Copper-Catalyzed Addition of H-P(O) Bonds to Arynes

Article abstract of DOI:10.1021/acs.joc.6b01776

An efficient P-arylation of secondary phosphine oxides has been achieved through the ligand-free copper-catalyzed addition of H-P(O) bonds to in situ generated arynes at room temperature. This transformation provides a straightforward route to the formation of the aryl-P bond with wide functional group compatibility, which produces arylphosphine oxides in up to 99% yield.

Full text of DOI:10.1021/acs.joc.6b01776

Subscriber access provided by CORNELL UNIVERSITY LIBRARY
Note
Copper-Catalyzed Addition of H-P(O) Bonds to Arynes
Qian Chen, Xinxing Yan, Chunxiao Wen, Jiekun Zeng, Yulin Huang, Xingguo Liu, and Kun Zhang
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.6b01776 • Publication Date (Web): 08 Sep 2016
Downloaded from http://pubs.acs.org on September 9, 2016
Just Accepted
“Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted
online prior to technical editing, formatting for publication and author proofing. The American Chemical
Society provides “Just Accepted” as a free service to the research community to expedite the
dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts
appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been
fully peer reviewed, but should not be considered the official version of record. They are accessible to all
readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered
to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published
in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just
Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor
changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers
and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors
or consequences arising from the use of information contained in these “Just Accepted” manuscripts.
The Journal of Organic Chemistry is published by the American Chemical Society.
1155 Sixteenth Street N.W., Washington, DC 20036
Published by American Chemical Society. Copyright © American Chemical Society.
However, no copyright claim is made to original U.S. Government works, or works
produced by employees of any Commonwealth realm Crown government in the course
of their duties.

Page 1 of 20
The Journal of Organic Chemistry
1
2
3
4
5
6
CopperꢀCatalyzed Addition of H−P(O) Bonds to Arynes
7
8
9
Qian Chen,* Xinxing Yan, Chunxiao Wen, Jiekun Zeng, Yulin Huang, Xingguo Liu, and Kun Zhang
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
School of Chemical Engineering and Light Industry, Guangdong University of Technology, Guangzhou,
Guangdong 510006, China
RECEIVED DATE (will be automatically inserted after manuscript is accepted).
ABSTRACT: An efficient Pꢀarylation of secondary phosphine oxides has been achieved through the
ligandꢀfree copperꢀcatalyzed addition of H−P(O) bonds to in situ generated arynes at room temperature.
This transformation provides a straightforward route to the formation of the aryl−P bond with wide
functional group compatibility, which produces arylphosphine oxides in up to 99% yield.
Organophosphorus compounds have attracted much attention due to their wide applications in
organic synthesis, medicinal chemistry, and material science.1 Over the past few decades, a
variety of useful synthetic methods for various organophosphorus compounds have been wellꢀ
developed.2 Currently, Pꢀarylation has been of particular interest owning to the significant roles
of arylphosphine complexes, which are the most important class of ligands in metalꢀcatalyzed
reactions.3 The transitionꢀmetalꢀcatalyzed Arbuzov or Hirao crossꢀcoupling reaction of aryl
halides with phosphorus nucleophiles provides an efficient Pꢀarylation protocol for the synthesis
of arylphosphonates and their derivatives,4 while ligands, high temperatures, or long reaction
1
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 2 of 20
times are generally required for the reaction conditions. On the other hand, the transitionꢀmetalꢀ
free C−P bond construction via the direct addition of phosphorus nucleophiles to arynes5 is
gradually developed.6 Most recently, our group achieved the Pꢀarylation of secondary phosphine
oxides with arynes to synthesize arylphosphine oxides.7 However, the reaction of Ar2P(O)H with
1
2
3
4
5
6
7
8
9
o
arynes was realized at an elevated temperature (80 C) with the assistance of excess Cs2CO3
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(Scheme 1, eq. 1). Simultaneously, the similar transformation under different reaction conditions
was reported by Zhang and coꢀworkers,8 while the Pꢀarylation of P(O)ꢀH compounds was also
achieved at 100 oC with excess Cs2CO3 (eq. 1). Thus, an efficient methodology for the synthesis
of important arylphosphine complexes based on readily available secondary phosphine oxides
under ambient conditions is still a significant issue.
Since Han and coꢀworkers invented the palladiumꢀcatalyzed hydrophosphorylation of alkynes
in 1996,9 various metalꢀcatalyzed additions of H−P(O) bond to the triple bond of terminal and
internal alkynes have been wellꢀdocumented using palladium,10 nickel,11 rhodium,12 copper,13
molybdenum,14 and ytterbium15 based catalysts (eqs. 2 and 3), which provide a convenient
method for the synthesis of alkenylphosphorus derivatives under mild conditions. To the best of
our knowledge, transitionꢀmetalꢀcatalyzed additions of H−P(O) bond to in situ generated arynes
remain unexplored. With our recent studies on the behaviors of arynes,7,16 we have been
interested in studying the addition of H−P(O) bonds to arynes catalyzed by the cheaper copper
salts. Herein, we report that the utilization of CuI as the catalyst for the Pꢀarylation of secondary
phosphine oxides with arynes provides a convenient and general approach to arylphosphine
oxides at room temperature.
Scheme 1. Overview of the Addition of H−P(O) Bonds to Triple Bonds
2
ACS Paragon Plus Environment

Page 3 of 20
The Journal of Organic Chemistry
Previous work:
O
1
2
3
4
R2
P
R2
O
Cs2CO3
R1
(1)
R2
P
H
R2
+
80 or 100 oC
R1
in situ
5
6
7
8
O
P
H
[M]/ligand
R1
R1
R2
R3
R1
R1
+
(2)
(3)
P(O)R2R3
M = Pd, Ni, Rh, Cu, Mo, Yb
9
R1
O
P
H
[M]/ligand
10
11
12
13
14
15
16
17
18
19
20
21
22
23
R2
R2
R1
+
P(O)R2
M = Pd, Rh, Cu
2
This work:
O
P
R2
R2
O
P
H
[Cu]
rt
R1
R2
R2
(4)
+
R1
in situ
The reaction conditions were tested by using a model reaction between readily available oꢀ
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
silylphenyl triflate benzyne precursor 1a and diphenylphosphine oxide 2a with a variety of
copper salts (10 mol %) in the presence of CsF in CH3CN at room temperature, and the results
were shown in Table 1. To our delight, the desired triphenylphosphine oxide 3aa was obtained
in 92% yield when Cu(OAc)2 without additional ligands was introduced (entry 2), while the
reaction gave 3aa in only 15% yield in the absence of the catalyst (entry 1).7 Switching the
copper salt from Cu(OAc)2 to CuBr2 or CuSO4 significantly decreased the yield (entries 3 and 4).
We then turned to screen copper(I) salts. CuOAc, CuOTf, CuCl, CuBr, and CuI showed good to
high catalytic activities (entries 5−9), and CuI was proved to be the optimum catalyst (99% yield,
entry 9). When the catalytic amount of CuI was decreased to 5 mol %, 3aa was still obtained in
99% yield (entry 10). It is noteworthy that triphenylene generated by Cu(I)ꢀcatalyzed
cyclotrimerization of benznye17 was not detected. Thus, we concluded that the optimized
combination for the addition of H−P(O) bonds to arynes was to use 5 mol % of CuI as the
catalyst, 4 equiv of CsF as the fluoride ion, and CH3CN as the solvent, and the reaction was set
at room temperature.
Table 1. Optimization of the Reaction Conditionsa
3
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 4 of 20
1
2
3
4
5
6
7
8
9
entry
[M] (mol %)
ꢀ
yield of 3aa (%)b
1
2
15
92
78
45
93
85
93
76
99
99
Cu(OAc)2 (10)
CuBr2 (10)
CuSO4 (10)
CuOAc (10)
CuOTf (10)
CuCl (10)
CuBr (10)
CuI (10)
3
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
4
5
6
7
8
9
10
CuI (5)
aReaction conditions: 1a (0.2 mmol), 2a (0.3 mmol), CsF (0.8 mmol) in CH3CN (4 mL) stirring at room temperature
b
1
under N2 for 16 h. Yield based on 1a was determined by H NMR analysis of crude products using an internal
standard.
To investigate the scope of the Pꢀarylation protocol, we applied the optimum conditions to the
reaction of a variety of aryne precursors with various diarylphosphine oxides, and the results are
illustrated in Table 2. Electronꢀrich and electronꢀpoor Ar2P(O)H 2a–2i were all well tolerated for the Pꢀ
arylation with arynes to smoothly produce the corresponding triarylphosphine oxides 3 in 50–99% yields.
It is noteworthy that the Pꢀarylation with 3,6ꢀdimethylꢀsubstituted aryne precursor 1c afforded the
sterically hindered triarylphosphine oxides 3ca–3cg with orthoꢀmethyl substitution in 78–91% yields,
and the Pꢀarylation of di(naphthalenꢀ1ꢀyl)phosphine oxide 2i afforded the bulky triarylphosphine oxides
3ai, 3bi, and 3ci in high yields. Unsymmetrical aryne precursors 1f and 1g were selected to study the
regioselectivity of this arylation procedure. The 3ꢀmethoxyꢀsubstituted silylaryl triflate 1f reacted cleanly
with arynes to generate 3fa, 3fd, and 3fe as a single isomer, which was in good agreement with the
regioselectivity reported in the literature.18 When 4ꢀmethylꢀsubstituted silylaryl triflate 1g was employed,
two isomers were obtained (metaꢀ3ga/paraꢀ3ga = 1.3:1), which further suggested that the reaction
involved an aryne mechanism.
4
ACS Paragon Plus Environment

Page 5 of 20
The Journal of Organic Chemistry
1
2
3
Table 2. Synthesis of Triarylphosphine Oxidesa,b
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
O
P
3ae, R = 4-OMe, 89%
3af, R = 3,5-dimethyl, 96%
3ag, R = 4-Cl, 99%
3aa, R = H, 95%
3ab, R = 3-Me, 98%
3ac, R = 3-OMe, 98%
3ad, R = 4-Me, 82%
R
R
R
R
3ah, R = 4-F, 99%
O
P
3ba, R = H, 95%
3bb, R = 3-Me, 91%
3be
, R = 4-OMe, 87%
3bf, R = 3,5-dimethyl, 92%
3bc, R = 3-OMe, 72% 3bg, R = 4-Cl, 83%
3bd, R = 4-Me, 85%
Me
Me
Me
O
3ce, R = 4-OMe, 85%
3cf, R = 3,5-dimethyl, 88%
3cg, R = 4-Cl, 91%
3ca, R = H, 90%
P
3cb, R = 3-Me, 85%
3cc, R = 3-OMe, 82%
3cd, R = 4-Me, 78%
R
R
R
R
Me
O
P
3da, R = H, 99%
3df, R = 3,5-dimethyl, 96%
3dc, R = 3-OMe, 88% 3dg, R = 4-Cl, 94%
3dd, R = 4-Me, 89%
3de, R = 4-OMe, 83%
O
P
O
3ai, R = H, 99%
3bi, R = 3,4-dimethyl, 90%
3ci, R = 2,5-dimethyl, 88%
P
MeO
R
R
OMe
3ea, 71%
O
P
O
P
O
P
R
1.3:1c
MeO
Me
3ga, 87%
3fa, R = H, 52%
3fd, R = Me, 50%
3fe, R = OMe, 75%
Me
aReaction conditions: 1 (0.2 mmol), 2 (0.3 mmol), CuI (0.01 mmol), CsF (0.8 mmol) in CH3CN (4 mL) stirring at room
temperature under N2 for 16 h. bIsolated yield based on 1. cRatio was determined by 1H NMR.
5
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 6 of 20
Having succeeded in the synthesis of triarylphosphine oxides, we then turned to the Pꢀarylation of
dialkylphosphine oxides with arynes (Scheme 2). To our delight, the reaction of dibutylphosphine oxide
2j or dicyclopentylphosphine oxide 2k with benzyne precursor 1a under the same conditions smoothly
afforded the desired dialkylphenylphosphine oxide 3aj or 3ak in excellent yield. To illustrate the further
synthetic utility of this method, the scaleꢀup of the reaction of 1a with diarylphosphine oxides was
attempted. When we increased the scale of the reaction from 0.2 to 2 mmol, the yields of 3aa and 3ah
only slightly decreased (Scheme 3).
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Scheme 2. Synthesis of Dialkylphenylphosphine Oxides
Scheme 3. Scaleꢀup of the Reaction
According to the experimental results and metalꢀcatalyzed addition of H−P(O) bonds to
alkynes,9ꢀ15 a plausible mechanism for the copperꢀcatalyzed addition of H−P(O) bonds to arynes
is outlined in Scheme 4. CuI first reacts with secondary phosphine oxides
2 and forms the
corresponding active [R2 P(O)Cu] intermediates 4.19 Insertion of in situ generated arynes
5
into
2
the Cu−P bonds of
4
gives arylcopper intermediates
6
. Protonolysis of
6
by secondary phosphine
. To further
oxides results in arylphosphine oxides
2
3
and regenerates the active catalysts 4
elucidate the mechanism of this reaction, the copperꢀcatalyzed reaction of benzyne precursor 1a
with diphenylphosphine oxide in the presence of D2O (2 equiv) afforded 3aa in 83% yield with
only 22% D incorporation at the orthoꢀposition. As a comparison, our previous work shows that
6
ACS Paragon Plus Environment

Page 7 of 20
The Journal of Organic Chemistry
trace amounts of water serves as the proton source when the reaction was carried out without
copper catalysts (Scheme 1, eq. 1).7 The difference between the two reactions suggests the
1
2
3
4
5
6
7
8
formation of the arylcopper intermediate
mainly trapped by leading to
6 from the intermediate 4 and benzyne 5, which is
2
3.
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Scheme 4. Proposed Mechanism
In conclusion, we have developed a ligandꢀfree copperꢀcatalyzed addition of H−P(O) bonds to
in situ generated arynes, which provides a highly efficient and convenient protocol for the
synthesis of arylphosphine oxides with wide functional group compatibility under ambient
conditions. To the best of our knowledge, this finding is the first example of transitionꢀmetalꢀ
catalyzed Pꢀarylation of P(O)ꢀH compounds with arynes. We envision that the reaction mode
outlined here will have potential applications in organic synthesis.
EXPERIMENTAL SECTION
General Details. All reactions were carried out under an atmosphere of nitrogen using ovenꢀdried
glassware and standard syringe/septa techniques. Acetonitrile was distilled from calcium hydride.
Petroleum ether refers to the petroleum fraction bp 40~60 °C. Commercial reagents were used without
7
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 8 of 20
purification unless otherwise noted. Aryne precursors were prepared according to the literature.20
Secondary phosphine oxides which were not commercially available were prepared according to the
literature.21 Flash chromatography was performed using the indicated solvent system on silica gel
1
2
3
4
5
6
7
8
1
standard grade 60 (230−400 mesh). H NMR spectra were recorded on a 400 MHz spectrometer. 13C
9
NMR spectra were recorded on a 100 MHz spectrometer. 31P NMR spectra were recorded on a 162
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
19
MHz spectrometer. F NMR spectra were recorded on a 376 MHz spectrometer. Chemical shifts are
1
13
reported relative to CDCl3 (δ 7.26 ppm) for H NMR and CDCl3 (δ 77.16 ppm) for C NMR. Highꢀ
resolution mass spectra (HRMS) were recorded on ESIꢀTOF. The known compounds 3aa,7 3ab,22 3ad,7
3ae,23 3af,7 3ah,23 3aj,7 3ak,7 3ba,7 3bd,7 3bf,7 3ca,7 3cd,7 3cf,7 3ea,24 3fa,6b 3fe,25 and 3ga26 showed
characterization data in full agreement with previously reported data.
General Procedure for the PꢀArylation of Secondary Phosphine Oxides. To a solution of 2ꢀ
(trimethylsilyl)phenyl triflate 1a (60 mg, 0.2 mmol) and diphenylphosphine oxide 2a (60 mg, 0.3 mmol)
in acetonitrile (4 mL) was added CuI (2 mg, 0.01 mmol, 5 mol %) and CsF (116 mg, 0.8 mmol) under
nitrogen atmosphere. The mixture was stirred at room temperature for 16 h. After removal of the
solvent, the residue was then purified by flash column chromatography on silica gel with petroleum
ether/ethyl acetate (2:1) to give the pure product 3aa (53 mg, 95%).
Triphenylphosphine oxide (3aa). White amorphous solid (53 mg, 95%):7 1H NMR (400 MHz,
13
CDCl3) δ 7.68–7.61 (m, 6H), 7.58–7.52 (m, 3H), 7.51–7.43 (m, 6H); C NMR (100 MHz, CDCl3) δ
31
132.6 (d, J = 103 Hz), 132.0 (d, J = 9.9 Hz), 131.9 (d, J = 2.7 Hz), 128.5 (d, J = 12.1 Hz); P NMR
(162 MHz, CDCl3) δ 29.1.
Phenyldiꢀmꢀtolylphosphine oxide (3ab). White amorphous solid (60 mg, 98%):22 1H NMR (400
MHz, CDCl3) δ 7.71–7.62 (m, 2H), 7.56 (d, J = 12.4 Hz, 2H), 7.54–7.52 (m, 1H), 7.48–7.42 (m, 2H),
13
7.39–7.37 (m, 1H), 7.34–7.31 (m, 5H), 2.36 (s, 6H); C NMR (100 MHz, CDCl3) δ 138.4 (d, J = 12.0
Hz), 133.2 (d, J = 104 Hz), 132.8 (d, J = 103 Hz), 132.7 (d, J = 2.8 Hz), 132.5 (d, J = 9.5 Hz), 132.1 (d,
J = 9.9 Hz), 131.8 (d, J = 2.7 Hz), 129.2 (d, J = 10.3 Hz), 128.3 (d, J = 4.7 Hz), 128.5 (d, J = 29.1 Hz),
21.4; 31P NMR (162 MHz, CDCl3) δ 29.6.
8
ACS Paragon Plus Environment

Page 9 of 20
The Journal of Organic Chemistry
1
Bis(3ꢀmethoxyphenyl)(phenyl)phosphine oxide (3ac). White amorphous solid (66 mg, 98%): H
1
2
NMR (400 MHz, CDCl3) δ 7.72–7.60 (m, 2H), 7.54 (t, J = 7.1 Hz, 1H), 7.50–7.40 (m, 2H), 7.40–7.31
(m, 2H), 7.28 (d, J = 13.1 Hz, 2H), 7.20–7.10 (m, 2H), 7.07 (d, J = 8.2 Hz, 2H), 3.79 (s, 6H); 13C NMR
(100 MHz, CDCl3) δ 159.5 (d, J = 14.9 Hz), 133.6 (d, J = 104 Hz), 132.2 (d, J = 104 Hz), 132.0 (d, J =
10.0 Hz), 131.9 (d, J = 2.7 Hz), 129.6 (d, J = 14.4 Hz), 128.4 (d, J = 12.2 Hz), 124.3 (d, J = 10.1 Hz),
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
31
118.2 (d, J = 2.6 Hz), 116.8 (d, J = 10.8 Hz), 55.4; P NMR (162 MHz, CDCl3) δ 29.9; HRMS (ESIꢀ
TOF) m/z: [M + Na]+ Calcd for C20H19O3PNa 361.0964; Found 361.0960.
Phenyldiꢀpꢀtolylphosphine oxide (3ad). White amorphous solid (50 mg, 82%):7 1H NMR (400
MHz, CDCl3) δ 7.66–7.61 (m, 2H), 7.55–7.47 (m, 5H), 7.43–7.39 (m, 2H), 7.23 (d, J = 6.6 Hz, 4H),
2.39 (s, 6H); 13C NMR (100 MHz, CDCl3) δ 142.3 (d, J = 2.6 Hz), 133.1 (d, J = 104 Hz), 132.3 (d, J =
10.2 Hz), 132.1 (d, J = 10.2 Hz), 131.8 (d, J = 2.5 Hz), 129.3 (d, J = 106 Hz), 129.2 (d, J = 12.5 Hz),
128.4 (d, J = 12.1 Hz), 21.6; 31P NMR (162 MHz, CDCl3) δ 29.3.
Bis(4ꢀmethoxyphenyl)(phenyl)phosphine oxide (3ae). White amorphous solid (60 mg, 89%):23 1
H
NMR (400MHz, CDCl3): δ 7.64−7.59 (m, 2H), 7.57−7.50 (m, 4H), 7.49−7.46 (m, 1H), 7.42−7.38 (m,
2H), 6.92 (dd, J = 8.9, 2.2 Hz, 4H), 3.79 (s, 6H); 13C NMR (100 MHz, CDCl3): δ 162.4 (d, J = 2.6 Hz),
134.0 (d, J = 11.2 Hz), 132.5 (d, J = 104 Hz), 132.0 (d, J = 10.1 Hz), 131.7 (d, J = 2.2 Hz), 128.4 (d, J =
12.8 Hz), 124.1 (d, J = 111 Hz), 114.1 (d, J = 13.1 Hz), 55.3; 31P NMR (162 MHz, CDCl3): δ 29.0.
Bis(3,5ꢀdimethylphenyl)(phenyl)phosphine oxide (3af). White amorphous solid (64 mg, 96%):7 1H
NMR (400 MHz, CDCl3) δ 7.71–7.62 (m, 2H), 7.54–7.50 (m, 1H), 7.47–7.42 (m, 2H), 7.26 (d, J = 12.0
Hz, 4H), 7.16 (s, 2H), 2.31 (s, 12H); 13C NMR (100 MHz, CDCl3) δ 138.1 (d, J = 12.7 Hz), 133.6 (d, J
= 2.8 Hz), 132.8 (d, J = 103 Hz), 132.1 (d, J = 104 Hz), 132.3 (d, J = 9.9 Hz), 131.9 (d, J = 2.7 Hz),
129.6 (d, J = 9.8 Hz), 128.3 (d, J = 12.0 Hz), 21.2; 31P NMR (162 MHz, CDCl3) δ 29.7.
1
Bis(4ꢀchlorophenyl)(phenyl)phosphine oxide (3ag). White amorphous solid (69 mg, 99%): H
NMR (400 MHz, CDCl3) δ 7.68–7.53 (m, 7H), 7.52–7.39 (m, 6H); 13C NMR (100 MHz, CDCl3) δ
138.8 (d, J = 3.3 Hz), 133.4 (d, J = 10.8 Hz), 132.3 (d, J = 2.7 Hz), 131.9 (d, J = 10.0 Hz), 131.6 (d, J =
31
106 Hz), 130.7 (d, J = 106 Hz), 129.0 (d, J = 12.8 Hz), 128.7 (d, J = 12.3 Hz); P NMR (162 MHz,
9
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 10 of 20
CDCl3) δ 27.7; HRMS (ESIꢀTOF) m/z: [M + Na]+ Calcd for C18H13Cl2OPNa 368.9973; Found
1
2
3
368.9970.
4
5
6
Bis(4ꢀfluorophenyl)(phenyl)phosphine oxide (3ah). White amorphous solid (62 mg, 99%):23 1
H
7
8
9
NMR (400 MHz, CDCl3) δ 7.69–7.60 (m, 6H), 7.58–7.52 (m, 1H), 7.50–7.44 (m, 2H), 7.18–7.14 (m,
4H); 13C NMR (100 MHz, CDCl3) δ 165.1 (dd, JCꢀF = 254 Hz, JCꢀP = 3.1 Hz), 134.5 (dd, JCꢀF = 11.7 Hz,
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
J
CꢀP =8.7 Hz), 132.3 (d, JCꢀP = 2.3 Hz), 132.2 (d, JCꢀP = 106 Hz), 132.1 (d, JCꢀP = 10.0 Hz), 128.8 (d, JCꢀP
= 12.1 Hz), 128.5 (dd, JCꢀP = 108 Hz, JCꢀF = 3.0 Hz), 116.1 (dd, JCꢀP = 21.6 Hz, JCꢀF = 13.6 Hz); 19F
NMR (376 MHz, CDCl3) δ ꢀ106.3; 31P NMR (162 MHz, CDCl3) δ 27.8.
Di(naphthalenꢀ1ꢀyl)(phenyl)phosphine oxide (3ai). White amorphous solid (75 mg, 99%): 1H NMR
(400 MHz, CDCl3) δ 8.72 (d, J = 8.4 Hz, 2H), 7.93 (d, J = 7.9 Hz, 2H), 7.82 (d, J = 7.9 Hz, 2H), 7.63
(dd, J = 11.8, 7.6 Hz, 2H), 7.52–7.31 (m, 7H), 7.28–7.10 (m, 4H); 13C NMR (100 MHz, CDCl3) δ 134.0
(d, J = 2.8 Hz), 133.9 (d, J = 3.9 Hz), 133.5 (d, J = 12.0 Hz), 133.2 (d, J = 2.8 Hz), 132.3 (d, J = 9.8
Hz), 131.9 (d, J = 2.6 Hz), 129.5 (d, J = 102 Hz), 128.7, 128.6 (d, J = 12.3 Hz), 127.9 (d, J = 5.4 Hz),
126.9 (d, J = 86.7 Hz), 124.2 (d, J = 14.5 Hz); 31P NMR (162 MHz, CDCl3) δ 36.3; HRMS (ESIꢀTOF)
m/z: [M + Na]+ Calcd for C26H19OPNa 401.1066; Found 401.1066.
Dibutyl(phenyl)phosphine oxide (3aj). Thick oil (47 mg, 99%):7 1H NMR (400 MHz, CDCl3) δ
7.71–7.66 (m, 2H), 7.52–7.48 (m, 1H), 7.44–7.37 (m, 2H), 2.36 (br, 2H), 2.08–1.80 (m, 4H), 1.57–1.31
13
(m, 6H), 0.78 (t, J = 7.1 Hz, 6H); C NMR (100 MHz, CDCl3) δ 132.1 (d, J = 2.6 Hz), 131.1 (d, J =
126 Hz), 130.5 (d, J = 9.1 Hz), 128.7 (d, J = 11.4 Hz), 28.8 (d, J = 69.2 Hz), 23.9 (d, J = 15.3 Hz), 23.3
(d, J = 4.0 Hz), 13.3; 31P NMR (162 MHz, CDCl3) δ 44.8.
Dicyclopentyl(phenyl)phosphine oxide (3ak). Thick oil (50 mg, 95%):7 1H NMR (400 MHz,
CDCl3) δ 7.72–7.68 (m, 2H), 7.51–7.46 (m, 1H), 7.42–7.38 (m, 2H), 2.36–2.28 (m, 2H), 2.01–1.76 (m,
13
4H), 1.70–1.41 (m, 12H); C NMR (100 MHz, CDCl3) δ 131.8 (d, J = 2.4 Hz), 131.3 (d, J = 2.4 Hz),
130.1 (d, J = 127 Hz), 128.3 (d, J = 10.7 Hz), 37.5 (d, J = 71.2 Hz), 27.0, 26.5 (d, J = 9.6 Hz), 26.0, 25.9
(d, J = 10.0 Hz); 31P NMR (162 MHz, CDCl3) δ 47.3.
10
ACS Paragon Plus Environment

Page 11 of 20
The Journal of Organic Chemistry
(3,4ꢀDimethylphenyl)diphenylphosphine oxide (3ba). White amorphous solid (58 mg, 95%):7 1H
NMR (400 MHz, CDCl3) δ 7.68–7.63 (m, 4H), 7.55–7.49 (m, 3H), 7.47–7.42 (m, 4H), 7.32–7.27 (m,
1H), 7.2–7.19 (m, 1H), 2.30 (s, 3H), 2.27 (d, J = 7.9 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 141.2 (d, J
= 2.9 Hz), 137.2 (d, J = 12.3 Hz), 133.4 (d, J = 100 Hz), 133.0 (d, J = 9.8 Hz), 132.0 (d, J = 9.9 Hz),
131.9 (d, J = 2.7 Hz), 129.7 (d, J = 2.8 Hz), 129.9 (d, J = 110 Hz), 129.6, 128.5 (d, J = 12.1 Hz), 19.9,
19.7; 31P NMR (162 MHz, CDCl3) δ 29.4.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
1
(3,4ꢀDimethylphenyl)diꢀmꢀtolylphosphine oxide (3bb). White amorphous solid (61 mg, 91%): H
NMR (400 MHz, CDCl3) δ 7.61–7.46 (m, 3H), 7.43–7.25 (m, 7H), 7.24–7.14 (m, 1H), 2.35 (s, 6H),
2.30 (s, 3H), 2.26 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 141.0 (d, J = 2.9 Hz), 138.3 (d, J = 11.9 Hz),
137.0 (d, J = 12.3 Hz), 132.9 (d, J = 9.8 Hz), 132.8 (d, J = 103 Hz), 132.5 (d, J = 2.5 Hz), 132.4 (d, J =
11.9 Hz), 129.6 (d, J = 2.4 Hz), 129.6 (d, J = 109 Hz), 129.5 (d, J = 5.1 Hz), 129.1 (d, J = 10.2 Hz),
128.1 (d, J = 12.9 Hz), 21.4, 19.9, 19.7; 31P NMR (162 MHz, CDCl3) δ 29.5; HRMS (ESIꢀTOF) m/z: [M
+ Na]+ Calcd for C22H23OPNa 357.1379; Found 357.1377.
(3,4ꢀDimethylphenyl)bis(3ꢀmethoxyphenyl)phosphine oxide (3bc). White amorphous solid (53 mg,
72%): 1H NMR (400 MHz, CDCl3) δ 7.56 (d, J = 12.2 Hz, 1H), 7.46–7.29 (m, 5H), 7.28–7.14 (m, 3H),
13
7.11 (d, J = 8.0 Hz, 2H), 3.85 (s, 6H), 2.36 (s, 3H), 2.32 (s, 3H); C NMR (100 MHz, CDCl3) δ 159.5
(d, J = 14.9 Hz), 141.2 (d, J = 2.9 Hz), 137.1 (d, J = 12.4 Hz), 134.1 (d, J = 103 Hz), 132.9 (d, J = 9.9
Hz), 129.7 (d, J = 4.4 Hz), 129.6 (d, J = 2.4 Hz), 129.5 (d, J = 14.2 Hz), 129.1 (d, J = 84.5 Hz), 124.3
31
(d, J = 10.1 Hz), 118.0 (d, J = 2.6 Hz), 116.7 (d, J = 10.7 Hz), 55.4, 19.9, 19.7; P NMR (162 MHz,
CDCl3) δ 29.8; HRMS (ESIꢀTOF) m/z: [M + Na]+ Calcd for C22H23O3PNa 389.1277; Found 389.1279.
(3,4ꢀDimethylphenyl)diꢀpꢀtolylphosphine oxide (3bd). White amorphous solid (57 mg, 85%):7 1
H
NMR (400 MHz, CDCl3) δ 7.56–7.48 (m, 5H), 7.30–7.28 (m, 1H), 7.26–7.23 (m, 4H), 7.20–7.15 (m,
1H), 2.39 (s, 6H), 2.29 (s, 3H), 2.26 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 142.1 (d, J = 2.5 Hz), 140.9
(d, J = 6.1 Hz), 137.0 (d, J = 12.2 Hz), 133.0 (d, J = 9.8 Hz), 132.1 (d, J = 10.2 Hz), 131.3 (d, J = 146
Hz), 130.5 (d, J = 106 Hz), 129.7 (d, J = 3.1 Hz), 129.5 (d, J = 6.0 Hz), 129.1 (d, J = 12.4 Hz), 21.6,
19.9, 19.7; 31P NMR (162 MHz, CDCl3) δ 29.4.
11
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 12 of 20
(3,4ꢀDimethylphenyl)bis(4ꢀmethoxyphenyl)phosphine oxide (3be). White amorphous solid (64 mg,
87%): 1H NMR (400 MHz, CDCl3) δ 7.56 (dd, J = 11.4, 8.7 Hz, 4H), 7.50–7.46 (m, 1H), 7.30–7.25 (m,
1H), 7.19–7.16 (m, 1H), 6.94 (dd, J = 8.7, 2.0 Hz, 4H), 3.83 (s, 6H), 2.29 (s, 3H), 2.25 (s, 3H); 13C
NMR (100 MHz, CDCl3) δ 162.3 (d, J = 2.7 Hz), 140.8 (d, J = 2.8 Hz), 136.9 (d, J = 12.3 Hz), 133.9 (d,
J = 11.2 Hz), 132.9 (d, J = 9.8 Hz), 130.3 (d, J = 107 Hz), 129.6, 129.5 (d, J = 1.8 Hz), 124.5 (d, J = 110
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
31
Hz), 113.9 (d, J = 13.1 Hz), 55.3, 19.9, 19.7; P NMR (162 MHz, CDCl3) δ 28.9; HRMS (ESIꢀTOF)
m/z: [M + Na]+ Calcd for C22H23O3PNa 389.1277; Found 389.1279.
(3,4ꢀDimethylphenyl)bis(3,5ꢀdimethylphenyl)phosphine oxide (3bf). White amorphous solid (67
mg, 92%):7 1H NMR (400 MHz, CDCl3) δ 7.51 (d, J = 12.0 Hz, 1H), 7.31–7.25 (m, 5H), 7.20–7.17 (m,
1H), 7.14 (s, 2H), 2.31 (s, 15H), 2.27 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 140.8 (d, J = 2.8 Hz),
138.0 (d, J = 12.7 Hz), 136.9 (d, J = 12.2 Hz), 133.4 (d, J = 2.8 Hz), 133.3 (d, J = 106 Hz), 133.0 (d, J =
9.6 Hz), 130.5 (d, J = 104 Hz), 129.6 (d, J = 9.8 Hz), 129.6 (d, J = 1.2 Hz), 128.7 (d, J = 11.4 Hz), 21.3,
19.9, 19.7; 31P NMR (162 MHz, CDCl3) δ 29.6.
Bis(4ꢀchlorophenyl)(3,4ꢀdimethylphenyl)phosphine oxide (3bg). White amorphous solid (62 mg,
83%): 1H NMR (400 MHz, CDCl3) δ 7.63–7.50 (m, 4H), 7.49–7.37 (m, 5H), 7.30–7.15 (m, 2H), 2.31 (s,
3H), 2.27 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 141.8 (d, J = 2.5 Hz), 138.6 (d, J = 3.1 Hz), 137.5 (d,
J = 12.5 Hz), 133.4 (d, J = 10.7 Hz), 132.8 (d, J = 10.0 Hz), 131.1 (d, J = 105 Hz), 129.9 (d, J = 13.2
31
Hz), 129.5 (d, J = 10.3 Hz), 128.9 (d, J = 12.7 Hz), 128.5 (d, J = 119 Hz), 19.9, 19.7; P NMR (162
MHz, CDCl3) δ 28.0; HRMS (ESIꢀTOF) m/z: [M + Na]+ Calcd for C20H17Cl2OPNa 397.0286; Found
397.0281.
(3,4ꢀDimethylphenyl)di(naphthalenꢀ1ꢀyl)phosphine oxide (3bi). White amorphous solid (73 mg,
90%): 1H NMR (400 MHz, CDCl3) δ 8.85 (d, J = 8.4 Hz, 2H), 8.02 (d, J = 8.0 Hz, 2H), 7.92 (d, J = 8.0
Hz, 2H), 7.65 (d, J = 12.2 Hz, 1H), 7.58–7.44 (m, 4H), 7.41–7.24 (m, 5H), 7.22–7.14 (m, 1H), 2.34 (s,
13
3H), 2.30 (s, 3H); C NMR (100 MHz, CDCl3) δ 141.2 (d, J = 2.7 Hz), 137.2 (d, J = 12.4 Hz), 134.2,
134.1 (d, J = 18.1 Hz), 133.4 (d, J = 12.0 Hz), 133.3 (d, J = 9.6 Hz), 133.0 (d, J = 2.7 Hz), 130.2 (d, J =
106 Hz), 129.9 (d, J = 10.3 Hz) , 129.7 (d, J = 78.1 Hz), 128.7, 128.0 (d, J = 5.4 Hz), 126.9 (d, J = 85.3
12
ACS Paragon Plus Environment

Page 13 of 20
The Journal of Organic Chemistry
Hz), 124.2 (d, J = 14.4 Hz), 19.9, 19.8; 31P NMR (162 MHz, CDCl3) δ 36.5; HRMS (ESIꢀTOF) m/z: [M
1
2
3
+ Na]+ Calcd for C28H23OPNa 429.1379; Found 429.1378.
4
5
6
(2,5ꢀDimethylphenyl)diphenylphosphine oxide (3ca). White amorphous solid (55 mg, 90%):7 1
H
7
8
9
NMR (400 MHz, CDCl3) δ 7.69–7.62 (m, 4H), 7.56–7.51 (m, 2H), 7.48–7.43 (m, 4H), 7.22 (d, J = 7.8
Hz, 1H), 7.17–7.14 (m, 1H), 6.88 (d, J = 14.4 Hz, 1H), 2.36 (s, 3H), 2.20 (s, 3H); 13C NMR (100 MHz,
CDCl3) δ 140.0 (d, J = 8.1 Hz), 134.7 (d, J = 12.8 Hz), 133.9 (d, J = 12.5 Hz), 132.9 (d, J = 104 Hz),
132.8 (d, J = 2.7 Hz), 131.9 (d, J = 9.7 Hz), 131.8, 131.7 (d, J = 2.8 Hz), 130.4 (d, J = 103 Hz), 128.5
(d, J = 12.0 Hz), 21.2 (d, J = 4.7 Hz), 20.9; 31P NMR (162 MHz, CDCl3) δ 31.7.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
1
(2,5ꢀDimethylphenyl)diꢀmꢀtolylphosphine oxide (3cb). White amorphous solid (57 mg, 85%): H
NMR (400 MHz, CDCl3) δ 7.57 (d, J = 12.3 Hz, 2H), 7.39–7.27 (m, 6H), 7.25–7.10 (m, 2H), 6.88 (d, J
13
= 14.3 Hz, 1H), 2.37 (s, 9H), 2.20 (s, 3H); C NMR (100 MHz, CDCl3) δ 139.9 (d, J = 8.1 Hz), 138.4
(d, J = 11.9 Hz), 134.5 (d, J = 12.7 Hz), 133.9 (d, J = 12.6 Hz), 132.8 (d, J = 105 Hz), 132.6 (d, J = 2.6
Hz), 132.4 (d, J = 2.8 Hz), 132.3 (d, J = 9.2 Hz), 131.7 (d, J = 11.1 Hz), 130.6 (d, J = 102 Hz), 128.9 (d,
31
J = 10.2 Hz), 128.2 (d, J = 12.9 Hz), 21.4, 21.2 (d, J = 4.6 Hz), 20.9; P NMR (162 MHz, CDCl3) δ
31.9; HRMS (ESIꢀTOF) m/z: [M + Na]+ Calcd for C22H23OPNa 357.1379; Found 357.1377.
(2,5ꢀDimethylphenyl)bis(3ꢀmethoxyphenyl)phosphine oxide (3cc). White amorphous solid (60 mg,
82%): 1H NMR (400 MHz, CDCl3) δ 7.39–7.25 (m, 4H), 7.24–7.00 (m, 6H), 6.85 (d, J = 14.5 Hz, 1H),
3.80 (s, 6H), 2.38 (s, 3H), 2.20 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 159.6 (d, J = 14.8 Hz), 140.0 (d,
J = 8.0 Hz), 134.6 (d, J = 12.8 Hz), 134.1 (d, J = 103 Hz), 133.8 (d, J = 12.7 Hz), 132.8 (d, J = 2.6 Hz),
131.8 (d, J = 11.1 Hz), 130.2 (d, J = 104 Hz), 129.6 (d, J = 14.4 Hz), 124.1 (d, J = 10.0 Hz), 118.0 (d, J
= 2.5 Hz), 116.6 (d, J = 10.5 Hz), 55.4, 21.1 (d, J = 4.7 Hz), 20.9; 31P NMR (162 MHz, CDCl3) δ 32.1;
HRMS (ESIꢀTOF) m/z: [M + Na]+ Calcd for C22H23O3PNa 389.1277; Found 389.1279.
(2,5ꢀDimethylphenyl)diꢀpꢀtolylphosphine oxide (3cd). White amorphous solid (52 mg, 78%):7 1H
NMR (400 MHz, CDCl3) δ 7.54–7.49 (m, 4H), 7.27–7.24 (m, 4H), 7.21 (d, J = 7.7 Hz, 1H), 7.17–7.12
(m, 1H), 6.89 (d, J = 14.2 Hz, 1H), 2.40 (s, 6H), 2.36 (s, 3H), 2.20 (s, 3H); 13C NMR (100 MHz, CDCl3)
δ 142.0 (d, J = 2.7 Hz), 139.9 (d, J = 8.1 Hz), 134.5 (d, J = 12.6 Hz), 133.9 (d, J = 12.5 Hz), 132.6 (d, J
13
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 14 of 20
= 2.5 Hz), 131.9 (d, J = 10.1 Hz), 131.7 (d, J = 11.0 Hz), 130.9 (d, J = 102 Hz), 129.9 (d, J = 101 Hz),
129.2 (d, J = 12.4 Hz), 21.6, 21.2 (d, J = 4.6 Hz), 21.0; 31P NMR (162 MHz, CDCl3) δ 31.8.
1
2
3
4
5
6
7
8
(2,5ꢀDimethylphenyl)bis(4ꢀmethoxyphenyl)phosphine oxide (3ce). White amorphous solid (62 mg,
85%): 1H NMR (400 MHz, CDCl3) δ 7.54 (dd, J = 11.4, 8.7 Hz, 4H), 7.21–7.18 (m, 1H), 7.15–7.1 (m,
1H), 6.95 (dd, J = 8.7, 2.0 Hz, 4H), 6.88 (d, J = 14.3 Hz, 1H), 3.84 (s, 6H), 2.36 (s, 3H), 2.20 (s, 3H);
13C NMR (100 MHz, CDCl3) δ 162.2 (d, J = 2.8 Hz), 139.8 (d, J = 8.1 Hz), 134.5 (d, J = 12.7 Hz),
133.9 (d, J = 12.6 Hz), 133.7 (d, J = 11.1 Hz), 132.5 (d, J = 2.6 Hz), 131.7 (d, J = 11.1 Hz), 131.2 (d, J
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
31
= 105 Hz), 124.4 (d, J = 110 Hz), 114.0 (d, J = 13.1 Hz), 55.3, 21.13 (d, J = 4.6 Hz), 20.9; P NMR
(162 MHz, CDCl3) δ 31.5; HRMS (ESIꢀTOF) m/z: [M + Na]+ Calcd for C22H23O3PNa 389.1277; Found
389.1279.
(2,5ꢀDimethylphenyl)bis(3,5ꢀdimethylphenyl)phosphine oxide (3cf). White amorphous solid (64
mg, 88%):7 1H NMR (400 MHz, CDCl3) δ 7.27–7.11 (m, 8H), 6.88 (d, J = 14.2 Hz, 1H), 2.36 (s, 3H),
2.31 (s, 6H), 2.21 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 139.9 (d, J = 8.0 Hz), 138.0 (d, J = 12.6 Hz),
134.4 (d, J = 12.7 Hz), 133.9 (d, J = 12.6 Hz), 133.4 (d, J = 2.8 Hz), 132.3 (d, J = 102 Hz), 132.5 (d, J =
2.6 Hz), 131.6 (d, J = 11.0 Hz), 130.8 (d, J = 102 Hz), 129.4 (d, J = 9.7 Hz), 21.3, 21.2, 21.0; 31P NMR
(162 MHz, CDCl3) δ 32.1.
Bis(4ꢀchlorophenyl)(2,5ꢀdimethylphenyl)phosphine oxide (3cg). White amorphous solid (68 mg,
91%): 1H NMR (400 MHz, CDCl3) δ 7.60–7.54 (m, 4H), 7.45 (d, J = 7.8 Hz, 4H), 7.25 (d, J = 8.5 Hz,
1H), 7.21–7.14 (m, 1H), 6.83 (d, J = 14.6 Hz, 1H), 2.36 (s, 3H), 2.22 (s, 3H); 13C NMR (100 MHz,
CDCl3) δ 140.0 (d, J = 8.3 Hz), 138.5 (d, J = 3.3 Hz), 134.9 (d, J = 13.0 Hz), 133.6 (d, J = 12.8 Hz),
133.2 (d, J = 3.8 Hz), 133.2 (d, J = 10.5 Hz), 132.1 (d, J = 11.3 Hz), 131.2 (d, J = 104 Hz), 129.5 (d, J =
104 Hz), 129.0 (d, J = 12.7 Hz), 21.1 (d, J = 4.7 Hz), 20.9; 31P NMR (162 MHz, CDCl3) δ 30.2; HRMS
(ESIꢀTOF) m/z: [M + Na]+ Calcd for C20H17Cl2OPNa 397.0286; Found 397.0281.
(2,5ꢀDimethylphenyl)di(naphthalenꢀ1ꢀyl)phosphine oxide (3ci). White amorphous solid (72 mg,
88%): 1H NMR (400 MHz, CDCl3) δ 8.81 (d, J = 8.4 Hz, 2H), 8.00 (d, J = 7.8 Hz, 2H), 7.90 (d, J = 8.0
Hz, 2H), 7.56–7.39 (m, 4H), 7.37–7.16 (m, 6H), 7.01 (d, J = 14.6 Hz, 1H), 2.42 (s, 3H), 2.09 (s, 3H);
14
ACS Paragon Plus Environment

Page 15 of 20
The Journal of Organic Chemistry
13C NMR (100 MHz, CDCl3) δ 140.2 (d, J = 8.0 Hz), 135.0 (d, J = 12.8 Hz), 134.3 (d, J = 7.8 Hz),
134.0 (d, J = 1.3 Hz), 133.9 (d, J = 5.2 Hz), 133.3 (d, J = 12.0 Hz), 133.1 (d, J = 2.7 Hz), 132.8 (d, J =
2.6 Hz), 131.9 (d, J = 11.3 Hz), 130.6 (d, J = 102 Hz), 129.5 (d, J = 100 Hz), 128.7, 128.1 (d, J = 5.0
1
2
3
4
5
6
31
7
8
Hz), 126.9 (d, J = 83.9 Hz), 124.3 (d, J = 14.4 Hz), 21.5 (d, J = 3.9 Hz), 20.9; P NMR (162 MHz,
9
CDCl3) δ 38.6; HRMS (ESIꢀTOF) m/z: [M + Na]+ Calcd for C28H23OPNa 429.1379; Found 429.1378.
(2,3ꢀDihydroꢀ1Hꢀindenꢀ5ꢀyl)diphenylphosphine oxide (3da). White amorphous solid (63 mg,
99%): 1H NMR (400 MHz, CDCl3) δ 7.71–7.63 (m, 4H), 7.57–7.50 (m, 3H), 7.47–7.42 (m, 4H), 7.41–
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
13
7.36 (m, 1H), 7.30–7.28 (m, 1H), 3.10–2.82 (m, 4H), 2.22–1.89 (m, 2H); C NMR (100 MHz, CDCl3)
δ 148.9 (d, J = 2.7 Hz), 144.7 (d, J = 12.9 Hz), 133.0 (d, J = 104 Hz), 132.1 (d, J = 9.9 Hz), 131.7 (d, J =
2.6 Hz), 130.3 (d, J = 11.0 Hz), 129.7 (d, J = 99.1 Hz), 128.4 (d, J = 12.1 Hz), 127.9 (d, J = 10.2 Hz),
31
124.4 (d, J = 13.6 Hz), 32.8 (d, J = 33.2 Hz), 25.2; P NMR (162 MHz, CDCl3) δ 30.0; HRMS (ESIꢀ
TOF) m/z: [M + Na]+ Calcd for C21H19OPNa 341.1066; Found 341.1068.
(2,3ꢀDihydroꢀ1Hꢀindenꢀ5ꢀyl)bis(3ꢀmethoxyphenyl)phosphine oxide (3dc). White amorphous solid
1
(67 mg, 88%): H NMR (400 MHz, CDCl3) δ 7.48 (d, J = 11.9 Hz, 1H), 7.36–7.17 (m, 6H), 7.11–7.03
13
(m, 2H), 6.99 (d, J = 7.9 Hz, 2H), 3.73 (s, 6H), 2.92–2.79 (m, 4H), 2.07–1.98 (m, 2H); C NMR (100
MHz, CDCl3) δ 159.5 (d, J = 14.8 Hz), 149.0 (d, J = 2.2 Hz), 144.7 (d, J = 12.9 Hz), 134.2 (d, J = 103
Hz), 130.2 (d, J = 11.1 Hz), 129.6 (d, J = 106 Hz), 129.5 (d, J = 8.1 Hz), 127.8 (d, J = 10.2 Hz), 124.4
(d, J = 13.9 Hz), 124.4 (d, J = 10.0 Hz), 118.0 (d, J = 2.0 Hz), 116.8 (d, J = 10.6 Hz), 55.4, 32.9, 32.6,
31
25.2; P NMR (162 MHz, CDCl3) δ 30.3; HRMS (ESIꢀTOF) m/z: [M + Na]+ Calcd for C23H23O3PNa
401.1277; Found 401.1275.
(2,3ꢀDihydroꢀ1Hꢀindenꢀ5ꢀyl)diꢀpꢀtolylphosphine oxide (3dd). White amorphous solid (62 mg,
89%): 1H NMR (400 MHz, CDCl3) δ 7.57–7.48 (m, 5H), 7.42–7.32 (m, 1H), 7.30–7.19 (m, 5H), 3.06–
13
2.79 (m, 4H), 2.39 (s, 6H), 2.14–1.98 (m, 2H); C NMR (100 MHz, CDCl3) δ 148.7 (d, J = 2.6 Hz),
144.6 (d, J = 12.8 Hz), 142.2 (d, J = 2.7 Hz), 132.1 (d, J = 10.2 Hz), 130.3 (d, J = 11.2 Hz), 130.1 (d, J
= 105 Hz), 130.0 (d, J = 105 Hz), 129.1 (d, J = 12.0 Hz), 127.9 (d, J = 10.2 Hz), 124.4 (d, J = 13.6 Hz),
15
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 16 of 20
32.9, 32.6, 25.2, 21.6; 31P NMR (162 MHz, CDCl3) δ 30.5; HRMS (ESIꢀTOF) m/z: [M + Na]+ Calcd for
C23H23OPNa 369.1379; Found 369.1380.
1
2
3
4
5
6
(2,3ꢀDihydroꢀ1Hꢀindenꢀ5ꢀyl)bis(4ꢀmethoxyphenyl)phosphine oxide (3de). White amorphous solid
1
7
8
(63 mg, 83%): H NMR (400 MHz, CDCl3) δ 7.61–7.49 (m, 5H), 7.40–7.32 (m, 1H), 7.27 (d, J = 6.6
9
13
Hz, 1H), 6.94 (d, J = 8.3 Hz, 4H), 3.83 (s, 6H), 3.03–2.79 (m, 4H), 2.17–1.98 (m, 2H); C NMR (100
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
MHz, CDCl3) δ 162.3 (d, J = 2.8 Hz), 148.6 (d, J = 2.8 Hz), 144.6 (d, J = 12.8 Hz), 133.9 (d, J = 11.2
Hz), 130.6 (d, J = 104 Hz), 130.2 (d, J = 11.0 Hz), 127.8 (d, J = 10.2 Hz), 124.5 (d, J = 110 Hz), 124.3
31
(d, J = 13.5 Hz), 113.9 (d, J = 13.1 Hz), 55.3, 32.9, 32.6, 25.2 ; P NMR (162 MHz, CDCl3) δ 29.7;
HRMS (ESIꢀTOF) m/z: [M + Na]+ Calcd for C23H23O3PNa 401.1277; Found 401.1275.
(2,3ꢀDihydroꢀ1Hꢀindenꢀ5ꢀyl)bis(3,5ꢀdimethylphenyl)phosphine oxide (3df). White amorphous
1
solid (72 mg, 96%): H NMR (400 MHz, CDCl3) δ 7.55 (d, J = 11.9 Hz, 1H), 7.42–7.33 (m, 1H), 7.28
(d, J = 12.3 Hz, 5H), 7.14 (s, 2H), 2.98–2.87 (m, 4H), 2.31 (s, 12H), 2.15–2.02 (m, 2H); 13C NMR (100
MHz, CDCl3) δ 148.6 (d, J = 2.7 Hz), 144.6 (d, J = 12.6 Hz), 137.9 (d, J = 12.7 Hz), 133.4 (d, J = 2.8
Hz), 132.8 (d, J = 103 Hz), 130.4 (d, J = 105 Hz), 130.2 (d, J = 11.0 Hz), 129.6 (d, J = 9.8 Hz), 127.9
(d, J = 10.1 Hz), 124.3 (d, J = 13.5 Hz), 32.9, 32.7, 25.2, 21.3; 31P NMR (162 MHz, CDCl3) δ 30.1;
HRMS (ESIꢀTOF) m/z: [M + Na]+ Calcd for C25H27OPNa 397.1692; Found 397.1689.
Bis(4ꢀchlorophenyl)(2,3ꢀdihydroꢀ1Hꢀindenꢀ5ꢀyl)phosphine oxide (3dg). White amorphous solid
1
(73 mg, 94%): H NMR (400 MHz, CDCl3) δ 7.62–7.55 (m, 4H), 7.49 (d, J = 12.2 Hz, 1H), 7.46–7.42
(m, 4H), 7.39–7.28 (m, 2H), 3.00–2.86 (m, 4H), 2.13–2.06 (m, 2H); 13C NMR (100 MHz, CDCl3) δ
149.5 (d, J = 2.7 Hz), 145.1 (d, J = 13.1 Hz), 138.6 (d, J = 3.3 Hz), 133.4 (d, J = 10.7 Hz), 131.2 (d, J =
105 Hz), 130.1 (d, J = 11.2 Hz), 129.4 (d, J = 107 Hz), 128.9 (d, J = 12.7 Hz), 127.7 (d, J = 10.4 Hz),
124.7 (d, J = 13.8 Hz), 33.0, 32.6, 25.2; 31P NMR (162 MHz, CDCl3) δ 28.4; HRMS (ESIꢀTOF) m/z: [M
+ Na]+ Calcd for C21H17Cl2OPNa 409.0286; Found 409.0281.
(3,4ꢀDimethoxyphenyl)diphenylphosphine oxide (3ea). White amorphous solid (48 mg, 71%):24 1
H
NMR (400 MHz, CDCl3) δ 7.69–7.61 (m, 4H), 7.53 (d, J = 6.3 Hz, 2H), 7.48–7.43 (m, 4H), 7.30 (dd, J
13
= 12.3, 1.4 Hz, 1H), 7.08–6.99 (m, 1H), 6.90 (d, J = 3.1 Hz, 1H), 3.90 (s, 3H), 3.83 (s, 3H); C NMR
16
ACS Paragon Plus Environment

Page 17 of 20
The Journal of Organic Chemistry
(100 MHz, CDCl3) δ 152.1 (d, J = 1.4 Hz), 149.2 (d, J = 14.8 Hz), 132.6 (d, J = 105 Hz), 132.1 (d, J =
9.9 Hz), 131.9 (d, J = 2.6 Hz), 128.4 (d, J = 12.1 Hz), 125.9 (d, J = 11.3 Hz), 123.8 (d, J = 110 Hz),
114.2 (d, J = 11.5 Hz), 110.7 (d, J = 15.4 Hz), 56.1, 55.9; 31P NMR (162 MHz, CDCl3) δ 29.9.
1
2
3
4
5
6
(3ꢀMethoxyphenyl)diphenylphosphine oxide (3fa). White amorphous solid (32 mg, 52%):6b 1
H
7
8
9
NMR (400 MHz, CDCl3) δ 7.69–7.64 (m, 4H), 7.56–7.53 (m, 2H), 7.48–7.44 (m, 4H), 7.38–7.28 (m,
2H), 7.16–7.06 (m, 2H), 3.80 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 159.6 (d, J = 15.0 Hz), 133.6 (d, J
= 104 Hz), 132.3 (d, J = 104 Hz), 132.1 (d, J = 9.9 Hz), 131.9 (d, J = 2.6 Hz), 129.6 (d, J = 14.4 Hz),
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
31
128.5 (d, J = 12.1 Hz), 124.4 (d, J = 10.0 Hz), 118.2 (d, J = 3.0 Hz), 116.8 (d, J = 10.6 Hz), 55.4; P
NMR (162 MHz, CDCl3) δ 29.4.
1
(3ꢀMethoxyphenyl)diꢀpꢀtolylphosphine oxide (3fd). White amorphous solid (34 mg, 50%): H
NMR (400 MHz, CDCl3) δ 7.53 (dd, J = 11.8, 8.0 Hz, 4H), 7.36–7.31 (m, 1H), 7.29–7.23 (m, 5H),
7.15–7.10 (m, 1H), 7.06–7.03 (m, 1H), 3.79 (s, 3H), 2.39 (s, 6H); 13C NMR (100 MHz, CDCl3) δ 159.5
(d, J = 14.8 Hz), 142.3 (d, J = 2.7 Hz), 134.4 (d, J = 103 Hz), 132.1 (d, J = 10.3 Hz), 129.9 (d, J = 106
Hz), 129.5 (d, J = 14.3 Hz), 129.2 (d, J = 12.5 Hz), 124.3 (d, J = 10.0 Hz), 118.0 (d, J = 2.6 Hz), 116.8
31
(d, J = 10.7 Hz), 55.4, 21.6; P NMR (162 MHz, CDCl3) δ 28.9; HRMS (ESIꢀTOF) m/z: [M + Na]+
Calcd for C21H21O2PNa 359.1171; Found 359.1174.
(3ꢀMethoxyphenyl)bis(4ꢀmethoxyphenyl)phosphine oxide (3fe). White amorphous solid (55 mg,
75%):25 1H NMR (400 MHz, CDCl3) δ 7.61–7.51 (m, 4H), 7.38–7.22 (m, 2H), 7.16–7.02 (m, 2H), 6.96
13
(d, J = 8.1 Hz, 4H), 3.84 (s, 6H), 3.79 (s, 3H); C NMR (100 MHz, CDCl3) δ 162.5 (d, J = 2.6 Hz),
159.6 (d, J = 14.8 Hz), 133.9 (d, J = 11.3 Hz), 132.5 (d, J = 101 Hz), 129.6 (d, J = 14.3 Hz), 124.4 (d, J
= 111 Hz), 124.3 (d, J = 10.2 Hz), 118.0 (d, J = 2.4 Hz), 116.8 (d, J = 13.0 Hz), 114.1 (d, J = 13.2 Hz),
55.5, 55.4; 31P NMR (162 MHz, CDCl3) δ 29.4.
Diphenyl(mꢀtolyl)phosphine oxide (metaꢀ3ga) and diphenyl(pꢀtolyl)phosphine oxide (paraꢀ3ga).
White amorphous solid (51 mg, 87%):26 two isomers in ∼1.3:1 ratio; 1H NMR (400 MHz, CDCl3) metaꢀ
3ga: δ 7.69–7.64 (m, 4H), 7.59–7.52 (m, 3H), 7.48–7.43 (m, 4H), 7.40–7.29 (m, 3H), 2.36 (s, 3H);
paraꢀ3ga: δ 7.69–7.64 (m, 4H) 7.58–7.49 (m, 4H), 7.47–7.42 (m, 4H), 7.28–7.25 (m, 2H), 2.40 (s, 3H);
17
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 18 of 20
13C NMR (100 MHz, CDCl3) metaꢀ3ga: δ 138.5 (d, J = 11.9 Hz), 132.5 (d, J = 102 Hz), 132.8 (d, J =
2.7 Hz), 132.5 (d, J = 9.4 Hz), 132.1 (d, J = 103 Hz), 132.1 (d, J = 9.9 Hz), 131.9 (d, J = 2.7 Hz), 129.1
(d, J = 10.2 Hz), 128.5 (d, J = 12.1 Hz), 128.3 (d, J = 12.9 Hz), 21.4; paraꢀ3ga: δ 142.4 (d, J = 2.8 Hz),
132.7 (d, J = 103 Hz), 132.1 (d, J = 10.1 Hz), 132.0 (d, J = 9.8 Hz), 131.8 (d, J = 2.8 Hz), 129.2 (d, J =
12.4 Hz), 129.1 (d, J = 106 Hz), 128.4 (d, J = 12.0 Hz), 21.6 (d, J = 1.0 Hz); 31P NMR (162 MHz,
CDCl3) metaꢀ3ga: δ 29.34; paraꢀ3ga: δ 29.29.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Supporting Information
Copies of 1H, 13C and 31P NMR spectra for 3. This material is available free of charge via the Internet at
http://pubs.acs.org.
Corresponding Author
*Eꢀmail: qianchen@gdut.edu.cn.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
This work was supported by the National Natural Science Foundation of China (21242002), the Science
and Technology Planning Project of Guangdong Province (2015A020211026), and 100 Young Talents
Programme of Guangdong University of Technology (220413506).
REFERENCES
(1) (a) Bhattacharya, A. K.; Thyagarajan, G. Chem. Rev. 1981
103, 3029. (c) George, A.; Veis, A. Chem. Rev. 2008 108, 4670. (d) Van der Jeught, S.; Stevens, C. V. Chem. Rev.
2009 109, 2672. (e) Wydysh, E. A.; Medghalchi, S. M.; Vadlamudi, A.; Townsend, C. A. J. Med. Chem. 2009 52
3317. (f) Spampinato, V.; Tuccitto, N.; Quici, S.; Calabrese, V.; Marletta, G.; Torrisi, A.; Licciardello, A. Langmuir
, 81, 415. (b) Tang, W.; Zhang, X. Chem. Rev. 2003,
,
,
,
,
2010
,
26, 8400. (g) Yu, P.; Lin, J. S.; Li, L. Angew. Chem., Int. Ed. 2014
137, 13768.
,
53, 11890. (h) Uraguchi, D.; Kinoshita, N.;
Kizu, T. J. Am. Chem. Soc. 2015
,
18
ACS Paragon Plus Environment

Page 19 of 20
The Journal of Organic Chemistry
(2) (a) Arbuzov, B. A. Pure Appl. Chem. 1964 , 307. (b) Bhattacharya, A. K.; Thyagarajan, G. Chem. Rev. 1981
,
9
,
,
1
2
3
81, 415. (c) Renard, P.ꢀY.; Vayron, P.; Leclerc, E.; Valleix, A.; Mioskowski, C. Angew. Chem., Int. Ed. 2003, 42
4
5
2389.
6
7
8
9
(3) (a) de Meijere, A.; Diederich, F. MetalꢀCatalyzed CrossꢀCoupling Reactions; WileyꢀVCH: Weinheim, 2004. (b)
Börner, A. Phosphorus Ligands in Asymmetric Catalysis: Synthesis and Application; WileyꢀVCH: Weinheim, 2008.
(c) Kamer, P. C. J.; van Leeuwen, P. W. N. M. Phosphorus(III) Ligands in Homogeneous Catalysis: Design and
Synthesis; WileyꢀVCH: Chichester, U.K., 2012.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(4) For recent reviews, see: (a) Jablonkai, E.; Keglevich, G. Curr. Org. Synth. 2014
Keglevich, G. Org. Prep. Proced. Int. 2014 46, 281.
(5) For recent reviews, see: (a) Tadross, P. M.; Stoltz, B. M. Chem. Rev. 2012
R.; Biju, A. T. Chem. Soc. Rev. 2012 41, 3140. For recent examples, see: (c) Shi, J.; Qiu, D.; Wang, J.; Xu, H.; Li, Y.
J. Am. Chem. Soc. 2015 137, 5670. (d) Chen, Y.; Willis, M. C. Org. Lett. 2015 17, 4786. (e) Bhojgude, S. S.;
Baviskar, D. R.; Gonnade, R. G.; Biju, A. T. Org. Lett. 2015 17, 6270. (f) Zeng, Y.; Li, G.; Hu, J. Angew. Chem., Int.
Ed. 2015 54, 10773. (g) Li, Y.; Chakrabarty, S.; MückꢀLichtenfeld, C.; Studer, A. Angew. Chem., Int. Ed. 2016
802. (h) Samineni, R.; Srihari, P.; Mehta, G. Org. Lett. 2016
2016 81, 3542.
(6) For selected examples, see: (a) Rémond, E.; Tessier, A.; Leroux, F. R.; Bayardon, J.; Jugé, S. Org. Lett. 2010
12, 1568. (b) Dhokale, R. A.; Mhaske, S. B. Org. Lett. 2013
A. T. Org. Lett. 2014 16, 5132. (d) Bhunia, A.; Kaicharla, T.; Porwal, D.; Gonnade, R. G.; Biju, A. T. Chem.
50, 11389. (e) Bayardon, J.; Bernard, J.; Rémond, E.; Rousselin, Y.; MalaceaꢀKabbara, R.; Jugé, S.
17, 1216. (f) Bayardon, J.; Rousselin, Y.; Jugé, S. Org. Lett. 2016 18, 2930.
81, 276.
72, 333.
, 11, 429. (b) Jablonkai, E.;
,
,
112, 3550. (b) Bhunia, A.; Yetra, S.
,
,
,
,
,
,
55
,
,
,
18, 2832. (i) Zhang, L.; Geng, Y.; Jin, Z. J. Org. Chem.
,
,
15, 2218. (c) Bhunia, A.; Roy, T.; Gonnade, R. G.; Biju,
,
Commun. 2014
,
,
Org. Lett. 2015
,
(7) Chen, Q.; Yan, X.; Du, Z.; Zhang, K.; Wen, C. J. Org. Chem. 2016
(8) Yang, G.; Shen, C.; Quan, M.; Zhang, W. Tetrahedron 2016
(9) Han, L.ꢀB.; Tanaka, M. J. Am. Chem. Soc. 1996 118, 1571.
(10) (a) Han, L.ꢀB.; Choi, N.; Tanaka, M. Organomettalics 1996
Angew. Chem., Int. Ed. 1998 37, 94. (c) Allen Jr., A.; Manke, D. R.; Lin, W. Tetrahedron Lett. 2000
Han, L.ꢀB.; Zhao, C.ꢀQ.; Tanaka, M. J. Org. Chem. 2001 66, 5929. (e) Han, L.ꢀB.; Zhao, C.ꢀQ.; Onozawa, S.; Goto,
M.; Tanaka, M. J. Am. Chem. Soc. 2002 124, 3842. (f) Allen Jr., A.; Ma, L.; Lin, W. Tetrahedron Lett. 2002 43
3707. (g) Han, L.ꢀB.; Ono, Y.; Shimada, S. J. Am. Chem. Soc. 2008 130, 2752. (h) Xu, Q.; Zhao, C.ꢀQ.; Han, L.ꢀB.
,
,
,
,
15, 3259. (b) Han, L.ꢀB.; Hua, R.; Tanaka, M.
41, 151. (d)
,
,
,
,
,
,
,
19
ACS Paragon Plus Environment

The Journal of Organic Chemistry
130, 12648. (i) Xu, Q.; Shen, R.; Ono, Y.; Nagahata, R.; Shimada, S.; Goto, M.; Han, L.ꢀB.
47, 2333.
(11) (a) Han, L.ꢀB.; Zhang, C.; Yazawa, H.; Shimada, S. J. Am. Chem. Soc. 2004
Y.; Yazawa, Y. Org. Lett. 2005 , 2909.
(12) (a) Zhao, C.ꢀQ.; Han, L.ꢀB.; Goto, M.; Tanaka, M. Angew. Chem., Int. Ed. 2001
Zhao C.ꢀQ.; Tanaka, M. J. Org. Chem. 2001 66, 5929.
(13) (a) Niu, M.; Fu, H.; Jiang, Y.; Zhao, Y. Chem. Commun. 2007, 272. (b) Trostyanskaya, I. G.; Beletskaya, I. B.
Tetrahedron 2014 70, 2556.
(14) Kuramshin, A. I.; Nikolaev, A. A.; Cherkasov, R. A. Mendeleev Commun. 2005
(15) Takaki, K.; Takeda, M.; Koshoji, G.; Shishido, T.; Takehira, K. Tetrahedron Lett. 2001
(16) (a) Chen, Q.; Zhang, C.; Chen, L.; Wen, C.; Du, Z.; Chen, H.; Zhang, K. Tetrahedron Lett. 2015
Wen, C.; Chen, Q.; He, Z.; Yan, X.; Zhang, C.; Du, Z.; Zhang, K. Tetrahedron Lett. 2015 56, 5470. (c) Chen, L.;
Zhang, C.; Wen, C.; Zhang, K.; Liu, W.; Chen, Q. Catal. Commun. 2015 65, 81.
(17) Xie, C.; Liu, L.; Zhang, Y.; Xu, P. Org. Lett. 2008 10, 2393.
(18) Liu, Z.; Larock, R. C. Org. Lett. 2004 , 99.
Page 20 of 20
J. Am. Chem. Soc. 2008
Chem. Commun. 2011
,
1
2
3
4
5
6
7
8
,
,
126, 5080. (b) Han, L.ꢀB.; Ono,
,
7
,
40, 1929. (b) Han, L.ꢀB.;
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
,
,
,
15, 155.
42, 6357.
,
,
56, 2094. (b)
,
,
,
,
6
(19) For the active [Ar2P(O)Cu] or [Ar2P(O)Ag] complexes formed by the interaction of copper or silver salts with
Ar2P(O)H, see: (a) Lemmen, T. H.; Goeden, G. V.; Huffman, J. C.; Geerts, R. L.; Caulton, K. G. Inorg. Chem. 1990
,
29, 3680. (b) Gelman, D.; Jiang, L.; Buchwald, S. L. Org. Lett. 2003
Eustache, J. Org. Lett. 2005, , 681. (d) Huang, C.; Tang, X.; Fu, H.; Jiang, Y.; Zhao, Y. J. Org. Chem. 2006
5020. (e) Kondoh, A.; Yorimitsu, H.; Oshima, K. J. Am. Chem. Soc. 2007 129, 4099. (f) Li, Y.ꢀM.; Sun, M.; Wang,
H.ꢀL; Tian, Q.ꢀP.; Yang, S.ꢀD. Angew. Chem. 2013 125, 4064.
(20) Himeshima, Y.; Sonoda, T.; Kobayashi, H. Chem. Lett. 1983
(21) (a) Hays, H. R. J. Org. Chem. 1968 33, 3690. (b) Harger, M. J. P.; Westlake, S. Tetrahedron 1982
(22) Haberhauer, G.; Ernst, S.; Wilch, C. Chem. Eur. J. 2011 17, 8643.
(23) Hu, G.; Chen, W.; Fu, T.; Peng, Z.; Qiao, H.; Gao, Y.; Zhao, Y. Org. lett
(24) Xu, W.; Zou, J.ꢀP.; Zhang, W. Tetrahedron Lett 2010 51, 2639.
(25) Guo, Y.; Fu, H.; Chen, H.; Li, X. Catal. Commun 2008 , 1842.
(26) Zhang, J.ꢀS.; Chen, T.; Yang, J.; Han, L.ꢀB. Chem. Commun. 2015
,
5
, 2315. (c) Thielges, S.; Bisseret, P.;
7
,
71,
,
,
,
12, 1211.
,
, 38, 1511.
,
.
2013, 15, 5362.
.
,
.
, 9
,
51, 7540.
20
ACS Paragon Plus Environment