of charge via the Internet at http://pubs.acs.org.
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J.; Ladeira, S.; Bouhadir, G.; Miqueu, K.; Bourissou, D. Chem.
Commun. 2011, 47, 8611−8613.
AUTHOR INFORMATION
Corresponding Author
*E-mail for L.W.: wululing@zju.edu.cn.
Notes
The authors declare no competing financial interest.
§Professor Huang passed away on March 6, 2010. He was fully
in charge of this project. Professor Luling Wu is helping to
finish all the projects with assistance from Professor Shengming
Ma.
■
(11) Goldwhite, H. Introduction to Phosphorus Chemistry; Cambridge
University Press: New York, 1981; Chapter 2.
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ACKNOWLEDGMENTS
■
We are grateful to the National Natural Science Foundation of
China (Project Nos. 20872127, 20732005, and J0830431), the
National Basic Research Program of China (973 Program,
2009CB825300), CAS Academician Foundation of Zhejiang
Province, and the Fundamental Research Funds for the Central
Universities for financial support.
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dx.doi.org/10.1021/jo400610q | J. Org. Chem. XXXX, XXX, XXX−XXX