Microwave-assisted periselective annulation of triarylphosphenes with aldehydes and ketones

Article abstract of DOI:10.1039/d0ob02011g

The reaction of diazo(aryl)methyl(diaryl)phosphine oxides with aldehydes and ketones generates benzo-δ-phosphinolactones in low to good yields with 1,1-diarylalk-1-enes as byproducts under microwave irradiation. Diazo(aryl)methyl(diaryl)phosphine oxides first undergo a Wolff rearrangement to form diaryl(aryl)phosphenes, which further react with aldehydes and ketones to afford benzo-δ-phosphinolactones and β-phosphinolactones. The latter are unstable under heating and fragment into the corresponding 1,1-diarylalk-1-enes and arylphosphine dioxides under reaction conditions. The arylphosphine dioxides become arylphosphonic acids during workup. The periselectivity in the annulation shows that the reaction of diaryl(aryl)phosphenes with most aldehydes and ketones favors phosphene phenyl participation in (4 + 2) annulation(2 + 2) annulation. This journal is

Full text of DOI:10.1039/d0ob02011g

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OrPgleanasice&dBoionmotoaledcjuulsatr mChaermgiinstsry
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DOI: 10.1039/D0OB02011G
Journal Name
ARTICLE
Microwave-assisted periselective annulation of triarylphosphenes
with aldehydes and ketones
Yun Luo,§ Zhicheng Fu,§ Xingyang Fu, Changle Du and Jiaxi Xu*
Received 00th January 20xx,
Accepted 00th January 20xx
The reaction of (diazo(aryl)methyl)(diaryl)phosphine oxides with aldehydes and ketones generates benzo--
phospholactones in low to good yields with 1,1-diarylalk-1-enes as byproducts under microwave irradiation.
(Diazo(aryl)methyl)(diaryl)phosphine oxides first undergo a Wolff rearrangement to form diaryl(aryl)phosphenes, which
further react with aldehydes and ketones to afford benzo--phospholactones and β-phospholactones. The latter are instable
under heating and fragment into the corresponding 1,1-diarylalk-1-enes and arylphosphine dioxides under reaction
conditions. The arylphosphine dioxides become arylphosphonic acids during workup. The periselectivity in the annulation
shows that the reaction of diaryl(aryl)phosphenes with most aldehydes and ketones favors phosphene phenyl participating
(4+2) annulation over (2+2) annulation.
DOI: 10.1039/x0xx00000x
www.rsc.org/
cycloaddition products, respectively (Scheme 1b). The
Introduction
annulated products benzo-
only very low yields in the previously reported methods from
phosphenes.3b-f,6 The benzo-
-phospholactones are very useful
-phospholactones were obtained in
Phosphenes, the phosphorus analogues of ketenes, should
be important intermediates and can be applied in some
nucleophilic additions, annulations, and cycloadditions.
However, compared with ketenes1 and sulfenes,2 only limited
attentions have been paid previously to the annulation and
cycloaddition of phosphenes.3,4 The phosphenes have been
prepared in situ previously via photo and thermal Wollf
rearrangements of diazomethylphosphine oxide derivatives3

and
retro-Diels-Alder
cycloadditions
of
2-
phosphabicyclo[2.2.2]octa-5,7-diene derivatives.4
Similar as active intermediate ketenes and sulfenes,
phosphenes undergo nucleophilic addition with nucleophiles,
such as water, alcohols, and amines,3a,b,4a,c,d and annulation or
cycloaddition with unsaturated compounds, including
aldehydes,3b,e,6 ketones,3c unsaturated aldehydes and
chalcones,3e,f,4a and 1,3-dienes (Scheme 1a,b).4a However, in the
previous photochemical reactions of diazomethylphosphine
oxide derivatives with aldehydes and ketones, besides (4+2)
annulation products, both the carbene insertion products (for
aldehydes) and the carbene cyclopropanation products (for
solvent benzene and for the C=C double bond of unsaturated
ketones) appear. Additionally, for the unsaturated ketones, the
dimers of the carbenes, 4-(alk-1-enyl)-1,2-oxaphosphetane 2-
oxides, and conjugated dienes generate as well (Scheme 1a).
The thermal reactions of phenylthiophosphene with 2,3-
dimethylbut-1,3-diene and chalcone give rise to [2+4]
§These two authors contribute equally
.
State Key Laboratory of Chemical Resource Engineering, Department of Organic
Chemistry, College of Chemistry, Beijing University of Chemical Technology, Beijing
100029, P. R. China. E-mail: jxxu@mail.buct.edu.cn; Fax: +86 10 64435565
Electronic Supplementary Information (ESI) available: Copies of 1H, 13C, and 19F NMR
Scheme 1. Annulation of phosphenes and unsaturated bonds.
spectra of products
3 and 4. See DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
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Organic & Biomolecular Chemistry
Page 2 of 12
ARTICLE
and important biological compounds.7 Thus, an efficient
Journal Name
64 12
15
16
PhCl
PhCl
PhCl
150
150
150
15
3
120
View Article Online
DOI: 10.1039/D0OB02011G
synthetic method for the preparation of -phospholactones,
especial benzo- -phospholactones, are in high demand. Herein,
we report a microwave-assisted periselective synthesis of
benzo- -phospholactones from

58
54
14
12

17e
aReaction conditions: 1a (0.2 mmol) and 2a (0.8 mmol) in 3 mL
of anhydrous solvent in a capped microwave reaction tube filled
with N2 were heated under microwave irradiation. bYield of the
isolated product. c2a (0.4 mmol). d2a (1.0 mmol). eUnder
classical oil-bath heating.

(diazo)arylmethyl(diaryl)phosphine oxides with aldehydes and
ketones in satisfactory yields in most cases (Scheme 1c).
Results and Discussion
Table 2. Scope of Aldehydes and Ketones.a
It is well known that microwave can accelerate some organic
reactions and improve the reaction selectivities and yields.8 The
microwave can promote the Wolff rearrangement of
diazomethyl ketones to ketenes and the subsequent
cycloaddition with imines.9 Thus, we envisioned that microwave
R2
yield/%b yield/%b
might
(diazo)arylmethyl(diaryl)phosphine oxides with aldehydes and
ketones. We first selected the reaction of
improve
the
annulation
of
entry
2
R1
3
66
60
55
63
65
47
48
46
62
69
65
66
76
48
63
40
54
56
54
71
72
55
29
trace
-
4
17
18
7
7
12
7
18
5
15
8
12
11
14
10
16
9
10
14
16
6
1
2
3
4
5
6
7
8
2a
2b
2c
2d
2e
2f
2g
2h
2i
2j
2k
2l
2m
2n
2o
2p
2q
2r
4-ClC6H4
4-BrC6H4
4-FC6H4
4-MeC6H4
4-iPrC6H4
4-MeOC6H4
4-NCC6H4
4-O2NC6H4
2-FC6H4
2-ClC6H4
2-BrC6H4
2-MeC6H4
2-MeOC6H4
3-ClC6H4
3-BrC6H4
3-MeC6H4
3-MeOC6H4
Ph
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
(diazo)phenylmethyl(diphenyl)phosphine oxide (1a) and 4-
chlorobenzaldehyde (2a) as a model reaction to optimize the
reaction conditions under the microwave irradiation. We
o
started solvent evaluation at 130 C. The results indicated that
a slightly high yield was obtained in chlorobenzene as solvent
for the desired benzo-
5). Further temperature screening was conducted in
chlorobenzene, revealing that 150 oC was the best choice (Table
1, entries 5 12). Both decreasing and increasing amounts of
-phospholactone 3a (Table 1, entries
1

9

10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
aldehyde 2a resulted in the lowering of the yield (Table 1,
entries 13 and 14). Neither lengthening nor shortening the
reaction time further improved the yield (Table 1, entries 15 and
16). Under classical oil-bath heating conditions, the reaction
needed a long time but with a relatively low yield (Table 1, entry
17). In each of optimization reactions, byproduct 2-(4-
chlorophenyl)-1,1-diphenylethene (4a) was obtained in low
yields varied from 5
21%.
2s
2t
2-Naph
2,6-Cl2C6H3
Table 1. Optimization on the Reaction Conditionsa
2u 2,4,6-Me3C6H2
2v
2w
2x
2y
8
2,4-Cl2C6H4
Pyridin-2-yl
Funan-2-yl
1H-indol-3-yl
n-Pentyl
Ph
11
NDc
10
-
Temp./ Time/
yield/%b
3a
yield/%b
4a
14
6
2z
H
31
32
27
trace
-
6
42
7
ND
-
entry Solvent
oC
min.
10
10
10
10
10
80
10
20
10
10
10
10
10
10
2aa
2ab
2ac
2ad
Ph
Me
Me
OMe
1
2
3
4
5
DCE
PhMe
MeCN
xylenes
PhCl
130
130
130
130
130
100
110
130
140
150
160
170
150
150
60
60
42
53
62
51
47
58
64
66
65
65
52
59
Ph
Bn
Ph
9
10
10
12
5
14
17
17
21
16
19
10
aReaction conditions: 1a (0.2 mmol) and
2
(0.8 mmol) in 3 mL of
anhydrous solvent in a capped microwave reaction tube filled
with N2 were heated under microwave irradiation. bYield of the
isolated product. cND = not determined.
6
PhCl
7
PhCl
8
PhCl
9
PhCl
With the optimal conditions in hand, the scope and generality
of aldehydes and ketones were investigated and the results are
summarized in Table 2. First of all, the reactions of different
para-substituted benzaldehydes 2b-2h were conducted; both
weak electron-withdrawing and electron-donating para-
substituted benzaldehydes gave the corresponding products
10
11
12
13c
14d
PhCl
PhCl
PhCl
PhCl
PhCl
2 | J. Name., 2012, 00, 1-3
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3a-3h in moderate to good yields. Most electron-donating and aReaction conditions:
ARTICLE
1
(0.2 mmol) and 2a (0.8 mmol) in 3 mL of
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weak electron-withdrawing para-substituted benzaldehydes anhydrous solvent in a capped microwaDveOIr:e10a.c10ti3o9n/Dt0uObBe02fi0l1le1Gd
gave the desired products in higher yields than those with with N2 were heated under microwave irradiation. bYield of the
c
strong electron-withdrawing para-substituents (Table 2, entries isolated product. The ratio of products
3 was determined on
1

8). All ortho-substituted benzaldehydes 2i-2m worked well, the basis of the 31P-NMR analysis and the structures of the
producing the desired products 3i-2m in good yields varied from isomeric products were assigned on the basis of the reaction
62 76% (Table 2, entries 13). Meta-substituted mechanism.
benzaldehydes 2n-2q were suitable substrates, resulting in the Besides aldehydes, ketones 2aa-2ac and ester 2ad were
products 3n-2q in satisfactory yields of 40 63% (Table 2, entries examined in the reaction as well (Table 2, entries 27 30).
14 17). Benzaldehyde 2r and naphthalene-2-carbaldehyde (2s Benzophenone (2aa) and acetophenone (2ab) gave rise to the

9



)
gave rise to the corresponding products 3r and 3s in 56% and corresponding products 3aa and 3ab in 32% and 27% yields,
54% yields, respectively (Table 2, entries 18 and 19). respectively (Table 2, entries 27 and 28). However, neither 1-
Polysubstituted benzaldehydes 2t-2v produced the desired phenylacetone nor methyl benzoate worked (Table 2, entries 29
products 3t-3v in good yields (Table 2, entries 20

22). and 30).
The
(diazo(aryl)methyl)diarylphosphine oxides
(Table 3). The reaction
fluorophenyl)methyl)diphenylphosphine oxide
scope
of
the
phosphene
precursors,
Furthermore, we also explored several heteroaryl substituted
aldehydes 2w-2y. Only six-membered heteroatom aromatic
pyridine-2-carbaldehyde (2w) generated the desired product
3w in 29% yield (Table 2, entry 23). Neither funan-2-
carbaldehyde (2x) nor 1H-indole-3-carbaldehyde (2y) worked
(Table 2, entries 24 and 25). Aliphatic aldehyde hexanal (2z) was
tested, affording the desired product 3z in 31% yield (Table 2,
entry 26).
1
were evaluated
of
(diazo(2-
1b) and 4-
(
chlorobenzaldehyde (2a) generated the desired products in 59%
yield in a pair of isomers 3ad and 3ad’ in a ratio of 99:1, showing
an excellent regioselectivity because 2-fluorophenyl group
could not locate in the same plane with the C=C double bond of
the phosphine due to steric hindrance (vide post). The reaction
of (diazo(4-methylphenyl)methyl)diphenylphosphine oxide (1c
)
-
Table 3. Scopes of Diazo Compounds
1
and aldehyde 2a produced a pair of isomeric benzo-

phospholactone derivatives 3ae and 3ae’ in 28% yield and 57:43
ratio. The reaction of (diazo(phenyl)methyl)di(4-
methylphenyl)phosphine oxide (1d) and aldehyde 2a only
generated a trace amount of benzo- -phospholactones 3af and
3af’ possibly because more electron-rich di(4-

methylphenyl)phenylphosphene difficultly underwent the
nucleophilic addition with aldehyde 2a (vide post). However,
the
relatively
electron-deficient
generated
di(4-
from
chlorophenyl)phenylphosphene
diazo(phenyl)methyl)di(4-chlorophenyl)phosphine oxide (1e
produced a pair of benzo- -phospholactones 3ag and 3ag’ in a
moderate yield of 53% in a ratio of 71:29.
)

A large gram-scale preparation of product 3a was carried out,
affording in 59% yield, and a further application of product 3k
was conducted in the Suzuki coupling with phenylboronic acid,
affording the desired product 5 in 42% yield (Scheme 2).
Scheme 2. Gram scaled reaction and application
In each of the reactions, the corresponding substituted 1,1-
diarylalk-1-ene derivatives were obtained in low yields ranged
from 6

18% as byproducts. To verify the generation pathway of
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ARTICLE
Journal Name
1,1-diarylalk-1-enes. Pure product 3a was treated under the
reaction conditions (Scheme 3). No reaction was observed,
indicating that 1,1-diarylalk-1-enes did not generated from the
transition state TS1, in which three phenyl groups VloiecwaAtreticolenOntlhinee
DOI: 10.1039/D0OB02011G
equatorial bond, to generate cyclized intermediate
D.
Intermediate
D further aromatizes into the final product 3r in
corresponding products
(Scheme 4).
3 under the reaction conditions
the presence of benzaldehyde (2r), which services as a base
here. In the last protonation step, the acid protonated
benzaldehyde (2rH+) accesses the carbanion from less steric top
side, yielding product 3r with the indicated stereostructure
(Scheme 5). The strong electron-withdrawing para-substituted
benzaldehydes give rise to the corresponding products in lower
yields than those with electron-donating substituents,
indicating that the carbonyl group nucleophilic attack step
should be the rate-limiting step.
For the phosphenes with two different aryl groups, the
electron-rich ones favor nucleophilically attacks the carbonyl
carbon (intramolecular Friedel-Craft alkylation), resulting in the
Scheme 3. Control Experiment.
formation of major regiomers of products 3.
Scheme 4. Periselective annulation of phosphenes with
aldehydes and ketones.
Kawashima and co-workers prepared 1,2-oxaphosphetane 2-
oxides through esterification of β-hydroxyalkylphosphinic acids
and investigated their thermal stability. They found that 1,2-
oxaphosphetane 2-oxides were thermal instable and
fragmented into the corresponding alkenes and phosphonic
acid derivatives after treatment with ethanol.10,11 On the basis
of the control experiment and the results mentioned above, we
concluded
(diazo)phenylmethyl(diphenyl)phosphine oxide
underwent Wolff rearrangement to
diphenyl(phenyl)phosphene ( ), which further reacted with
aldehydes and ketones to give (4+2) annulation products,
that
the
reaction
of
first
(
1a
)
a
generate
A
benzo-
(2+2)

-phospholactones
annulation product
3
, periselectively companying with
-phospholactones, 1,2-
β
oxaphosphetane 2-oxides
oxaphosphetane 2-oxides
the corresponding alkenes
6
6
, as minor products. However, 1,2-
were instable and fragmented into
4
and phenylphosphine dioxide,10,11
which was converted into phenylphosphonic acid during
workup (Scheme 4).
The reaction mechanism is proposed on the basis of the
previous results on the reaction of phosphenes with cyclic
Scheme 5. Plausible mechanism for the formation of 1,3,4-
triphenyl-1,4-dihydrobenzo[d][1,2]oxaphosphinine 3-oxide (3r)
.
imines12 and the stereostructure of products
3
(Scheme 5).
1a first
undergoes a Wolff rearrangement under microwave heating to
Diazo(phenyl)methyl(diphenyl)phosphine oxide
(
)
There are other two possible pathways to generate product
3r. One is that the intermediate
B undergoes a disrotatary 6e
generate
diphenylmethylidene(phenyl)phosphine
oxide
electrocyclization to yield intermediate
into product 3r through intermediate
Diels-Alder cycloaddition of the phosphene
F
G
, which can aromatize
. Dearomatic hetero-
and benzaldehyde
(phosphene
A
). The oxygen atom of benzaldehyde (2r
)
nucleophilically attacks the phosphene
A
to generate
A
zwitterionic intermediate
B
, which resonates into another
. The electron-rich phenyl group in
C nucleophilically attacks the carbonyl
(2r) is another possible pathway through transition state TS2
.
zwitterionic intermediate
the benzylcarbanion in
C
However, the cycloaddition would give intermediate
H
, which
would aromatize into cis,trans-3r rather than product 3r
(Scheme 5). Arylmethylphosphonochloridate-generated
arylphosphenes also underwent a stepwise annulation with α,
carbon (intramolecular Friedel-Craft alkylation) from the Si-face
of the benzaldehyde (2r) through a chair-like six-membered ring

-
4 | J. Name., 2012, 00, 1-3
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ARTICLE
unsaturated ketones rather than cycloaddition.5 Thus, the amount of white solid was formed during thVeiewtiAmrticele. OTnlhinee
DOI: 10.1039/D0OB02011G
process of stepwise nucleophilic additions and aromatization is resulting solid was filtered off and washed with petroleum ether
more reasonable mechanism.
for several times. The obtained solid was dissolved in 40 mL of
tetrahydrofuran. After addition of p-toluene sulfonic acid
hydrate (12 mmol, 2.28 g), the mixture was stirred at room
temperature for 5 h. The resulting solid was filtered off and
washed with tetrahydrofuran for several times. The obtained
solid was dissolved in 30 mL of 15% aqueous ammonia, and the
mixture was stirred at room temperature for 1 h. The mixture
was extracted with chloroform (3 × 20 mL). The combined
organic phase was dried over anhydrous sodium sulfate. After
removal of part of the solvent, isoamyl nitrite (12 mmol, 1.44 g)
and glacial acetic acid (5 mmol, 0.3 mL) were added. After
refluxing for 1 h, the mixture was washed successively with
saturated NaHCO3 solution and brine, dried over anhydrous
sodium sulfate, and concentrated. The residue was purified by
column chromatography on silica gel with petroleum and ethyl
acetate (PE:EA = 5:1 to 3:1, v/v) as eluent.
Conclusions
We developed
(diazo(aryl)methyl)(diaryl)phosphine oxides with aldehydes and
ketones for the improved preparation of benzo-
a
microwave-assisted reaction of

-
phospholactones from phosphene chemistry. Under microwave
irradiation, (diazo(aryl)methyl)(diaryl)phosphine oxides first
undergoes
(aryl)phosphenes, which further react with aldehydes and
ketones to afford benzo- -phospholactones and β-
a
Wolff rearrangement to form diaryl

phospholactones. The latter are instable and fragment into 1,1-
diarylalk-1-enes and phenylphosphine dioxide under reaction
conditions. The periselectivity in the annulation shows that the
reaction of diaryl(aryl)phosphenes with aldehydes and ketones
favors the phosphene phenyl participating (4+2) annulation
with aldehydes and ketones over (2+2) annulation of the C=P
bond of the phosphenes with them. Carbocyclic aromatic
aldehydes show more activity than heteroaryl aldehydes,
aliphatic aldehydes, and ketones.
(Diazo(phenyl)methyl)diphenylphosphine oxide (1a)
o
Orange crystals (1.02 g, 32%); mp. 162–164 C (Lit.3e mp.
o
155–156 C). IR (KBr) ν (cm-1) 3055, 2923, 2073, 1594, 1493,
1
1438, 1196, 1117, 1099, 951. H NMR (400 MHz, CDCl3) δ 7.82
(m, 4H), 7.60 – 7.54 (m, 2H), 7.53 – 7.46 (m, 4H), 7.29 – 7.21 (m,
4H), 7.11 – 7.06 (m, 1H). 13C NMR (101 MHz, CDCl3) δ 132.6 (d,
J = 2.4 Hz), 131.8 (d, J = 10.2 Hz), 130.8 (d, J = 113.2 Hz), 129.2,
128.9 (d, J = 12.9 Hz), 127.2 (d, J = 7.6 Hz), 125.3, 123.8 (d, J =
3.5 Hz), 52.8 (d, J = 119.1 Hz). 31P NMR (162 MHz, CDCl3) δ 26.64.
HRMS (ESI) calcd for C19H16N2OP+ [M+H]+ m/z: 319.0995; found
319.0990.
Experimental
General Information
Melting points were measured on a melting point apparatus
and are uncorrected. H, 13C, 31P, and 19F NMR spectra were
recorded on a 400 MHz NMR spectrometer. Chemical shifts are
reported in ppm and referenced to tetramethylsilane (TMS) as
internal standards (for CDCl3, tetramethylsilane 0 ppm for H
and CDCl3 77.00 ppm for 13C). IR spectra (KBr pellets, v (cm−1))
were taken on an FT-IR spectrometer. The high-resolution mass
spectra were obtained under ESI ionization using an LC/MSD
TOF mass spectrometer. Microwave reactions were performed
1
General Procedure for the Synthesis of
δ-Phospholactones 3
1
Diazo compound (0.2 mmol) and aldehydes
1
2
(0.8 mmol)
were added into an 8 mL microwave tube. The tube was
charged with N2 and added 3 mL of dry PhCl. The resultant
mixture was stirred in a microwave reactor for 10 min at 150 °C.
After cooling to room temperature, PhCl was removed and the
residue was subjected to flash column chromatography
(PE:CH2Cl2 = 5:1, v/v to PE:EA = 5:1, v/v to PE:EA = 1:1, v/v) to
with
a
CEM Discover microwave reactor. Column
chromatography was carried out on silica gel (200−300 mesh)
with a mixture of petroleum ether (PE, 60 °C−90 °C) and ethyl
acetate (EA) as the eluent. All reactions were followed by thin-
layer chromatography (TLC) where practical, using silica gel 60
F254 fluorescent treated silica gel plates, which were visualized
under UV light (254 nm). Commercial-grade reagents and
solvents were used without further purification unless
otherwise noted, anhydrous solvent was purified with the
standard process. Liquid aldehydes were washed with saturated
NaHCO3 for several times and dried over anhydrous Na2SO4
afford alkenes 4 and phospholactones 3.
rel-(1R,3R,4S)-1-(4-Chlorophenyl)-3,4-diphenyl-1,4-
dihydrobenzo[d][1,2]oxaphosphinine 3-oxide (3a)
o
Colorless crystals (56 mg, 66%). mp. 263–265 C (Lit.3e mp.
o
243–245 C). IR (KBr) ν (cm-1) 3059, 2845, 1599, 1233, 1121,
1090, 980, 804. 1H NMR(400 MHz, CDCl3) δ 7.52 – 7.41 (m, 5H),
7.37 – 7.28 (m, 2H), 7.27 – 7.18 (m, 4H), 7.18 – 7.07 (m, 4H),
6.88 – 6.82 (m, 2H), 6.78 (d, J = 7.4 Hz, 1H), 6.74 (d, J = 5.9 Hz,
1H), 4.80 (d, J = 24.6 Hz, 1H). 13C NMR (101 MHz, CDCl3) δ 137.2
(d, J = 6.3 Hz), 137.0 (d, J = 9.3 Hz), 134.8, 134.5 (d, J = 4.5 Hz),
134.2 (d, J = 5.1 Hz), 132.7, 132.6, 130.3 (d, J = 5.3 Hz), 129.8 (d,
J = 9.2 Hz), 129.7, 129.0, 128.7, 128.4, 128.3 (d, J = 140.6 Hz),
128.0 (d, J = 13.3 Hz), 127.3 (d, J = 2.5 Hz), 127.1, 126.8, 78.0 (d,
J = 6.0 Hz), 49.4 (d, J = 81.0 Hz). 31P NMR (162 MHz, CDCl3) δ
35.58. HRMS (ESI) calculated for C26H21ClO2P+ [M+H]+ 431.0962,
found 431.0964.
before using. (diazo)arylmethyl(diaryl)phosphine oxide
in this work were synthesized according the method from
reported procedures.3e,12,13
1 used
Procedure
for
the
Synthesis
of
(Diazo)phenylmethyl(diphenyl)phosphine oxide (1a).
Benzaldazine13 (5 mmol, 0.75 g) and diphenylphosphine oxide
(10 mmol, 2.02 g) were dissolved in 40 mL of toluene. The
solution was stirred at room temperature overnight and a large
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Organic & Biomolecular Chemistry
Page 6 of 12
ARTICLE
Journal Name
rel-(1R,3R,4S)-1-(4-Bromophenyl)-3,4-diphenyl-1,4-
132.7 (d, J = 9.3 Hz), 132.4 (d, J = 2.4 Hz), 130.3 (d, J = 5.3 Hz),
View Article Online
dihydrobenzo[d][1,2]oxaphosphinine 3-oxide (3b)
129.9 (d, J = 9.1 Hz), 128.42 (d, J = 139.9 DHOz)I:, 1102.180.3396/D, 102O8B.0320(d11,GJ
o
Colorless crystals (58 mg, 61%). mp. 238–239 C. IR (KBr) ν = 1.8 Hz), 127.9 (d, J = 13.2 Hz), 127.2, 127.1 (d, J = 2.6 Hz), 127.0,
(cm-1) 3060, 2844, 1490, 1455, 1438, 1233, 1122, 978, 890. H 126.8, 78.7 (d, J = 6.2 Hz), 49.4 (d, J = 81.4 Hz), 33.9, 23.9. 31P
1
NMR(400 MHz, CDCl3) δ 7.63 (d, J = 7.7 Hz, 2H), 7.49 – 7.39 (m, NMR (162 MHz, CDCl3) δ 35.50. HRMS (ESI) calcd for C29H28O2P+
3H), 7.37 – 7.29 (m, 2H), 7.28 – 7.08 (m, 8H), 6.85 (d, J = 6.8 Hz, [M+H]+ m/z: 439.1821; found 439.1826.
2H), 6.78 (d, J = 7.4 Hz, 1H), 6.72 (d, J = 5.7 Hz, 1H), 4.80 (d, J =
24.5 Hz, 1H). 13C NMR (101 MHz, CDCl3) δ 137.6 (d, J = 9.1 Hz), rel-(1R,3R,4S)-1-(4-Methoxyphenyl)-3,4-diphenyl-1,4-
137.1 (d, J = 6.2 Hz), 134.6 (d, J = 4.6 Hz), 134.2 (d, J = 5.0 Hz), dihydrobenzo[d][1,2]oxaphosphinine 3-oxide (3f)
o
132.7, 132.6, 132.0, 130.3 (d, J = 5.3 Hz), 130.0, 129.9 (d, J = 9.2
Colorless crystals (40 mg, 47%). mp. 243–244 C (Lit.3e mp.
Hz), 128.7, 128.4 (d, J = 1.6 Hz), 128.2 (d, J = 140.1 Hz), 128.0 (d, 271 oC). 1H NMR (400 MHz, CDCl3) δ 7.50 – 7.45 (m, 2H), 7.44 –
J = 13.3 Hz), 127.3 (d, J = 2.5 Hz), 127.1, 126.8, 123.0, 78.0 (d, J 7.40 (m, 1H), 7.37 – 7.32 (m, 2H), 7.26 – 7.09 (m, 8H), 7.04 –
= 5.9 Hz), 49.5 (d, J = 81.2 Hz). 31P NMR (162 MHz, CDCl3) δ 35.58. 7.00 (m, 2H), 6.91 – 6.82 (m, 3H), 6.71 (d, J = 5.5 Hz, 1H), 4.77
HRMS (ESI) calcd for C26H21BrO2P+ [M+H]+ m/z: 475.0457; found (d, J = 24.0 Hz, 1H), 3.87 (s, 3H). 31P NMR (162 MHz, CDCl3) δ
475.0461.
35.43. HRMS (ESI) calculated for C27H24O3P+ [M+H]+ 427.1458,
found 427.1454.
rel-(1R,3R,4S)-1-(4-Fluorophenyl)-3,4-diphenyl-1,4-
dihydrobenzo[d][1,2]oxaphosphinine 3-oxide (3c)
Colorless crystals (46 mg, 55%). mp. 218–219 C. IR (KBr) ν dihydrobenzo[d][1,2]oxaphosphinin-1-yl)benzonitrile (3g)
(cm-1) 3062, 2848, 1511, 1231, 1157, 1121, 978, 888. H NMR
rel-(1R,3R,4S)-4-(3-Oxido-3,4-diphenyl-1,4-
o
1
o
Colorless crystals (40 mg, 48%). mp. 274–275 C. IR (KBr) ν
(400 MHz, CDCl3) δ 7.58 – 7.50 (m, 2H), 7.48 – 7.40 (m, 1H), 7.37 (cm-1) 3061, 2925, 2851, 2229, 1599, 1439, 1233, 1121, 986, 863.
– 7.29 (m, 2H), 7.28 – 7.08 (m, 10H), 6.86 (d, J = 6.7 Hz, 2H), 6.79 1H NMR (400 MHz, CDCl3) δ 7.81 (d, J = 7.6 Hz, 2H), 7.69 (d, J =
(d, J = 7.5 Hz, 1H), 6.75 (d, J = 5.8 Hz, 1H), 4.80 (d, J = 24.5 Hz, 7.6 Hz, 2H), 7.53 – 7.42 (m, 1H), 7.36 – 7.21 (m, 6H), 7.20 – 7.10
1H). 13C NMR (101 MHz, CDCl3) δ 162.9 (d, JC-F = 248.1 Hz), 137.4 (m, 4H), 6.89 – 6.78 (m, 3H), 6.71 (d, J = 7.6 Hz, 1H), 4.84 (d, J =
(d, J = 6.3 Hz), 134.7 (d, J = 4.5 Hz), 134.5 (d, J = 3.1 Hz), 134.4 (d, 24.9 Hz, 1H). 13C NMR (101 MHz, CDCl3) δ 143.4 (d, J = 9.2 Hz),
J = 3.2 Hz), 134.2 (d, J = 5.2 Hz), 132.7, 132.6, 132.6 (d, J = 2.7 136.5 (d, J = 6.2 Hz), 134.3 (d, J = 5.1 Hz), 134.1 (d, J = 4.6 Hz),
Hz), 130.3 (d, J = 5.3 Hz), 130.2 (d, J = 8.3 Hz), 129.9 (d, J = 9.1 132.8 (d, J = 2.3 Hz), 132.7, 132.6, 130.3 (d, J = 5.3 Hz), 129.9 (d,
Hz), 128.7, 128.4 (d, J = 1.7 Hz), 128.3 (d, JC-P = 140.1 Hz), 128.0 J = 8.9 Hz), 129.0, 128.9, 128.5 (d, J = 1.8 Hz), 128.1 (d, J = 13.3
(d, J = 13.3 Hz), 127.3 (d, J = 2.7 Hz), 127.1, 126.9, 115.8 (d, J = Hz), 128.0 (d, J = 141.2 Hz), 127.4 (d, J = 2.6 Hz), 127.3, 126.4,
21.7 Hz), 78.0 (d, J = 6.0 Hz), 49.4 (d, J = 81.2 Hz). 19F NMR (377 118.4, 112.9, 77.6 (d, J = 5.9 Hz), 49.5 (d, J = 80.8 Hz). 31P NMR
MHz, CDCl3) δ -112.50. 31P NMR (162 MHz, CDCl3) δ 35.60. (162 MHz, CDCl3)
δ 35.81. HRMS (ESI) calculated for
HRMS (ESI) calculated for C26H21FO2P+ [M+H]+ 415.1258, found C27H21NO2P+ [M+H]+ 422.1304, found 422.1312.
415.1264.
rel-(1R,3R,4S)-1-(4-Nitrophenyl)-3,4-diphenyl-1,4-
rel-(1R,3R,4S)-1-(4-Methylphenyl)-3,4-diphenyl-1,4-
dihydrobenzo[d][1,2]oxaphosphinine 3-oxide (3h)
dihydrobenzo[d][1,2]oxaphosphinine 3-oxide (3d)
Yellow crystals (41 mg, 46%). mp. 277–278 oC. IR (KBr) ν (cm-
o
Colorless crystals (52 mg, 63%). mp. 272–273 C (Lit.3e mp. 1) 3361, 2975, 2894, 1523, 1349, 1266, 1232, 1089, 1049, 880,
241–242 oC). IR (KBr) ν (cm-1) 3060, 2920, 1439, 1232, 1121, 976. 858. 1H NMR (400 MHz, CDCl3) δ 8.37 (d, J = 7.8 Hz, 2H), 7.77 (t,
1H NMR (400 MHz, CDCl3) δ 7.47 – 7.40 (m, 3H), 7.38 – 7.27 (m, J = 13.8 Hz, 2H), 7.54 – 7.43 (m, 1H), 7.37 – 7.11 (m, 10H), 6.86
4H), 7.26 – 7.06 (m, 8H), 6.91 – 6.80 (m, 3H), 6.72 (d, J = 5.6 Hz, (t, J = 8.0 Hz, 3H), 6.71 (d, J = 7.6 Hz, 1H), 4.86 (d, J = 25.0 Hz,
1H), 4.79 (d, J = 24.2 Hz, 1H), 2.43 (s, 3H). 13C NMR (101 MHz, 1H). 13C NMR (101 MHz, CDCl3) δ 148.2, 145.2 (d, J = 9.2 Hz),
CDCl3) δ 138.8, 137.7 (d, J = 6.2 Hz), 135.7 (d, J = 9.2 Hz), 135.0 136.4 (d, J = 6.2 Hz), 134.3 (d, J = 5.2 Hz), 134.0 (d, J = 4.4 Hz),
(d, J = 4.6 Hz), 134.1 (d, J = 5.2 Hz), 132.7 (d, J = 9.2 Hz), 132.5 (d, 132.9 (d, J = 2.1 Hz), 132.7 (d, J = 9.3 Hz), 130.4 (d, J = 5.3 Hz),
J = 2.0 Hz), 130.3 (d, J = 5.3 Hz), 129.8 (d, J = 9.2 Hz), 129.4, 129.9 (d, J = 8.9 Hz), 129.12, 129.08, 128.5 (d, J = 1.5 Hz), 128.1
128.44 (d, J = 140.1 Hz), 128.4, 128.3, 127.9 (d, J = 13.3 Hz), (d, J = 13.3 Hz), 127.9 (d, J = 139.8 Hz), 127.5 (d, J = 2.5 Hz), 127.3,
127.1, 127.0, 78.7 (d, J = 6.2 Hz), 49.4 (d, J = 81.3 Hz), 21.3. 31
P
126.4, 124.0, 77.4 (d, J = 6.2 Hz), 49.5 (d, J = 80.8 Hz). 31P NMR
NMR (162 MHz, CDCl3) δ 35.48. HRMS (ESI) calculated for (162 MHz, CDCl3) δ 35.88. HRMS (ESI) calcd for C26H21NO4P+
C27H24O2P+ [M+H]+ 411.1508, found 411.1502.
[M+H]+ m/z: 442.1203; found 442.1208.
rel-(1R,3R,4S)-1-(4-Isopropylphenyl)-3,4-diphenyl-1,4-
dihydrobenzo[d][1,2]oxaphosphinine 3-oxide (3e)
rel-(1S,3R,4S)-1-(2-Fluorophenyl)-3,4-diphenyl-1,4-
dihydrobenzo[d][1,2]oxaphosphinine 3-oxide (3i)
o
o
1
Colorless crystals (57 mg, 65%). mp. 123–125 C. 1H NMR
Colorless crystals (51 mg, 62%). mp. 251–252 C. H NMR
(400 MHz, CDCl3) δ 7.51 – 7.44 (m, 2H), 7.44 – 7.32 (m, 5H), 7.29 (400 MHz, CDCl3) δ 7.61 (td, J = 7.5, 1.5 Hz, 1H), 7.50 – 7.42 (m,
– 7.05 (m, 8H), 6.90 – 6.84 (m, 3H), 6.74 (d, J = 5.6 Hz, 1H), 4.79 2H), 7.40 – 7.08 (m, 12H), 7.04 (d, J = 6.5 Hz, 1H), 6.91 – 6.81 (m,
(d, J = 23.9 Hz, 1H), 2.97 (h, J = 6.9 Hz, 1H), 1.31 (s, 3H), 1.30 (s, 3H), 4.83 (d, J = 25.6 Hz, 1H). 13C NMR (101 MHz, CDCl3) δ 160.5
3H). 13C NMR (101 MHz, CDCl3) δ 149.6, 137.7 (d, J = 6.3 Hz), (d, JC-F = 249.0 Hz), 136.8 (d, J = 5.8 Hz), 134.3 (d, J = 5.0 Hz),
136.0 (d, J = 9.0 Hz), 135.2 (d, J = 5.0 Hz), 134.1 (d, J = 5.2 Hz), 134.2 (d, J = 4.6 Hz), 132.9 (d, J = 9.3 Hz), 132.7 (d, J = 2.9 Hz),
6 | J. Name., 2012, 00, 1-3
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Organic & Biomolecular Chemistry
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ARTICLE
130.8 (d, J = 8.3 Hz), 130.6 (d, J = 5.5 Hz), 129.8 (d, J = 3.4 Hz), 140.0 Hz), 128.7, 128.5 (d, J = 8.3 Hz), 128.3 (d, J = 1.4 Hz), 128.2,
View Article Online
DOI: 10.1039/D0OB02011G
127.9 (d, J = 13.3 Hz), 127.2 (d, J = 2.3 Hz), 126.9, 126.6 (d, J =
129.5 (d, J = 8.9 Hz), 128.7, 128.5 (d, J = 2.6 Hz), 128.4 (d, JC-P
=
140.5 Hz), 128.1 (d, J = 13.2 Hz), 127.4 (d, J = 3.2 Hz), 127.3, 9.4 Hz), 126.3, 121.0, 110.7, 73.1 (d, J = 5.7 Hz), 55.5, 49.9 (d, J
126.1, 125.8 (dd, JC-F, C-P = 12.8, 9.6 Hz), 124.8 (d, J = 3.6 Hz), = 79.8 Hz). 31P NMR (162 MHz, CDCl3) δ 34.84. HRMS (ESI) calcd
115.9 (d, J = 21.2 Hz), 73.3 (dd, JC-P, C-F = 5.9, 3.6 Hz), 49.7 (d, J = for C27H24O3P+ [M+H]+ m/z: 427.1458; found 427.1466.
80.5 Hz). 31P NMR (162 MHz, CDCl3) δ 35.60. 19F NMR (377 MHz,
CDCl3) δ -116.07. HRMS (ESI) calculated for C26H21FO2P+ [M+H]+ rel-(1R,3R,4S)-1-(3-Chlorophenyl)-3,4-diphenyl-1,4-
415.1258, found 415.1262.
dihydrobenzo[d][1,2]oxaphosphinine 3-oxide (3n)
o
Colorless crystals (41 mg, 48%). mp. 209–210 C. IR (KBr) ν
1
rel-(1S,3R,4S)-1-(2-Chlorophenyl)-3,4-diphenyl-1,4-
dihydrobenzo[d][1,2]oxaphosphinine 3-oxide (3j)
(cm-1) 3062, 2848, 1438, 1233, 1121, 983, 866. H NMR (400
MHz, CDCl3) δ 7.55 (s, 1H), 7.49 – 7.41 (m, 4H), 7.38 – 7.29 (m,
o
1
Colorless crystals (59 mg, 70%). mp. 268–269 C. H NMR 2H), 7.29 – 7.19 (m, 4H), 7.19 – 7.09 (m, 4H), 6.85 (d, J = 6.6 Hz,
(400 MHz, CDCl3) δ 7.72 – 7.66 (m, 1H), 7.53 – 7.09 (m, 15H), 2H), 6.80 (d, J = 7.3 Hz, 1H), 6.73 (d, J = 5.9 Hz, 1H), 4.81 (d, J =
6.91 – 6.84 (m, 2H), 6.77 – 6.70 (m, 1H), 4.91 (d, J = 27.6 Hz, 1H). 24.7 Hz, 1H). 13C NMR (101 MHz, CDCl3) δ 140.4 (d, J = 9.2 Hz),
13C NMR (101 MHz, CDCl3) δ 136.8 (d, J = 5.3 Hz), 135.9 (d, J = 137.0 (d, J = 6.3 Hz), 134.7, 134.5 (d, J = 4.6 Hz), 134.2 (d, J = 5.1
9.8 Hz), 134.7 (d, J = 4.8 Hz), 133.3, 133.0 (d, J = 9.5 Hz), 132.7 Hz), 132.7, 132.6, 130.3 (d, J = 5.3 Hz), 130.0, 129.8 (d, J = 9.1
(d, J = 1.9 Hz), 130.8 (d, J = 5.6 Hz), 129.9, 129.5, 128.7, 128.6 (d, Hz), 129.1, 128.7, 128.4 (d, J = 1.8 Hz), 128.3, 128.2 (d, J = 140.2
J = 140.5 Hz), 128.4 (d, J = 2.5 Hz), 128.1 (d, J = 13.4 Hz), 127.52, Hz), 128.0 (d, J = 13.3 Hz), 127.3 (d, J = 2.6 Hz), 127.2, 126.8,
127.47 (d, J = 2.6 Hz), 127.1, 126.2, 75.1 (d, J = 5.4 Hz), 50.0 (d, 126.5, 77.9 (d, J = 5.9 Hz), 49.4 (d, J = 81.0 Hz). 31P NMR (162
J = 79.2 Hz). 31P NMR (162 MHz, CDCl3) δ 34.95. HRMS (ESI) calcd MHz, CDCl3) δ 35.66. HRMS (ESI) calcd for C26H21ClO2P+ [M+H]+
for C26H21ClO2P+ [M+H]+ m/z: 431.0962; found 431.0970.
m/z: 431.0962; found 431.0973.
rel-(1S,3R,4S)-1-(2-bromophenyl)-3,4-diphenyl-1,4-
dihydrobenzo[d][1,2]oxaphosphinine 3-oxide (3k)
rel-(1R,3R,4S)-1-(3-Bromophenyl)-3,4-diphenyl-1,4-
dihydrobenzo[d][1,2]oxaphosphinine 3-oxide (3o)
o
1
o
1
Colorless crystals (62 mg, 65%). mp. 273–274 C. H NMR
Colorless crystals (60 mg, 63%). mp. 235–236 C. H NMR
(400 MHz, CDCl3) δ 7.72 – 7.65 (m, 2H), 7.52 – 7.42 (m, 2H), 7.36 (400 MHz, CDCl3) δ 7.70 (s, 1H), 7.58 (d, J = 7.9 Hz, 1H), 7.51 –
– 7.15 (m, 10H), 7.14 – 7.08 (m, 2H), 6.91 – 6.85 (m, 2H), 6.72 7.40 (m, 2H), 7.39 – 7.07 (m, 11H), 6.90 – 6.81 (m, 2H), 6.79 (d,
(d, J = 7.4 Hz, 1H), 4.92 (d, J = 27.9 Hz, 1H). 31P NMR (162 MHz, J = 7.1 Hz, 1H), 6.73 (d, J = 5.9 Hz, 1H), 4.84 (d, J = 24.8 Hz, 1H).
CDCl3) δ 34.78. HRMS (ESI) calcd for C26H21BrO2P+ [M+H]+ m/z: 13C NMR (101 MHz, CDCl3) δ 140.7 (d, J = 9.2 Hz), 137.0 (d, J =
475.0457; found 475.0450.
6.2 Hz), 134.5 (d, J = 4.8 Hz), 134.2 (d, J = 5.2 Hz), 132.74, 132.65,
132.1, 131.2, 130.4, 130.3 (d, J = 1.9 Hz), 129.8 (d, J = 9.0 Hz),
128.8, 128.4 (d, J = 2.7 Hz), 128.1 (d, J = 140.2 Hz), 128.0 (d, J =
13.3 Hz), 127.3 (d, J = 3.2 Hz), 127.2 (d, J = 0.4 Hz), 127.0, 126.8
rel-(1R,3R,4S)-1-(2-Methylphenyl)-3,4-diphenyl-1,4-
dihydrobenzo[d][1,2]oxaphosphinine 3-oxide (3l)
Colorless crystals (54 mg, 66%). mp. 281–282 C. H NMR (d, J = 0.9 Hz), 122.8, 77.9 (d, J = 6.2 Hz), 49.4 (d, J = 81.0 Hz). 31
P
o
1
(400 MHz, CDCl3) δ 7.61 – 7.54 (m, 1H), 7.46 (t, J = 7.4 Hz, 1H), NMR (162 MHz, CDCl3) δ 35.65. HRMS (ESI) calcd for
7.37 – 7.10 (m, 13H), 6.96 (d, J = 7.2 Hz, 1H), 6.88 (d, J = 7.6 Hz, C26H21BrO2P+ [M+H]+ m/z: 475.0457; found 475.0467.
2H), 6.72 (d, J = 7.6 Hz, 1H), 4.89 (d, J = 26.7 Hz, 1H), 2.40 (s, 3H).
13C NMR (101 MHz, CDCl3) δ 137.3 (d, J = 5.4 Hz), 136.4 (d, J = rel-(1R,3R,4S)-1-(3-Methylphenyl)-3,4-diphenyl-1,4-
8.3 Hz), 136.2, 134.9 (d, J = 4.9 Hz), 133.8 (d, J = 4.5 Hz), 132.9 dihydrobenzo[d][1,2]oxaphosphinine 3-oxide (3p)
o
1
(d, J = 9.1 Hz), 132.6 (d, J = 2.8 Hz), 130.7 (d, J = 5.6 Hz), 130.5,
Colorless crystals (33 mg, 56%). mp. 192–193 C. H NMR
128.9 (d, J = 8.5 Hz), 128.7 (d, J = 141.3 Hz), 128.6 (d, J = 4.8 Hz), (400 MHz, CDCl3) δ 7.44 (td, J = 7.5, 1.3 Hz, 1H), 7.40 – 7.31 (m,
128.4 (d, J = 2.5 Hz), 128.1, 128.0, 127.3 (d, J = 3.1 Hz), 127.0, 5H), 7.28 – 7.07 (m, 9H), 6.91 – 6.85 (m, 2H), 6.83 (d, J = 7.2 Hz,
126.6, 126.5, 75.5 (d, J = 5.0 Hz), 49.9 (d, J = 79.8 Hz), 19.5. 31
P
1H), 6.72 (d, J = 5.9 Hz, 1H), 4.82 (d, J = 24.6 Hz, 1H), 2.43 (s, 3H).
NMR (162 MHz, CDCl3) δ 35.33. HRMS (ESI) calcd for C27H24O2P+ 13C NMR (101 MHz, CDCl3) δ 138.4, 138.4 (d, J = 9.0 Hz), 137.8
[M+H]+ m/z: 411.1508; found 411.1519.
(d, J = 6.2 Hz), 134.8 (d, J = 4.7 Hz), 134.2 (d, J = 5.2 Hz), 132.8 (d,
J = 9.3 Hz), 132.5 (d, J = 2.9 Hz), 130.4 (d, J = 5.4 Hz), 129.7 (d, J
= 9.1 Hz), 129.6, 129.0, 128.6, 128.44, 128.41 (d, J = 140.3 Hz),
128.3 (d, J = 2.6 Hz), 127.9 (d, J = 13.4 Hz), 127.2 (d, J = 3.1 Hz),
rel-(1S,3R,4S)-1-(2-Methoxyphenyl)-3,4-diphenyl-1,4-
dihydrobenzo[d][1,2]oxaphosphinine 3-oxide (3m)
o
Colorless crystals (65 mg, 76%). mp. 235–236 C. IR (KBr) ν 127.1 (d, J = 0.9 Hz), 127.0, 125.4, 78.8 (d, J = 6.3 Hz), 49.4 (d, J
(cm-1) 3062, 2938, 2839, 1602, 1494, 1438, 1249, 1232, 1122, = 81.1 Hz), 21.5. 31P NMR (162 MHz, CDCl3) δ 35.56. HRMS (ESI)
1
979, 907. H NMR (400 MHz, CDCl3) δ 7.58 (dd, J = 7.6, 1.6 Hz, calcd for C27H24O2P+ [M+H]+ m/z: 411.1508; found 411.1497.
1H), 7.47 – 7.38 (m, 2H), 7.37 – 7.30 (m, 2H), 7.27 – 7.14 (m, 8H),
7.11 – 7.05 (m, 2H), 7.01 (d, J = 7.4 Hz, 1H), 6.91 – 6.85 (m, 2H), rel-(1R,3R,4S)-1-(3-Methoxyphenyl)-3,4-diphenyl-1,4-
6.78 (dd, J = 8.3, 6.8 Hz, 1H), 4.85 (d, J = 26.9 Hz, 1H), 3.84 (s, dihydrobenzo[d][1,2]oxaphosphinine 3-oxide (3q)
o
3H). 13C NMR (101 MHz, CDCl3) δ 156.8, 138.0 (d, J = 5.3 Hz),
Colorless crystals (46 mg, 54%). mp. 175–176 C. IR (KBr) ν
134.5 (d, J = 4.7 Hz), 133.8 (d, J = 4.4 Hz), 132.9 (d, J = 9.2 Hz), (cm-1) 3061, 2837, 1599, 1493, 1438, 1231, 1121, 986, 927, 927,
132.4 (d, J = 2.0 Hz), 130.7 (d, J = 5.4 Hz), 129.8, 128.9 (d, J = 877. 1H NMR (400 MHz, CDCl3) δ 7.47 – 7.30 (m, 4H), 7.27 – 7.07
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(m, 10H), 7.01 – 6.97 (m, 1H), 6.89 – 6.83 (m, 3H), 6.72 (d, J = 37.89. HRMS (ESI) calcd for C26H20Cl2O2P+ [M+H]+ m/z: 465.0572;
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5.7 Hz, 1H), 4.79 (d, J = 24.3 Hz, 1H), 3.84 (s, 3H). 13C NMR (101 found 465.0581.
DOI: 10.1039/D0OB02011G
MHz, CDCl3) δ 159.8, 140.0 (d, J = 9.1 Hz), 137.5 (d, J = 6.3 Hz),
134.9 (d, J = 4.6 Hz), 134.0 (d, J = 5.1 Hz), 132.7 (d, J = 9.2 Hz), rel-(1R,3R,4S)-1-Mesityl-3,4-diphenyl-1,4-
132.5 (d, J = 2.1 Hz), 130.3 (d, J = 5.3 Hz), 129.8, 129.7, 128.5, dihydrobenzo[d][1,2]oxaphosphinine 3-oxide (3u)
o
1
128.4 (d, J = 140.2 Hz), 128.3 (d, J = 1.7 Hz), 127.9 (d, J = 13.2
Colorless crystals (63 mg, 72%). mp. 264–265 C. H NMR
Hz), 127.2 (d, J = 2.7 Hz), 127.0 (d, J = 4.8 Hz), 120.6, 114.1 (d, J (400 MHz, CDCl3) δ 7.44 – 7.35 (m, 3H), 7.27 – 7.06 (m, 9H), 6.95
= 3.4 Hz), 78.6 (d, J = 6.1 Hz), 55.3, 49.4 (d, J = 81.2 Hz). 31P NMR (s, 2H), 6.91 – 6.86 (m, 2H), 6.83 (d, J = 7.6 Hz, 1H), 4.87 (d, J =
(162 MHz, CDCl3) δ 35.43. HRMS (ESI) calcd for C27H24O3P+ 27.1 Hz, 1H), 2.42 (s, 3H), 2.33 (s, 3H), 2.30 (s, 3H). 13C NMR (101
[M+H]+ m/z: 427.1458; found 427.1448.
MHz, CDCl3) δ 138.3 (d, J = 11.7 Hz), 137.1, 137.0 (d, J = 4.6 Hz),
135.2 (d, J = 4.4 Hz), 134.4 (d, J = 4.7 Hz), 132.6 (d, J = 9.4 Hz),
132.4 (d, J = 2.8 Hz), 131.1, 130.7 (d, J = 5.5 Hz), 130.2 (d, J = 8.4
Hz), 129.2 (d, J = 9.0 Hz), 129.1, 128.40 (d, J = 140.9 Hz), 128.4,
rel-(1R,3R,4S)-1,3,4-Triphenyl-1,4-
dihydrobenzo[d][1,2]oxaphosphinine 3-oxide (3r) 6
Colorless crystals (45 mg, 56%). mp. 265–266 oC (Sub.) (Lit.6 128.3 (d, J = 2.6 Hz), 127.9 (d, J = 13.4 Hz), 127.1, 125.5 (d, J =
mp. 254–257 oC). IR (KBr) ν (cm-1) 3060, 2844, 1231, 1121, 976, 1.1 Hz), 74.4 (d, J = 6.3 Hz), 49.8 (d, J = 80.0 Hz), 21.9, 20.9, 20.5.
887, 848. 1H NMR (400 MHz, CDCl3) δ 7.56 (d, J = 7.5 Hz, 2H), 31P NMR (162 MHz, CDCl3) δ 37.24. HRMS (ESI) calcd for
7.52 – 7.39 (m, 4H), 7.39 – 7.30 (m, 2H), 7.28 – 7.06 (m, 8H), C29H28O2P+ [M+H]+ m/z: 439.1821; found 439.1816.
6.87 (d, J = 6.6 Hz, 2H), 6.81 (d, J = 7.5 Hz, 1H), 6.76 (d, J = 5.7
Hz, 1H), 4.81 (d, J = 24.5 Hz, 1H). 13C NMR (101 MHz, CDCl3) δ rel-(1R,3R,4S)-1-(2,4-Dichlorophenyl)-3,4-diphenyl-1,4-
138.5 (d, J = 9.0 Hz), 137.6 (d, J = 6.3 Hz), 134.8 (d, J = 4.5 Hz), dihydrobenzo[d][1,2]oxaphosphinine 3-oxide (3v)
o
1
134.2 (d, J = 5.0 Hz), 132.7 (d, J = 9.2 Hz), 132.5 (d, J = 2.1 Hz),
Colorless crystals (51 mg, 55%). mp. 294–295 C. H NMR
130.4 (d, J = 5.3 Hz), 129.7 (d, J = 9.1 Hz), 128.9, 128.7, 128.5, (400 MHz, CDCl3) δ 7.62 (d, J = 8.4 Hz, 1H), 7.54 (d, J = 2.1 Hz,
128.4 (d, J = 140.2 Hz), 128.3, 128.0, 127.9, 127.2 (d, J = 2.5 Hz), 1H), 7.52 – 7.45 (m, 1H), 7.42 – 7.38 (m, 1H), 7.33 – 7.08 (m,
127.0, 78.7 (d, J = 6.1 Hz), 49.5 (d, J = 81.1 Hz). 31P NMR (162 11H), 6.91 – 6.82 (m, 2H), 6.71 (d, J = 7.1 Hz, 1H), 4.90 (d, J =
MHz, CDCl3) δ 35.50.
27.6 Hz, 1H). 13C NMR (101 MHz, CDCl3) δ 136.3 (d, J = 5.1 Hz),
135.2, 134.7 (d, J = 4.4 Hz), 134.6, 134.0, 132.9 (d, J = 9.4 Hz),
132.8 (d, J = 3.8 Hz), 130.7 (d, J = 5.6 Hz), 130.2, 129.3, 128.9,
128.7 (d, J = 8.3 Hz), 128.5 (d, J = 2.4 Hz), 128.4 (d, J = 140.4 Hz),
rel-(1R,3R,4S)-1-(Naphthalen-2-yl)-3,4-diphenyl-1,4-
dihydrobenzo[d][1,2]oxaphosphinine 3-oxide (3s)
Colorless crystals (48 mg, 54%). mp. 214–215 C (Lit.3e mp. 128.2, 128.0 (d, J = 11.6 Hz), 127.5 (d, J = 3.0 Hz), 127.2, 126.0,
o
o
248-249 C). IR (KBr) ν (cm-1) 3060, 2848, 1599, 1439, 1232, 74.7 (d, J = 5.2 Hz), 49.9 (d, J = 79.2 Hz). 31P NMR (162 MHz,
1121, 986, 950, 905, 813. H NMR (400 MHz, CDCl3) δ 8.02 (s, CDCl3) δ 35.03. HRMS (ESI) calcd for C26H20Cl2O2P+ [M+H]+ m/z:
1
1H), 7.96 (d, J = 8.4 Hz, 1H), 7.93 – 7.86 (m, 2H), 7.64 (dd, J = 8.8, 465.0572; found 465.0568.
2.0 Hz, 1H), 7.57 – 7.51 (m, 2H), 7.46 – 7.36 (m, 3H), 7.28 – 7.21
(m, 3H), 7.19 – 7.10 (m, 5H), 6.96 – 6.88 (m, 3H), 6.81 (d, J = 8.0 rel-(1R,3R,4S)-3,4-Diphenyl-1-(pyridin-2-yl)-1,4-
Hz, 1H), 4.86 (d, J = 24.6 Hz, 1H). 13C NMR (101 MHz, CDCl3) δ dihydrobenzo[d][1,2]oxaphosphinine 3-oxide (3w)
137.5 (d, J = 6.2 Hz), 135.7 (d, J = 9.2 Hz), 134.7 (d, J = 4.7 Hz),
Yellow crystals (23 mg, 29%). mp. 244–246 oC. 1H NMR (400
134.2 (d, J = 5.2 Hz), 133.4, 133.0, 132.7 (d, J = 9.2 Hz), 132.5 (d, MHz, CDCl3) δ 8.78 – 8.73 (m, 1H), 7.84 (td, J = 7.7, 1.8 Hz, 1H),
J = 2.8 Hz), 130.4 (d, J = 5.4 Hz), 129.7 (d, J = 9.0 Hz), 128.7, 128.5, 7.65 (d, J = 7.9 Hz, 1H), 7.48 – 7.09 (m, 12H), 6.98 – 6.90 (m, 3H),
128.4 (d, J = 140.1 Hz), 128.3 (d, J = 2.5 Hz), 128.2, 128.0, 127.9 6.86 (d, J = 5.2 Hz, 1H), 4.79 (d, J = 23.8 Hz, 1H). 13C NMR (101
(d, J = 3.0 Hz), 127.8, 127.2 (d, J = 3.1 Hz), 127.1 (d, J = 8.1 Hz), MHz, CDCl3) δ 158.1 (d, J = 10.3 Hz), 149.3, 137.1, 136.4 (d, J =
126.6 (d, J = 13.9 Hz), 125.4, 78.9 (d, J = 6.2 Hz), 49.5 (d, J = 81.0 7.2 Hz), 134.8 (d, J = 4.7 Hz), 133.6 (d, J = 5.6 Hz), 132.8 (d, J =
Hz). 31P NMR (162 MHz, CDCl3) δ 35.54. HRMS (ESI) calculated 9.3 Hz), 132.6 (d, J = 2.8 Hz), 130.4 (d, J = 5.4 Hz), 129.9 (d, J =
for C30H24O2P+ [M+H]+ 447.1508, found 447.1504.
9.1 Hz), 128.5, 128.29 (d, J = 2.7 Hz), 128.25 (d, J = 140.2 Hz),
128.0, 127.9, 126.5 (d, J = 0.7 Hz), 123.4, 122.4, 79.1 (d, J = 6.2
Hz), 49.3 (d, J = 81.6 Hz). 31P NMR (162 MHz, CDCl3) δ 35.48.
HRMS (ESI) calcd for C25H21NO2P+ [M+H]+ m/z: 398.13044; found
rel-(1R,3R,4S)-1-(2,6-Dichlorophenyl)-3,4-diphenyl-1,4-
dihydrobenzo[d][1,2]oxaphosphinine 3-oxide (3t)
o
1
Colorless crystals (66 mg, 76%). mp. 264–265 C. H NMR 398.13040.
(400 MHz, Chloroform-d) δ 7.56 (d, J = 7.6 Hz, 1H), 7.52 – 7.37
(m, 5H), 7.35 – 7.18 (m, 5H), 7.17 – 7.05 (m, 4H), 6.90 (d, J = 7.3 rel-(1R,3R,4S)-1-Pentyl-3,4-diphenyl-1,4-
Hz, 2H), 6.81 (d, J = 7.5 Hz, 1H), 4.84 (d, J = 25.7 Hz, 1H). 13C NMR dihydrobenzo[d][1,2]oxaphosphinine 3-oxide (3z)
(101 MHz, Chloroform-d) δ 136.7, 136.3, 135.1 (d, J = 4.8 Hz),
Colorless liquid (24 mg, 31%). 1H NMR (400 MHz, CDCl3) δ
134.9 (d, J = 5.4 Hz), 134.7 (d, J = 4.5 Hz), 132.7 (d, J = 9.7 Hz), 7.89 –7.82 (m, 2H), 7.67 – 7.59 (m, 2H), 7.58 –7.53 (m, 1H), 7.51
132.4 (d, J = 2.9 Hz), 130.6, 130.5 (d, J = 2.6 Hz), 130.2 (d, J = 9.6 – 7.44 (m, 2H), 7.43 – 7.34 (m, 2H), 7.27 – 7.16 (m, 6H), 6.69 (d,
Hz), 128.5 (d, J = 9.3 Hz), 128.2 (d, J = 2.8 Hz), 128.0 (d, J = 141.5 J = 4.4 Hz, 1H), 2.31 – 2.12 (m, 2H), 1.40 (dt, J = 15.0, 7.5 Hz, 2H),
Hz), 127.8 (d, J = 13.5 Hz), 127.2, 127.0 (d, J = 3.3 Hz), 125.0, 73.9 1.22 – 1.13 (m, 2H), 1.12 – 1.02 (m, 2H), 0.80 (t, J = 7.2 Hz, 3H).
(d, J = 5.4 Hz), 49.5 (d, J = 80.7 Hz). 31P NMR (162 MHz, CDCl3) δ 13C NMR (101 MHz, CDCl3) δ 172.3 (d, J = 7.3 Hz), 132.9, 132.5
(d, J = 2.1 Hz), 132.4 (d, J = 2.1 Hz), 132.3, 132.2, 131.7 (d, J = 9.1
8 | J. Name., 2012, 00, 1-3
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Hz), 131.0, 130.0, 129.3, 128.7 (d, J = 4.0 Hz), 128.5 (d, J = 4.3 6.84 (d, J = 6.8 Hz, 2H), 6.76 (d, J = 7.0 Hz, 1H), 6.73 – 6.68 (m,
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DOI: 10.1039/D0OB02011G
Hz), 128.3 (d, J = 4.0 Hz), 72.8 (d, J = 85.5 Hz), 34.2, 31.1, 29.8, 3H), 6.57 (s, 1H), 4.77 (d, J = 10.1 Hz, 1H, 3ae), 4.71 (d, J = 9.4
24.5, 22.3, 13.9. 31P NMR (162 MHz, CDCl3) δ -50.00. HRMS (ESI) Hz, 1H, 3ae’), 2.27 (s, 3H, 3ae), 2.25 (s, 3H, 3ae’). 13C NMR (101
calcd for C25H28O2P+ [M+H]+ m/z: 391.1821; found 391.1822.
MHz, CDCl3) δ 137.6 (d, J = 6.9 Hz), 137.3, 137.1 (d, J = 5.6 Hz),
135.0, 133.1, 133.0, 132.9, 132.8, 131.4 (d, J = 3.4 Hz), 131.3,
130.5 (d, J = 4.9 Hz), 130.3 (d, J = 9.3 Hz), 130.0, 129.9, 129.8 (d,
J = 5.8 Hz), 129.4 (d, J = 12.3 Hz), 129.0 (d, J = 13.2 Hz), 128.7 (d,
rel-(3R,4S)-1,1,3,4-Tetraphenyl-1,4-dihydrobenzo[d][1,2]oxa-
phosphinine 3-oxide (3aa)
Yellow oil (30 mg, 32%). 1H NMR (400 MHz, CDCl3) δ 7.53 – J = 9.0 Hz), 128.5 (d, J = 4.4 Hz), 128.3 (d, J = 4.3 Hz), 128.2 (d, J
7.49 (m, 1H), 7.44 – 7.29 (m, 13H), 7.27 – 7.22 (m, 4H), 7.19 – = 4.2 Hz), 128.0, 127.9 (d, J = 7.2 Hz), 127.7 (d, J = 5.8 Hz), 127.4
7.13 (m, 1H), 7.09 – 7.05 (m, 3H), 6.85 (dd, J = 7.4, 1.6 Hz, 1H), (d, J = 2.4 Hz), 127.3, 127.0, 126.9, 78.3 (d, J = 5.7 Hz), 49.8 (d, J
6.63 – 6.58 (m, 2H), 4.36 (d, J = 30.6 Hz, 1H). 13C NMR (101 MHz, = 12.2 Hz), 49.0 (d, J = 7.4 Hz), 29.9, 21.4. 31P NMR (162 MHz,
CDCl3) δ 144.1 (d, J = 9.5 Hz), 142.5 (d, J = 2.0 Hz), 141.4 (d, J = CDCl3) δ 35.87, 35.49. HRMS (ESI) calcd for C27H23ClO2P+ [M+H]+
6.3 Hz), 134.9 (d, J = 4.5 Hz), 133.2 (d, J = 9.2 Hz), 132.6 (d, J = m/z: 445.1119; found 445.1120.
2.8 Hz), 132.0 (d, J = 4.8 Hz), 131.3 (d, J = 5.9 Hz), 131.2, 129.8,
129.3 (d, J = 1.8 Hz), 128.9 (d, J = 2.4 Hz), 128.6, 128.5, 128.4, rel-(1R,3R,4S)-1,3,4-Tris(4-chlorophenyl)-1,4-
128.40, 128.39, 128.4, 128.3, 128.2, 127.6 (d, J = 2.7 Hz), 126.7 dihydrobenzo[d][1,2]oxaphosphinine 3-oxide (3ag) and
(d, J = 1.6 Hz), 91.9 (d, J = 8.7 Hz), 50.4 (d, J = 77.0 Hz). 31P NMR (1R,3R,4S)-7-chloro-1,3-bis(4-chlorophenyl)-4-phenyl-1,4-
(162 MHz, CDCl3) δ 31.36. HRMS (ESI) calcd for C32H26O2P+ dihydrobenzo[d][1,2]oxaphosphinine 3-oxide (3ag’)
1
[M+H]+ m/z: 473.1665; found 473.1655.
Yellow oil (53 mg, 53%, 3ag
:
3ag’ = 71:29). H NMR (400
MHz, CDCl3) δ 7.52 – 7.38 (m, 8H), 7.30 – 7.20 (m, 12H), 7.19 –
7.09 (m, 4H), 7.06 (d, J = 7.8 Hz, 2H), 6.88 – 6.64 (m, 8H), 4.84
(d, J = 25.0 Hz, 1H, 3ag’), 4.78 (d, J = 22.8 Hz, 1H, 3ag). 13C NMR
rel-(1R,3R,4S)-1-Methyl-1,3,4-triphenyl-1,4-dihydrobenzo[d]
[1,2]oxaphosphinine 3-oxide (3ab)
o
1
Colorless crystals (22 mg, 27%). mp. 120–122 C. H NMR (101 MHz, CDCl3) δ 139.9 (d, J = 3.2 Hz), 139.7 (d, J = 3.3 Hz),
(400 MHz, CDCl3) δ 7.66 – 7.54 (m, 4H), 7.53 – 7.43 (m, 2H), 7.42 138.9 (d, J = 6.2 Hz), 137.4 (d, J = 5.6 Hz), 136.6 (d, J = 9.4 Hz),
– 7.32 (m, 7H), 7.32 – 7.24 (m, 2H), 7.22 – 7.06 (m, 4H), 4.49 (d, 136.3 (d, J = 9.0 Hz), 135.5, 135.2, 134.3, 134.2, 134.1, 133.8 (d,
J = 17.5 Hz, 1H), 3.58 (d, J = 10.8 Hz, 3H). 13C NMR (101 MHz, J = 4.8 Hz), 133.7 (d, J = 3.3 Hz), 133.5, 132.7, 132.6 (d, J = 3.8
CDCl3) δ 136.8 (d, J = 6.9 Hz), 136.2, 133.1 (d, J = 9.4 Hz), 132.1, Hz), 131.9 (d, J = 4.7 Hz), 131.6 (d, J = 9.4 Hz), 130.3 (d, J = 5.1
132.1, 132.0, 131.2, 129.8 (d, J = 126.0 Hz), 129.7, 129.7, 129.6, Hz), 129.8 (d, J = 6.8 Hz), 129.5, 129.2, 129.1 (d, J = 4.0 Hz), 128.9,
129.6, 128.5 (d, J = 16.3 Hz), 128.2 (d, J = 12.5 Hz), 128.0, 127.8, 128.7, 128.8 (d, J = 10.1 Hz), 128.5, 127.8 (d, J = 2.1 Hz), 127.5,
127.0 (d, J = 15.1 Hz), 54.3 (d, J = 94.7 Hz), 51.9 (d, J = 6.9 Hz), 127.4, 127.1, 126.0, 78.6 (d, J = 5.8 Hz), 77.8 (d, J = 5.9 Hz), 48.8
29.7. 31P NMR (162 MHz, CDCl3) δ 41.03. HRMS (ESI) calcd for (d, J = 81.4 Hz). 31P NMR (162 MHz, CDCl3) δ 35.06, 34.09. HRMS
C27H24O2P+ [M+H]+ m/z: 411.1508; found 411.1505.
(ESI) calcd for C26H19Cl3O2P+ [M+H]+ m/z: 499.0183; found
499.0176.
rel-(1R,3R,4S)-1-(4-Chlorophenyl)-5-fluoro-3,4-diphenyl-1,4-
dihydrobenzo[d][1,2]oxaphosphinine 3-oxide (3ad’)
(2-(4-Chlorophenyl)ethene-1,1-diyl)dibenzene (4a)14
Colorless crystals (10 mg, 17%). mp. 79–80 oC 1H NMR (400
o
1
White solid (53 mg, 59%). mp. 115–117 C. H NMR (400 MHz, CDCl3) δ 7.48 – 7.40 (m, 8H), 7.35 – 7.29 (m, 2H), 7.20 (d,
MHz, CDCl3) δ 7.55 – 7.38 (m, 8H), 7.31 – 7.21 (m, 4H), 7.08 (d, J = 8.6 Hz, 2H), 7.08 (s, 1H), 7.06 (s, 1H), 7.04 (s, 1H). 13C NMR
J = 7.2 Hz, 1H), 6.97 (t, J = 7.5 Hz, 1H), 6.89 – 6.72 (m, 4H), 5.17 (101 MHz, CDCl3) δ 143.2, 143.0, 139.9, 135.8, 132.3, 130.7,
(d, J = 22.4 Hz, 1H). 13C NMR (101 MHz, CDCl3) δ 162.0 (d, J = 5.9 130.2, 128.7, 128.2, 128.1, 127.7, 127.6, 127.5, 126.7.
Hz), 159.5 (d, J = 5.9 Hz), 137.9 (d, J = 8.7 Hz), 136.9 (d, J = 6.6
Hz), 135.1, 133.1 (d, J = 5.2 Hz), 132.9 (d, J = 2.1 Hz), 132.6 (d, J (2-(4-Bromophenyl)ethene-1,1-diyl)dibenzene (4b)15
= 9.4 Hz), 131.1 (d, J = 9.8 Hz), 130.8, 130.1, 129.3, 129.2 (d, J =
2.6 Hz), 129.0, 128.5 (dd, JC-F = 15.0 Hz, JC-P = 7.4 Hz), 128.07 (d, 1H NMR (400 MHz, CDCl3) δ 7.36 – 7.27 (m, 8H), 7.24 (d, J = 8.3
J = 13.3 Hz), 127.6, 127.2 (d, J = 6.7 Hz), 124.2, 124.0 (dd, JC-F
Hz, 2H), 7.20 – 7.15 (m, 2H), 6.87 (d, J = 7.7 Hz, 3H). 13C NMR
Yellow crystals (12 mg, 18%). mp. 76–77 oC (Lit.3e mp. 77 oC).
=
14.2 Hz, JC-P = 4.8 Hz), 115.6 (d, J = 22.6 Hz), 78.1 (d, J = 5.8 Hz), (101 MHz, CDCl3) δ 143.4, 143.0, 139.9, 136.3, 131.1, 131.0,
41.2 (d, J = 83.6 Hz). 31P NMR (162 MHz, CDCl3) δ 35.06. HRMS 130.2, 128.8, 128.2, 127.7, 127.6, 127.6, 126.8, 120.5.
(ESI) calcd for C26H20ClFO2P+ [M+H]+ m/z: 449.0868; found
449.0872.
(2-(4-Fluorophenyl)ethene-1,1-diyl)dibenzene (4c)14
Yellow oil (4 mg, 7%). 1H NMR (400 MHz, CDCl3) δ 7.37 – 7.27
(m, 8H), 7.22 – 7.15 (m, 2H), 7.01 – 6.95 (m, 2H), 6.92 (s, 1H),
rel-(1R,3R,4S)-1-(4-Chlorophenyl)-3-phenyl-4-(4-
methylphenyl)-1,4-dihydrobenzo[d][1,2]oxaphosphinine 3- 6.86 – 6.77 (m, 2H). 13C NMR (101 MHz, CDCl3) δ 143.2, 142.4,
oxide (3ae) and (1R,3R,4S)-1-(4-chlorophenyl)-5-methyl-3,4- 140.1, 133.5, 131.1 (d, J = 7.2 Hz), 130.3, 128.7, 128.2, 127.5,
diphenyl-1,4-dihydrobenzo[d][1,2]oxaphosphinine
(3ae’)
Colorless liquid (24 mg, 28%, 3ae
(400 MHz, CDCl3) δ 7.48 – 7.46 (d, J = 8.9 Hz, 7H), 7.44 – 7.28 (m,
9H), 7.24 – 7.10 (m, 8H), 7.07 – 7.05 (m, 2H), 6.99 – 6.94 (m, 3H), (m, 8H), 7.23 – 7.19 (m, 2H), 6.97 – 6.88 (m, 5H), 2.26 (s, 3H).
3-oxide 126.9, 115.0, 114.8. 19F NMR (377 MHz, CDCl3) δ -114.83.
1
:
3ae’ = 43:57). H NMR (2-(4-Methylphenyl)ethene-1,1-diyl)dibenzene (4d)16
Yellow oil (4 mg, 7%). 1H NMR (400 MHz, CDCl3) δ 7.37 – 7.26
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13C NMR (101 MHz, CDCl3) δ 143.5, 141.7, 140.6, 136.6, 134.5,
Journal Name
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14
130.4, 129.4, 128.7, 128.6, 128.2, 128.1, 127.5, 127.32, 127.29, (2-(2-Methoxyphenyl)ethene-1,1-diyl)diDbOenI:z1e0.n10e3(94/Dm0)OB02011G
1
21.2.
Yellow oil (8 mg, 14%). H NMR (400 MHz, CDCl3) δ 7.36 –
7.23 (m, 8H), 7.21 – 7.16 (m, 2H), 7.15 – 7.07 (m, 2H), 6.86 –
6.81 (m, 1H), 6.79 – 6.74 (m, 1H), 6.59 (td, J = 7.6, 1.2 Hz, 1H),
(2-(4-Methoxyphenyl)ethene-1,1-diyl)dibenzene (4f)16
Yellow solid (4 mg, 7%). mp. 83–84 oC (Lit.3e mp. 82–83 oC). 3.82 (s, 3H). 13C NMR (101 MHz, CDCl3) δ 157.8, 143.8, 142.5,
1H NMR (400 MHz, CDCl3) δ 7.36 – 7.29 (m, 7H), 7.28 – 7.26 (m, 140.6, 130.6, 130.3, 128.3, 128.0, 128.0, 127.3, 127.1, 126.6,
1H), 7.24 – 7.19 (m, 2H), 6.98 – 6.90 (m, 3H), 6.70 – 6.64 (m, 2H), 123.3, 119.8, 110.3, 55.4.
3.75 (s, 3H). 13C NMR (101 MHz, CDCl3) δ 158.4, 143.6, 140.6,
140.6, 130.8, 130.4, 130.1, 128.7, 128.2, 127.6, 127.4, 127.3, (2-(3-Chlorophenyl)ethene-1,1-diyl)dibenzene (4n)18
1
127.2, 113.4, 55.1.
Yellow oil (11 mg, 10%). H NMR (400 MHz, CDCl3) δ 7.39 –
7.29 (m, 8H), 7.22 – 7.15 (m, 2H), 7.10 – 6.98 (m, 3H), 6.91 –
6.84 (m, 2H). 13C NMR (101 MHz, CDCl3) δ 144.1, 142.9, 139.8,
4-(2,2-Diphenylvinyl)benzonitrile (4g)15
Yellow oil (10 mg, 18%). mp. 122–123 oC 1H NMR (400 MHz, 139.2, 133.8, 130.2, 129.5, 129.1, 128.7, 128.3, 127.8, 127.7,
CDCl3) δ 7.42 – 7.30 (m, 10H), 7.19 – 7.13 (m, 2H), 7.08 (d, J = 127.6, 127.5, 126.7, 126.6.
8.0 Hz, 2H), 6.94 (s, 1H). 13C NMR (101 MHz, CDCl3) δ 146.2,
142.5, 142.1, 139.4, 131.7, 130.1, 129.9, 128.9, 128.3, 128.3, (2-(3-Bromophenyl)ethene-1,1-diyl)dibenzene (4o)21
1
128.1, 127.8, 126.1, 119.0, 109.7.
Yellow oil (11 mg, 16%). H NMR (400 MHz, CDCl3) δ 7.37 –
7.28 (m, 8H), 7.24 – 7.15 (m, 4H), 6.97 (t, J = 7.8 Hz, 1H), 6.92 –
6.86 (m, 2H). 13C NMR (101 MHz, CDCl3) δ 144.2, 142.9, 139.7,
(2-(4-Nitrophenyl)ethene-1,1-diyl)dibenzene (4h)17
Yellow crystals (3 mg, 5%). mp. 156–157 oC (Lit.3e mp. 243– 139.5, 132.5, 130.2, 129.6, 129.4, 128.7, 128.3, 127.9, 127.8,
245 oC). 1H NMR (400 MHz, CDCl3) δ 8.01 – 7.95 (m, 2H), 7.41 – 127.7, 127.6, 126.4, 122.0.
7.32 (m, 8H), 7.20 – 7.09 (m, 4H), 7.00 (s, 1H). 13C NMR (101
MHz, CDCl3) δ 147.0, 145.9, 144.3, 142.4, 139.3, 130.1, 130.0, (2-(3-Methylphenyl)ethene-1,1-diyl)dibenzene (4p)14
128.9, 128.5, 128.4, 128.2, 127.8, 125.7, 123.3.
Colorless oil (5 mg, 9%). 1H NMR (400 MHz, CDCl3) δ 7.36 –
7.26 (m, 8H), 7.23 – 7.18 (m, 2H), 7.00 (t, J = 7.6 Hz, 1H), 6.96 –
6.90 (m, 2H), 6.85 (d, J = 1.7 Hz, 1H), 6.79 (d, J = 7.7 Hz, 1H), 2.18
(2-(2-Fluorophenyl)ethene-1,1-diyl)dibenzene (4i)18
1
Yellow oil (8 mg, 15%). H NMR (400 MHz, CDCl3) δ 7.39 – (s, 3H). 13C NMR (101 MHz, CDCl3) δ 143.5, 142.4, 140.5, 137.4,
7.27 (m, 8H), 7.22 – 7.15 (m, 2H), 7.13 – 7.03 (m, 2H), 7.03 – 137.3, 130.5, 130.3, 128.6, 128.3, 128.2, 127.6, 127.4, 127.3,
6.95 (m, 1H), 6.82 – 6.73 (m, 2H). 13C NMR (101 MHz, CDCl3) δ 126.5, 21.3.
161.0 (d, J = 247.9 Hz), 144.5, 143.1, 140.0, 130.3, 128.5, 128.3
(d, J = 8.6 Hz), 128.2, 127.9, 127.8, 127.5, 125.4 (d, J = 13.2 Hz), (2-(3-Methoxyphenyl)ethene-1,1-diyl)dibenzene (4q)16
1
123.2 (d, J = 3.0 Hz), 120.0 (d, J = 4.9 Hz), 115.3, 115.1. 19F NMR
(377 MHz, CDCl3) δ -115.68.
Yellow oil (6 mg, 10%). H NMR (400 MHz, CDCl3) δ 7.38 –
7.27 (m, 8H), 7.25 – 7.21 (m, 2H), 7.07 (t, J = 7.9 Hz, 1H), 6.96 (s,
1H), 6.72 – 6.63 (m, 2H), 6.55 – 6.48 (m, 1H), 3.50 (s, 3H). 13C
NMR (101 MHz, CDCl3) δ 159.0, 143.2, 142.7, 140.5, 138.6,
(2-(2-Chlorophenyl)ethene-1,1-diyl)dibenzene (4j)17
Colorless oil (5 mg, 8%). 1H NMR (400 MHz, CDCl3) δ 7.38 – 130.3, 128.9, 128.7, 128.2, 128.0, 127.5, 127.4, 122.5, 113.7,
7.31 (m, 6H), 7.25 (t, J = 3.2 Hz, 3H), 7.17 – 7.12 (m, 2H), 7.09 (s, 113.5, 54.8.
1H), 7.07 – 7.02 (m, 1H), 6.90 – 6.80 (m, 2H). 13C NMR (101 MHz,
CDCl3) δ 144.6, 142.9, 139.7, 136.2, 134.6, 131.1, 130.6, 129.2, Ethene-1,1,2-triyltribenzene (4r)14
1
128.3, 128.2, 128.1, 127.9, 127.5, 125.9, 125.0.
Yellow oil (7 mg, 14%). H NMR (400 MHz, CDCl3) δ 7.36 –
7.27 (m, 8H), 7.23 – 7.18 (m, 2H), 7.16 – 7.08 (m, 3H), 7.03 (d, J
= 7.3 Hz, 2H), 6.97 (s, 1H). 13C NMR (101 MHz, CDCl3) δ 143.4,
(2-(2-Bromophenyl)ethene-1,1-diyl)dibenzene (4k)19
1
Yellow oil (8 mg, 12%). H NMR (400 MHz, CDCl3) δ 7.57 – 142.6, 140.3, 137.4, 130.4, 129.5, 128.6, 128.18, 128.15, 127.9,
7.52 (m, 1H), 7.39 – 7.31 (m, 5H), 7.27 – 7.22 (m, 3H), 7.16 – 127.6, 127.5, 127.4, 126.7.
7.09 (m, 2H), 7.02 (s, 1H), 7.00 – 6.89 (m, 2H), 6.85 – 6.79 (m,
1H). 13C NMR (101 MHz, CDCl3) δ 144.4, 142.8, 139.6, 138.1, 2-(2,2-Diphenylvinyl)naphthalene (4s)14
132.4, 131.4, 130.6, 128.24, 128.22, 128.11, 128.05, 127.9,
127.4, 126.5, 125.1.
Yellow oil (10 mg, 16%). 1H NMR (400 MHz, CDCl3) δ 7.70 (dd,
J = 6.0, 3.4 Hz, 1H), 7.64 – 7.60 (m, 1H), 7.56 (s, 1H), 7.52 (d, J =
8.6 Hz, 1H), 7.40 – 7.36 (m, 4H), 7.34 – 7.29 (m, 6H), 7.26 – 7.22
(m, 2H), 7.13 (s, 1H), 7.05 (dd, J = 8.6, 1.8 Hz, 1H). 13C NMR (101
(2-(2-Methylphenyl)ethene-1,1-diyl)dibenzene (4l)20
1
Yellow oil (6 mg, 11%). H NMR (400 MHz, CDCl3) δ 7.38 – MHz, CDCl3) δ 143.4, 143.0, 140.4, 135.1, 133.3, 132.25, 130.6,
7.28 (m, 5H), 7.24 – 7.18 (m, 3H), 7.15 – 7.07 (m, 3H), 7.06 – 129.1, 128.7, 128.2, 128.0, 127.7, 127.6, 127.5, 127.5, 127.2,
7.01 (m, 1H), 6.98 (s, 1H), 6.89 – 6.80 (m, 2H), 2.32 (s, 3H). 13C 127.1, 125.9, 125.8.
NMR (101 MHz, CDCl3) δ 143.6, 143.3, 140.2, 137.0, 130.7,
129.7, 129.7, 128.2, 128.1, 127.5, 127.3, 127.1, 126.8, 125.2, (2-(2,6-Dichlorophenyl)ethene-1,1-diyl)dibenzene (4t)
20.2.
10 | J. Name., 2012, 00, 1-3
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Yellowish crystals (4 mg, 6%). mp. 78–79 C. H NMR (400 There are no conflicts of interest to declare.
ARTICLE
o
1
View Article Online
DOI: 10.1039/D0OB02011G
MHz, CDCl3) δ 7.43 – 7.33 (m, 5H), 7.21 – 7.13 (m, 5H), 7.09 –
7.01 (m, 3H), 6.74 (s, 1H). 13C NMR (101 MHz, CDCl3) δ 147.4,
142.2, 139.7, 136.1135.1, 129.7, 128.4, 128.4, 128.2, 128.1,
Acknowledgements
+
127.7, 127.6, 127.5, 122.5. HRMS (ESI) calcd for C20H15Cl2
This work was supported by the National Natural Science
Foundation of China (No. 21772010).
[M+H]+ m/z: 325.0545; found 325.05450.
(2-Mesitylethene-1,1-diyl)dibenzene (4u)22
Yellow oil (5 mg, 8%). 1H NMR (400 MHz, CDCl3) δ 7.39 – 7.31
(m, 5H), 7.16 – 7.10 (m, 3H), 7.00 – 6.94 (m, 2H), 6.80 (s, 1H),
6.76 (s, 2H), 2.23 (s, 3H), 2.07 (s, 6H). 13C NMR (101 MHz, CDCl3)
δ 144.2, 143.6, 140.4, 136.2, 136.0, 133.9, 129.8, 128.4, 128.1,
128.0, 127.7, 127.5, 127.4, 127.1, 21.0, 20.4.
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Yellow crystals (20 mg, 42%). mp. 141–142 oC. 1H NMR (400
MHz, CDCl3) δ 7.74 – 7.68 (m, 1H), 7.57 – 7.52 (m, 2H), 7.50 –
7.41 (m, 3H), 7.41 – 7.34 (m, 5H), 7.33 – 7.29 (m, 2H), 7.27 –
7.22 (m, 3H), 7.21 – 7.11 (m, 3H), 7.10 – 7.03 (m, 1H), 6.92 –
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133.1 (d, J = 9.3 Hz), 132.7, 130.9 (d, J = 5.3 Hz), 130.4 (d, J = 7.2
Hz), 129.3, 129.2, 129.1, 129.0 (d, J = 7.3 Hz), 128.8 (d, J = 3.9
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Conflicts of interest
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