Employing Arynes for the Generation of Aryl Anion Equivalents and Subsequent Reaction with Aldehydes

Article abstract of DOI:10.1021/acs.joc.8b01549

Arynes are highly reactive intermediates, which are utilized for the electrophilic arylation of various X-H bonds (X = O, N, S etc.). Herein, a new synthetic strategy is demonstrated, where arynes are converted into aryl anion equivalents by treatment with phosphines and a base. The addition of phosphines to arynes form the phosphonium salts, which in the presence of a carbonate base generates the aryl anion equivalent. Subsequent addition of the aryl anions with aldehydes afforded the secondary alcohols.

Full text of DOI:10.1021/acs.joc.8b01549

Subscriber access provided by Service des bibliothèques | Université de Sherbrooke
Note
Employing Arynes for the Generation of Aryl Anion
Equivalents and Subsequent Reaction with Aldehydes
Rahul N Gaykar, Anup Bhunia, and Akkattu T. Biju
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.8b01549 • Publication Date (Web): 10 Jul 2018
Downloaded from http://pubs.acs.org on July 10, 2018
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 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 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.
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 27
The Journal of Organic Chemistry
1
2
3
4
5
6
Employing Arynes for the Generation of Aryl Anion Equivalents
and Subsequent Reaction with Aldehydes
7
8
9
Rahul N. Gaykar,† Anup Bhunia,‡ and Akkattu T. Biju*,†
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
† Department of Organic Chemistry, Indian Institute of Science, Bangaloreꢀ560012, India
‡Organic Chemistry Division, CSIRꢀNational Chemical Laboratory (CSIRꢀNCL), Dr. Homi
Bhabha Road, Pune 411008, India
Eꢀmail: atbiju@iisc.ac.in
ABSTRACT: Arynes are highly reactive intermediates, which are utilized for the electrophilic
arylation of various XꢀH bonds (X = O, N, S etc.). Herein, a new synthetic strategy is
demonstrated, where arynes are converted into aryl anion equivalents by treating with
phosphines and a base. The addition of phosphines to arynes form the phosphonium salts, which
in the presence of a carbonate base generates the aryl anion equivalent. Subsequent addition of
the aryl anions with aldehydes afforded the secondary alcohols.
Ever since the seminal discovery of 2ꢀtrimethylsilylaryl triflates as a precursor for the
mild and convenient generation of arynes,1 the chemistry of this highly reactive intermediate has
witnessed a resurgence of interest in the last three decades.2 The inherent strain in the CꢀC triple
bond of aryne has been exploited in various pericyclic reactions,3 insertion reactions,4
multicomponent reactions,5 molecular rearrangements,6 and transitionꢀmetalꢀcatalyzed
reactions.7 Moreover arynes are widely employed for the electrophilic arylation of XꢀH bonds (X
= O, N, S etc.)2l and even for the activated CꢀH bonds (Scheme 1a).8 Interestingly, however, the
use of arynes for the generation of aryl anions, and thereby for the nucleophilic arylation
reactions, to the best of our knowledge is not reported. This will be interesting as this method
1
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 2 of 27
1
2
3
4
5
6
7
8
9
will obviate the use of aryl organometallic reagents for the arylation reactions. Herein, we
demonstrate the use of arynes for the generation of aryl anion equivalents and subsequent
interception with aldehydes for the synthesis of secondary alcohols (Scheme 1b). For this, arynes
are initially treated with phosphines for the in situ generation of phosphonium salts,9 which in the
presence of a carbonate base generates the aryl anion equivalent. It may be noted in this context
that the nucleophileꢀtriggered generation of aryl anion intermediates from arynes followed by
their interception with a thirdꢀcomponent is known in the literature.2d
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. TransitionꢀMetalꢀFree Arylation Using Arynes
We have recently reported the aryne multicomponent coupling triggered by phosphines
using aldehydes/activated ketones as the thirdꢀcomponent for the synthesis of stable
pentacovalent phosphoranes based on the benzooxaphosphole system.10 In this reaction, the
initial 1,3ꢀzwitterionic intermediate generated from phosphine and aryne was intercepted with
the carbonyl moiety in a formal [3+2] cycloaddition allowing the synthesis of phosphorous
heterocycles.11,12 In this context, we envisioned that if the initially formed 1,3ꢀdiplole is
protonated by water to generate the phosphonium salt, followed by the addition of a carbonate
base to the phosphonium salt could eventually generate the aryl anion, which could intercept the
aldehyde to form the secondary alcohol. Related aryl anion generation from tetraaryl
phosphonium salt was recently uncovered by Xiao and coꢀworkers13a and McNally and coꢀ
workers.14
2
ACS Paragon Plus Environment

Page 3 of 27
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
9
The present study was initiated by the treatment of PPh3 with aryne generated from 2ꢀ
(trimethylsilyl) aryl triflate 2a1 (using KF and 18ꢀcrownꢀ6) for the in situ formation of the
tetraphenyl phosphonium salt followed by the reaction with 4ꢀchlorobenzaldehyde 1a in the
presence of Cs2CO3.15 Interestingly, under these conditions, the reaction afforded the benzhydrol
derivative 3a in 75% yield (Scheme 2).16,17 Notably, the benzooxaphosphole derivative
(multicomponent adduct)10 was not observed under these conditions. The addition of water was
necessary for the smooth formation of the phosphonium salt, and Cs2CO3 was found to be the
best carbonate base source for the reaction (over other bases including SrCO3 and K2CO3)
probably due to the better solubility in THF. The high affinity between oxygen and phosphorus
(for the release of Ph3P=O) may be the driving force for the smooth generation of the aryl anion
intermediate and subsequent interception with aldehyde.
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. Nucleophilic Arylation of Aldehydes Using Arynes
With the optimized reaction conditions in hand, we then examined the scope and
limitations of the present arylation method (Scheme 3). The in situ generated aryl anion was
smoothly added to a range of aromatic aldehydes bearing halogens, electronꢀreleasing, neutral
and –withdrawing groups at the 4ꢀposition of the ring thereby affording diverse benzhydrol
derivatives in moderate to good yield (3a-3j). This indicates that the electronic nature of the
aldehydes did not significantly influence the outcome of this nucleophilic arylation. Moreover,
this nucleophilic arylation was well tolerated by aldehydes having substituents at the 3ꢀposition,
2ꢀposition as well as diꢀ and triꢀsubstitution to furnish the desired products in moderate to good
3
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 4 of 27
1
2
3
4
5
6
7
8
9
yields (3k-3t). In addition, heterocyclic aldehydes are found to be good coupling partner for
arylation using arynes to afford the aryl heteroaryl methanol derivatives in moderate yield (3u,
3v). Interestingly, linear and branched aliphatic aldehydes and α,βꢀunsaturated aldehydes
underwent smooth nucleophilic arylation thus expanding the scope of this reaction (3w-3ab).
Notably, the reaction using geranial afforded the corresponding alcohol in 50% yield. The
enolizable aldehydes did not undergo the aldol condensation or direct addition to arynes under
the present reaction conditions.
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 3. Substrate Scope of the Reactiona
PPh3 (3.0 equiv), H2O (2.2 equiv)
KF (4.0 equiv), 18-crown 6 (4.0 equiv)
OH
O
TMS
+
R
R
H
Cs2CO3 (4.0 equiv), THF, 0 °C - 65 °C
24 h, then HCl, (75%)
TfO
1
2a
3
R1 = Cl, , 75%
3a
OH
R1 = Br, , 60%
3b
R2
R2 = Br, , 56%
R1 = F, 3c, 67%
3k
R2 = NO2, , 51%
OH
R1 = H, , 54%
3l
3d
R1 = Me, , 69%
3e
R1 = OMe, 3f, 69%b
R3 OH
R1
R1 = Ph, , 77%
3g
R3 = Me,
, 67%
R1 = CN, , 58%
3m
3h
b
R3 = Cl, , 62%
R1 = CO2Me, , 79%
3n
3i
R1 = CF3, , 68%
3j
OH
OMe OH
OH
MeO
MeO
MeO
Cl
Cl
b
b
3o
, 66%
3p
, 68%
3q
, 64%
OH
OH
OH
MeO
MeO
b
OMe
3r
, 60%
3s
, 73%
3t
, 63%
OH
OH
OH
OH
Me
S
Ph
S
b
3u
, 44%
3v
, 32%
3w
, 53%
3x
, 47%
OH
Ph OH
OH
Ph
Ph
HO
b
b
b
3y
, 75%
3z
, 50%
3aa
, 63%
3ab
, 50%
a
All reactions are performed on 0.25 mmol scale of 1 otherwise indicated. For details on experimental
procedure, see the Supporting Information. b Reactions performed on 0.5 mmol scale.
4
ACS Paragon Plus Environment

Page 5 of 27
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
9
Next, we focused our attention on tolerance of the present method with substituents on
arynes as well as on phosphines. Performing the reaction under the standard conditions using
aryne generated from 2b afforded the alcohol 3ac in 48% along with 3a in 11% (Scheme 4, eq
1). The alcohol 3ac was formed from the aryl anion generated from the sesamolꢀderived aryne
(formed from 2b) and the generation of unsubstituted aryl anion from the phosphonium salt upon
interception with 1a could result in the formation of 3a. The preferential formation of 3ac in this
case could be due to the stabilization of the aryl anion generated from 2b due to the inductive
effect of the two oxygen atoms. Moreover, when the reaction was carried out using aryne
generated from 2c, the alcohol 3ad was formed in 8% and 3a in 28% (eq 2). In addition,
employing the aryne generated from 2d in the present arylation reaction afforded the alcohol
(generated from the aryne moiety) in traces, and the product 3a was formed in 66% (eq 3). The
Scheme 4. Variation of Arynes
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
low reactivity of the aryl anion generated from 2c and 2d may be due to the presence of electronꢀ
releasing groups, which makes the anion less stable and may readily abstract a proton from the
trace water present in the medium.
5
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 6 of 27
1
2
3
4
5
6
7
8
9
When the reaction was carried out under the standard conditions using triꢀpꢀ
methoxyphenyl phosphine, the reaction furnished a mixture of secondary alcohols 3a and 3af in
24% and 19% yield respectively (Scheme 5, eq 4). The formation of 3a in slightly higher yield
may be due to the better leaving group ability of the phenyl group over the pꢀmethoxyphenyl
group in the initially formed phosphonium salt. Disappointingly, the attempted reaction with the
triꢀpꢀtrifluoromethylphenyl phosphine as the nucleophilic trigger did not afford the expected
products 3ag and 3a (eq 5). This may be due to the less nucleophilicity of the phosphine for the
formation of the tetraaryl phosphonium salt.
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 5. Variation of Phosphines
To demonstrate the role of water in the generation of the tetraaryl phosphonium salt and
the aryl anion generation thereof, a reaction was performed in the absence of water. This reaction
did not afford the expected alcohol product 3a, but resulted in the formation of the
benzooxaphosphole 4a in 49% yield (Scheme 6).10a In this case, the initially formed 1,3ꢀ
zwitterion from phosphine and aryne instead of protonation underwent a formal [3+2] annulation
with the aldehyde moiety leading to the formation of 4a.
Scheme 6. Reaction in the Absence of H2O
6
ACS Paragon Plus Environment

Page 7 of 27
The Journal of Organic Chemistry
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
A proposed mechanism of this nucleophilic arylation using arynes is shown in Scheme 7.
The reaction proceeds via the generation of aryne from 2a using the fluoride source.
Nucleophilic addition of phosphine to aryne forms the 1,3ꢀzwitterionic intermediate 5, which
gets protonated in the presence of H2O to form the tetraaryl phosphonium triflate 6. In the
absence of H2O, the intermediate 5 undergoes a formal [3+2] annulation with aldehyde to form
the benzoxaphosphole derivative. The phosphonium could be converted into the alcohol in two
pathways. In pathway 1, the nucleophilic attack of Cs2CO3 on the phosphonium cation generates
a trigonal bipyramidal tetraaryloxy phosphorane intermediate 7, where the carbonate and the aryl
moiety are in the axial position. Simultaneous decarboxylation and nucleophilic attack of the
generated aryl moiety (via the elimination of Ph3P=O) on the aldehyde followed by protonation
could generate the alcohol 3. Alternatively, the decomposition of Cs2CO3 in presence of H2O
could generate CsOH (pathway 2). The addition of CsOH to the salt 6 could generate the
pentavalent phosphorus intermediate 8, which upon deprotonation in the presence of base
generates the oxyanionic phosphorane intermediate 9. The elimination of aryl anion from 9 (via
the elimination of Ph3P=O) followed by addition to aldehyde and a subsequent protonation could
generate the alcohol 3. It is reasonable to believe that the elimination of stable Ph3P=O may be
the driving force for the generation of aryl anion either from intermediates 7 or 9. Although the
addition of carbonate to 6 generating the intermediate 7 is preferred, the CsOH addition to 6
leading to intermediate 8 cannot be ruled out at this stage because of the presence of H2O in the
reaction medium. Moreover, the reactions performed using substituted arynes (Scheme 4, eqs 1ꢀ
3), and with phosphine derivative (Scheme 5, eq 4) indicate that the aryl group migration in the
7
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 8 of 27
1
2
3
4
present reaction could be either from the aryne source or from the aryl group attached to the
5
6
phosphorus.
7
8
Scheme 7. Proposed Mechanism of the Reaction
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
This nucleophilic arylation using arynes was not limited to aldehydes as the electrophiles,
but instead activated ketones such as isatins can easily be arylated using this method resulting in
the formation tertiary alcohols. For instance, treatment of Nꢀmethyl isatin 10a with aryne
generated from 2a under the present reaction conditions afforded the oxindole derivative 11a in
73% yield (Scheme 8).18 The reaction afforded moderate yield of desired product with Nꢀbenzyl
isatin and 5ꢀmethoxy isatin as substrates under identical reaction conditions.
Scheme 8. Nucleophilic Arylation of Isatins Using Arynesa
a See the Supporting Information for details
8
ACS Paragon Plus Environment

Page 9 of 27
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
9
In conclusion, we have demonstrated the nucleophilic arylation of aldehydes/isatins by
the action of a carbonate base on in situ generated tetraaryl phosphonium salts formed by the
addition of phosphines to arynes. Although arynes are widely used for the electrophilic arylation
of various elementꢀelement bonds, the present method utilizes arynes as aryl anion equivalents
for the nucleophilic arylation reactions. The reaction tolerates various functional groups and the
desired secondary/tertiary alcohols are formed in moderate to good yields.
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
Experimental Section
General Information:
Unless otherwise specified, all reactions were carried out under an atmosphere of argon in flameꢀ
dried reaction vessels with Teflon screw caps. Reaction temperatures are reported as the
temperature of the bath surrounding the reaction vessel. 30 °C corresponds to the room
temperature of the lab, when the experiments were carried out. THF was freshly purified by
distillation over Naꢀbenzophenone and was transferred under argon. 18ꢀCrownꢀ6 was
recrystallized from dry CH3CN, and KF was dried by heating at 110 °C for 12 h and left to cool
under argon. The aldehydes were purchased from commercial sources and were purified either
by distillation (for liquids) or washing with NaHCO3 after dissolving in ether or dichloromethane
(for solids), prior to use. Phosphines were purchased from commercial sources and used as
received. The 2ꢀ(trimethylsilyl)phenyl trifluoromethanesulfonate 2a and the other symmetric and
13
unsymmetric aryne precursors were synthesized following literature procedure.1b,19 1H and C
NMR spectra were recorded in CDCl3 as solvent. Chemical shifts (δ) are given in ppm. The
residual solvent signals were used as references and the chemical shifts converted to the TMS
scale (CDCl3: δH = 7.26 ppm, δC = 77.16 ppm). HRMS measurements were carried out using
9
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 10 of 27
1
2
3
4
5
6
ESI method and ionꢀtrap mass analyzer. Infrared (IR) spectra were recorded on an FTꢀIR
spectrometer as thin films using NaCl plates.
7
8
9
General Procedure for the Reaction involving Phosphine, Aryne and Aldehydes: To a flameꢀ
dried screwꢀcapped test tube equipped with a magnetic stir bar was added the phosphine (0.197
g, 0.75 mmol), KF (0.058 g, 1.0 mmol) and 18ꢀcrownꢀ6 (0.264 g, 1.0 mmol). Then the screwꢀ
capped tube was evacuated and backfilled with argon. The mixture was dissolved in THF (4.0
mL) under argon atmosphere and subsequently cooled the reaction mixture to 0 °C and kept
stirring for five minutes. To the stirring solution, aryne precursor 2a (1.0 mmol) was added and
continued stirring for another five minutes followed by addition of the water (0.010 g, 10.0 ꢁL,
0.55 mmol). Then the reaction mixture was stirred at 0 °C for 30 minutes. Then aldehyde 1 (0.25
mmol) was added followed by subsequent addition of Cs2CO3 (0.326 g, 1.0 mmol) at 0 °C. Then
the reaction mixture was slowly warmed to rt and kept stirring for 24 h at 65 °C. After 24 h, the
reaction was quenched using 3N HCl (0.25 ml) and subsequent workꢀup in CH2Cl2 (3 x 30 mL).
The organic layer dried over Na2SO4 and solvent was evaporated, and the crude residue was
purified by column chromatography on silica gel (230ꢀ400 mesh) (Petroleum ether/EtOAc =
85/15) to afford the corresponding benzhydrol derivatives 3 in moderate to good yields.
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
General Procedure for the Reaction Involving Phosphine, Aryne and Isatins: To a flameꢀ
dried screwꢀcapped test tube equipped with a magnetic stir bar was added the phosphine (0.197
g, 0.75 mmol), KF (0.058 g, 1.0 mmol) and 18ꢀcrownꢀ6 (0.264 g, 1.0 mmol). Then the screwꢀ
capped tube was evacuated and backfilled with argon. The mixture was dissolved in THF (4.0
mL) under argon atmosphere and subsequently cooled the reaction mixture to 0 °C and kept
stirring for five minutes. To the stirring solution aryne precursor 2a (1 mmol) was added and
continued stirring for another five minutes followed by addition of the water (0.010 g, 10.0 ꢁL,
10
ACS Paragon Plus Environment

Page 11 of 27
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
9
0.55 mmol). Then the reaction mixture was stirred at 0 °C for 30 minutes. Then isatin 10 (0.25
mmol) was added followed by the subsequent addition of Cs2CO3 (0.326 g, 1.0 mmol) at 0 °C.
Then the reaction mixture was slowly warmed to rt and kept stirring for 24 h at 65 °C. After 24
h, the reaction was quenched using 3N HCl (3 mL) and subsequent workꢀup in CH2Cl2 (3 x 30
mL). The organic layer dried over Na2SO4 and solvent was evaporated, and the crude residue
was purified by column chromatography on silica gel (230ꢀ400 mesh) (Petroleum ether/EtOAc =
85/15) to afford the corresponding benzhydrol derivatives 11 in moderate to good yields.
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-Chlorophenyl)(phenyl)methanol (3a):20 Pale yellow solid, 0.041 g in 0.25 mmol scale, 75%
1
yield. Rf (Pet. ether /EtOAc = 80/20): 0.53; H NMR (400 MHz, CDCl3) δ 7.31ꢀ7.20 (m, 9H),
5.69 (s,1H), 2.46 (s, 1H). 13C NMR (100 MHz, CDCl3) δ 143.5, 142.3, 133.3, 128.7, 128.7,
+
128.0, 127.9, 126.6, 75.6. HRMS (ESI) calculated [MꢀOH] for C13H10Cl: 201.0466, found:
201.0468. FTIR (cm-1) 3597, 3411, 3020, 2884, 2402, 1594, 1489, 1216, 1180, 1018, 925.
(4-Bromophenyl)(phenyl)methanol (3b):21 Pale yellow solid, 0.039 g in 0.25 mmol scale, 60%
1
yield. Rf (Pet. ether /EtOAc = 80/20): 0.53; H NMR (400 MHz, CDCl3) δ 7.48 (d, J = 8.2 Hz,
2H), 7.36ꢀ2.26 (m, 7H), 5.79 (s, 1H), 2.40 (s, 1H). 13C NMR (100 MHz, CDCl3) δ 143.5, 142.9,
131.6, 128.8, 128.3, 128.0, 126.6, 121.5, 75.7. HRMS (ESI) calculated [MꢀOH] + for C13H10Br:
244.9960, found: 244.9965. FTIR (cm-1) 3600, 3400, 3020, 2402, 1593, 1486, 1410, 1216, 1019,
926.
(4-Fluorophenyl)(phenyl)methanol (3c):22 Pale yellow solid, 0.034 g in 0.25 mmol scale, 67%
1
yield. Rf (Pet. ether /EtOAc = 80/20): 0.56; H NMR (400 MHz, CDCl3) δ 7.38ꢀ7.28 (m, 7H),
7.04 (t, J = 8.7 Hz, 2H), 5.84 (s, 1H), 2.32 (bs, 1H). 13C NMR (100 MHz, CDCl3) δ 162.3 (d, J
= 246.7 Hz), 143.8, 139.7 (d, J = 2.9 Hz), 128.7, 128.4 (d, J = 8.6 Hz), 127.9, 126.6, 115.4 (d, J
11
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 12 of 27
1
2
3
4
5
= 21.4 Hz), 75.7. HRMS (ESI) calculated [MꢀOH] + for C13H10F: 185.0761, found: 185.0760.
FTIR (cm-1) 3412, 1601, 1505, 1219, 1167, 1025, 925, 854.
6
7
8
Diphenylmethanol (3d):23 Yellow solid, 0.025 g in 0.25 mmol scale, 54% yield. Rf (Pet. ether
9
1
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
/EtOAc = 80/20): 0.61; H NMR (400 MHz, CDCl3) δ 7.42ꢀ7.41 (m, 4H), 7.39ꢀ7.36 (m, 4H),
7.32ꢀ7.29 (m, 2H), 5.86 (s, 1H), 2.38 (bs, 1H). 13C NMR (100 MHz, CDCl3) δ 143.9, 128.6,
127.7, 126.7, 76.4. HRMS (ESI) calculated [MꢀOH] + for C13H11: 167.0855, found: 167.0853.
FTIR (cm-1) 3597, 3414, 3020, 2402, 1597, 1489, 1446, 1216, 1026, 924.
Phenyl(p-tolyl)methanol (3e):21 Yellow solid, 0.034 g in 0.25 mmol scale, 69% yield. Rf (Pet.
1
ether /EtOAc = 80/20): 0.57; H NMR (400 MHz, CDCl3) δ 7.38 (d, J = 7.2 Hz, 2H), 7.33 (t, J
= 7.2 Hz, 2H), 7.26 (d, J = 8.0 Hz, 3H), 7.15 (d, J = 7.9 Hz, 2H), 5.81 (s, 1H), 2.33 (s, 3H), 2.17
(bs, 1H). 13C NMR (100 MHz, CDCl3) δ 144.1, 141.1, 137.4, 129.3, 128.6, 127.6, 126.7, 126.6,
+
76.2, 21.2. HRMS (ESI) calculated [MꢀOH] for C14H13: 181.1012, found: 181.1015. FTIR
(cm-1) 3596, 3411, 3019, 2924, 1614, 1504, 1216, 1372, 1029, 926.
(4-Methoxyphenyl)(phenyl)methanol(3f):22 Yellow solid, 0.074 g in 0. 5 mmol scale, 69%
1
yield. Rf (Pet. ether /EtOAc = 80/20): 0.38; H NMR (400 MHz, CDCl3) δ 7.39ꢀ7.34 (m, 4H),
13
7.31ꢀ7.29 (m, 3H), 6.89 (d, J= 8.3 Hz, 2H), 5.80 (s, 1H), 3.81 (s, 3H), 2.46 (s, 1H). C NMR
(100 MHz, CDCl3) δ 159.1, 144.1, 136.3, 128.5, 128.0, 127.5, 126.5, 113.9, 75.8, 55.4. HRMS
(ESI) calculated [MꢀOH] + for C14H13O: 197.0961, found: 197.0964. FTIR (cm-1) 3415, 3062,
2954, 2838, 1610, 1508, 1454, 1300, 1176, 1031, 923.
[1,1'-Biphenyl]-4-yl(phenyl)methanol (3g):21 Yellow solid, 0.050 g in 0.25 mmol scale, 77%
1
yield). Rf (Pet. ether /EtOAc = 80/20): 0.50; H NMR (400 MHz, CDCl3) δ 7.63ꢀ7.60 (m, 4H),
7.49ꢀ7.45 (m, 6H), 7.42ꢀ7.39 (m, 3H), 7.35ꢀ7.31 (m, 1H), 5.89 (s, 1H), 2.52 (s, 1H). 13C NMR
(100 MHz, CDCl3) δ 143.9, 142.9, 140.9, 140.5, 128.9, 128.7, 127.7, 127.4, 127.3, 127.2, 127.1,
12
ACS Paragon Plus Environment

Page 13 of 27
The Journal of Organic Chemistry
1
2
3
4
5
126.7, 76.1. HRMS (ESI) calculated [MꢀOH] + for C19H15: 243.1168, found: 243.1172. FTIR
(cm-1) 3596, 3412, 3020, 2402, 1597, 1486, 1371, 1216, 1032, 923.
6
7
8
4-(Hydroxy(phenyl)methyl)benzonitrile (3h):24 Yellow solid, 0.030 g in 0.25 mmol scale, 58%
9
1
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
yield. Rf (Pet. ether /EtOAc = 80/20): 0.35; H NMR (400 MHz, CDCl3) δ 7.64 (d, J = 7.5 Hz,
2H), 7.54 (d, J = 7.9 Hz, 2H), 7.40ꢀ7.32 (m, 5H), 5.88 (s, 1H), 2.53 (bs, 1H). 13C NMR (100
MHz, CDCl3) δ 149.0, 142.9, 132.4, 129.0, 128.4, 127.1, 126.8, 119.0, 111.2, 75.7. HRMS
(ESI) calculated [MꢀOH] + for C14H10N: 192.0808, found: 192.0806. FTIR (cm-1) 3435, 2231,
111, 1716, 1495, 1275, 1033, 922, 806, 757.
Methyl 4-(hydroxy(phenyl)methyl)benzoate (3i):21 Yellow solid, 0.048 g in 0.25 mmol scale,
79% yield. Rf (Pet. ether /EtOAc = 80/20): 0.34; 1H NMR (400 MHz, CDCl3) δ 7.99 (d, J = 8.2
Hz, 2H), 7.46 (d, J = 8.1 Hz, 2H), 7.35ꢀ7.27 (m, 5H), 5.87 (s, 1H), 3.89 (s, 3H), 2.46 (s, 1H). 13C
NMR (100 MHz, CDCl3) δ 167.1, 148.8, 143.4, 129.9, 129.4, 128.8, 128.1, 126.8, 126.5, 76.0,
52.2. HRMS (ESI) calculated [MꢀOH] + for C15H13O2: 225.0910, found: 225.0908. FTIR (cm-1)
3430, 3020, 1715, 1610, 1442, 1374, 1283, 1184, 1026, 926.
Phenyl(4-(trifluoromethyl)phenyl)methanol (3j):25 Yellow solid, 0.043 g in 0.25 mmol scale,
68% yield). Rf (Pet. ether /EtOAc = 95/05): 0.53; 1H NMR (400 MHz, CDCl3) δ 7.61 (d, J = 8.0
Hz, 2H), 7.52 (d, J = 8.0 Hz, 2H), 7.37ꢀ7.27 (m, 5H), 5.87 (s, 1H), 2.40 (bs, 1H). 13C NMR (100
MHz, CDCl3) δ 147.6, 143.3, 129.8 (d, J = 32.2 Hz), 128.9, 128.2, 126.8, 126.8, 125.0 (q, J =
+
3.4 Hz), 75.9. HRMS (ESI) calculated [MꢀOH] for C14H10F3: 235.0729, found: 235.0727.
FTIR (cm-1) 3597, 3397, 3021, 2926, 2403, 1617, 1489, 1325, 1125, 923.
(3-Bromophenyl)(phenyl)methanol (3k):26 Yellow solid, 0.037 g in 0.25 mmol scale, 56%
1
yield. Rf (Pet. ether /EtOAc = 80/20): 0.60; H NMR (400 MHz, CDCl3) δ 7.59 (s, 1H), 7.43ꢀ
7.30 (m, 7H), 7.24ꢀ7.20 (m, 1H), 5.80 (s, 1H), 2.30 (bs, 1H).13C NMR (100 MHz, CDCl3) δ
13
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 14 of 27
1
2
3
4
5
6
7
8
146.1, 143.3, 130.7, 130.2, 129.6, 128.8, 128.6, 128.1, 127.7, 126.7, 125.2, 122.8, 75.7. HRMS
(ESI) calculated [MꢀOH] + for C13H10Br: 244.9960, found: 244.9958. FTIR (cm-1) 3383, 1584,
1217, 1179, 1078, 1029, 913, 758.
9
(3-Nitrophenyl)(phenyl)methanol (3l):27 Yellow solid, 0.029 g in 0.25 mmol scale, 51% yield.
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
Rf (Pet. ether /EtOAc = 95/05): 0.51; H NMR (400 MHz, CDCl3) δ 8.29 (s, 1H), 8.11 (d, J =
8.0 Hz, 1H), 7.71 (d, J = 7.6 Hz, 1H), 7.49 (t, J = 8.0 Hz, 1H), 7.37ꢀ7.30 (m, 5H), 5.91 (s, 1H),
2.56 (s, 1H). 13C NMR (100 MHz, CDCl3) δ 148.3, 145.9, 142.9, 132.6, 129.5, 129.1, 128.5,
+
126.8, 122.6, 121.4, 75.5. HRMS (ESI) calculated [M+Na] for C13H11NO3Na: 252.0637,
found: 252.0635. FTIR (cm-1) 3554, 3376, 3068, 2925, 1714, 1528, 1350, 1187, 1032.
Phenyl(o-tolyl)methanol (3m):26 Viscous yellow oil, 0.033 g in 0.25 mmol scale, 67% yield. Rf
(Pet. ether /EtOAc = 80/20): 0.63; 1H NMR (400 MHz, CDCl3) δ 7.56 (d, J = 7.6 Hz, 1H), 7.37ꢀ
13
7.36 (m, 4H), 7.32ꢀ7.17 (m, 4H), 6.02 (s, 1H), 2.28 (s, 3H), 2.20 (bs, 1H). C NMR (100 MHz,
CDCl3) δ 143.0, 141.6, 135.5, 130.7, 128.6, 127.7, 127.7, 127.2, 126.4, 126.3, 73.5, 19.5.
HRMS (ESI) calculated [MꢀOH] + for C14H13: 181.1012, found: 181.1010. FTIR (cm-1) 3369,
1812, 1593, 1483, 1455, 1377, 1258, 1179, 1020, 919, 755.
(2-Chlorophenyl)(phenyl)methanol (3n):28 Yellow solid, 0.067 g, in 0.5 mmol scale, 62%
1
yield. Rf (Pet. ether /EtOAc = 80/20): 0.60; H NMR (400 MHz, CDCl3) δ 7.63 (d, J = 7.3 Hz,
1H), 7.43ꢀ7.41 (m, 2H), 7.38ꢀ7.31 (m, 5H), 7.27ꢀ7.23 (m, 1H), 6.24 (s, 1H), 2.53 (s, 1H). 13C
NMR (100 MHz, CDCl3) δ 142.3, 141.1, 132.6, 129.7, 128.9, 128.6, 128.1, 127.9, 127.2, 127.0,
72.8. HRMS (ESI) calculated [MꢀOH] + for C13H10Cl: 201.0466, found: 201.0469. FTIR (cm-1)
3365, 3064, 3030, 2919, 1955, 1584, 1445, 1391, 1184, 1024, 951.
(2,3-Dimethoxyphenyl)(phenyl)methanol (3o):29 Yellow solid, 0.080 g in 0.5 mmol scale, 66%
1
yield. Rf (Pet. ether /EtOAc = 80/20): 0.48; H NMR (400 MHz, CDCl3) δ 7.42 (d, J = 7.5 Hz,
14
ACS Paragon Plus Environment

Page 15 of 27
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
9
2H), 7.35 (t, J = 7.5 Hz, 2H), 7.27 (t, J = 7.0 Hz, 1H), 7.09 (t, J = 7.8 Hz, 1H), 7.00 (d, J = 7.5
Hz, 1H), 6.90 (d, J = 8.0 Hz, 1H), 6.04 (s, 1H), 3.87 (s, 3H), 3.62 (s, 3H), 3.18 (bs, 1H). 13C
NMR (100 MHz, CDCl3) δ 152.7, 146.4, 144.1, 137.7, 128.3, 127.2, 126.4, 124.1, 119.8, 112.0,
72.39, 60.5, 55.8. HRMS (ESI) calculated [MꢀOH] + for C15H15O2: 227.1067, found: 227.1064.
FTIR (cm-1) 3419, 3017, 2937, 2839, 2403, 1590, 1478, 1270, 1080, 921.
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
(3,4-Dimethoxyphenyl)(phenyl)methanol (3p):30 Yellow oil, 0.083 g in 0.5 mmol scale, 68%
1
yield. Rf (Pet. ether /EtOAc = 80/20): 0.26; H NMR (400 MHz, CDCl3) δ7.38ꢀ7.27 (m, 5H),
6.92 (bs, 1H), 6.88 (d, J = 7.8 Hz, 1H), 6.82 (d, J = 8.2 Hz, 1H), 5.78 (s, 1H), 3.85 (s, 3H), 3.84
(s, 3H), 2.43 (s, 1H).13C NMR (100 MHz, CDCl3) δ 149.1, 148.5, 144.0, 136.6, 128.5, 127.6,
+
126.5, 119.0, 111.0, 109.8, 76.0, 56.0, 55.9. HRMS (ESI) calculated [MꢀOH] for C15H15O2:
227.1067, found: 227.1064. FTIR (cm-1) 3597, 3419, 3019, 2963, 2840, 1596, 1513, 1456, 1259,
1029, 927.
(3,4-Dichlorophenyl)(phenyl)methanol (3q):31 Yellow oil (0.040 g, 64% yield). Rf (Pet. ether
/EtOAc = 80/20): 0.53; 1H NMR (400 MHz, CDCl3) δ 7.50 (s, 1H), 7.40ꢀ7.31 (m, 6H), 7.19 (d,
J = 8.0 Hz, 1H), 5.75 (s, 1H), 2.49 (s, 1H). 13C NMR (100 MHz, CDCl3) δ 144.0, 143.0, 132.6,
+
131.5, 130.5, 128.9, 128.5, 128.3, 126.7, 125.9, 75.2. HRMS (ESI) calculated [MꢀOH] for
C13H9Cl2: 235.0076, found: 235.0074. FTIR (cm-1) 3587, 3379, 3020, 2881, 1593, 1464, 1391,
1216, 1185, 1030, 891.
Naphthalen-2-yl(phenyl)methanol (3r):20 Yellow solid, (0.070 g in 0.25 mmol scale, 60%
1
yield. Rf (Pet. ether /EtOAc = 80/20): 0.50; H NMR (400 MHz, CDCl3) δ 7.91 (s, 1H), 7.86ꢀ
7.81 (m, 3H), 7.54ꢀ7.49 (m, 2H), 7.46ꢀ7.44 (m, 3H), 7.37 (t, J = 7.3 Hz, 2H), 7.31 (t, J = 7.0 Hz,
1H), 5.98 (s, 1H), 2.60 (s, 1H). 13C NMR (100 MHz, CDCl3) δ 143.7, 141.2, 133.3, 133.0,
128.6, 128.4, 128.2, 127.8, 127.8, 126.8, 126.3, 126.1, 125.1, 124.9, 76.4. HRMS (ESI)
15
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 16 of 27
1
2
3
4
+
calculated [MꢀOH] for C17H13: 217.1012, found: 217.1010. FTIR (cm-1) 3384, 3057, 2874,
5
6
1951, 1597, 1497, 1366, 1160, 1028, 957.
7
8
9
Phenyl(pyren-1-yl)methanol (3s):32 Yellow solid, 0.056 g in 0.25 mmol scale, 73% yield. Rf
(Pet. ether /EtOAc = 80/20): 0.54; 1H NMR (400 MHz, CDCl3) δ 8.32 (d, J = 9.2 Hz, 1H), 8.20ꢀ
8.16 (m, 4H), 8.07ꢀ8.0 (m, 4H), 7.48 (d, J = 7.3 Hz, 2H), 7.37ꢀ7.28 (m, 3H), 6.87 (s, 1H), 2.62
(bs, 1H). 13C NMR (100 MHz, CDCl3) δ 143.7, 136.7, 131.4, 131.1, 130.7, 128.7, 128.2, 127.9,
127.7, 127.6, 127.1, 126.1, 125.5, 125.3, 125.1, 125.0, 124.9, 124.8, 123.2, 73.7. HRMS (ESI)
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
+
calculated [MꢀOH] for C23H15: 291.1168, found: 291.1163. FTIR (cm-1) 3421, 1724, 1595,
1522, 1424, 1216, 1045, 923, 846, 765.
Phenyl(3,4,5-trimethoxyphenyl)methanol (3t):33 Yellow solid, 0.043 g in 0.25 mmol scale,
1
63% yield. Rf (Pet. ether /EtOAc = 80/20): 0.26; H NMR (400 MHz, CDCl3) δ 7.41ꢀ7.34 (m,
4H), 7.31ꢀ7.27 (m, 1H), 6.62 (s, 2H), 5.77 (s, 1H), 3.83 (s, 9H), 3.79 (bs, 1H). 13C NMR (100
MHz, CDCl3) δ 153.3, 143.7, 139.6, 137.2, 128.6, 127.7, 126.6, 103.5, 76.3, 60.9, 56.1. HRMS
(ESI) calculated [MꢀOH] + for C16H17O3: 257.1172, found: 257.1167. FTIR (cm-1) 3490, 1889,
1592, 1501, 1458, 1331, 1231, 1129, 1057, 921, 819.
Phenyl(thiophen-2-yl)methanol (3u):34 Viscous yellow oil, 0.042 g in 0.5 mmol scale, 44%
1
yield. Rf (Pet. Ether /EtOAc = 80/20): 0.61; H NMR (400 MHz, CDCl3) δ 7.48ꢀ7.28 (m, 6H),
6.98ꢀ6.91 (m, 2H), 6.06 (s, 1H), 2.62 (bs, 1H). 13C NMR (100 MHz, CDCl3) δ 148.2, 143.2,
128.6, 128.1, 126.8, 126.4, 125.5, 125.0, 72.5. HRMS (ESI) calculated [MꢀOH] + for C11H9S:
173.0419, found: 173.0417. FTIR (cm-1) 3376, 1594, 1442, 1216, 1038, 759, 703, 703.
Phenyl(thiophen-3-yl)methanol (3v):35 Viscous yellow oil, 0.015 g in 0.25 mmol scale, 32%
1
yield. Rf (Pet. ether/EtOAc = 80/20): 0.22; H NMR (400 MHz, CDCl3) δ 7.43ꢀ7.36 (m, 4H),
7.33ꢀ7.28 (m, 2H), 7.21 (s, 1H), 7.03 (d, J = 4.9 Hz, 1H), 5.91 (s, 1H ), 2.31 (bs, 1H). 13C NMR
16
ACS Paragon Plus Environment

Page 17 of 27
The Journal of Organic Chemistry
1
2
3
4
(100 MHz, CDCl3) δ 145.4, 143.5, 128.7, 127.9, 126.6, 126.5, 126.4, 121.8, 73.0. HRMS (ESI)
5
6
+
calculated [MꢀOH] for C11H9S: 173.0419, found: 173.0418. FTIR (cm-1) 3391, 1647, 1592,
7
8
1485, 1452, 1412, 1279, 1224, 1149, 839, 766.
9
1-Phenylpropan-1-ol (3w):23 Yellow oil, 0.018 g in 0.25 mmol scale, 53% yield. Rf (Pet. ether
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
/EtOAc = 80/20): 0.48; H NMR (400 MHz, CDCl3) δ 7.40ꢀ7.35 (m, 4H), 7.32ꢀ7.28 (m, 1H),
4.62 (t, J = 6.6 Hz, 1H), 1.94 (s, 1H), 1.89ꢀ1.74 (m, 2H), 0.94 (t, J = 7.3 Hz, 3H). 13C NMR (100
MHz, CDCl3) δ 144.7, 128.5, 127.6, 126.1, 76.2, 32.0, 10.3. HRMS (ESI) calculated [MꢀOH] +
for C9H11: 119.0855, found: 119.0857. FTIR (cm-1) 3601, 3412, 3018, 2969, 2930, 1597, 1456,
1217, 1090, 972.
1,3-Diphenylpropan-1-ol (3x):21 Yellow solid, 0.025 g in 0.25 mmol scale, 47% yield. Rf (Pet.
1
ether /EtOAc = 80/20): 0.60; H NMR (400 MHz, CDCl3) δ 7.38ꢀ7.37 (m, 4H), 7.32ꢀ7.29 (m,
3H), 7.22ꢀ7.21 (m, 3H), 4.70 (dd, 1J = 5.7 Hz, 2J = 7.4 Hz, 1H), 2.81ꢀ2.65 (m, 2H), 2.20ꢀ2.02 (m,
2H), 1.95 (bs, 1H). 13C NMR (100 MHz, CDCl3) δ 144.7, 141.9, 128.6, 128.6, 128.5, 127.8,
+
126.1, 126.0, 74.0, 40.6, 32.2. HRMS (ESI) calculated [M+Na] for C15H16ONa: 235.1093,
found: 235.1092. FTIR (cm-1) 3389, 3019, 2930, 1612, 1491, 1451, 1374, 1318, 1216, 1050,
922.
Cyclohexyl(phenyl)methanol (3y):24 Colorless oil, 0.071 g in 0.5 mmol scale, 75% yield. Rf
1
(Pet. ether /EtOAc = 80/20): 0.61; H NMR (400 MHz, CDCl3) δ 7.38ꢀ7.28 (m, 5H), 4.38 (d, J
= 7.2 Hz, 1H), 2.02ꢀ1.99 (m, 1H), 1.88 (s, 1H), 1.80ꢀ1.77 (m, 1H), 1.67ꢀ1.60 (m, 3H), 1.41ꢀ1.38
(m, 1H), 1.27ꢀ1.02 (m, 4H), 0.99ꢀ0.93 (m, 1H). 13C NMR (100 MHz, CDCl3) δ 143.8, 128.3,
+
127.5, 126.8, 79.5, 45.1, 29.4, 29.0, 26.6, 26.2, 26.1. HRMS (ESI) calculated [MꢀOH] for
C13H17: 173.1325, found: 173.1324. FTIR (cm-1) 3606, 3419, 3019, 2929, 2856, 1587, 1368,
1216, 1067, 922.
17
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 18 of 27
1
2
3
4
1,3-Diphenylprop-2-en-1-ol (3z):36 Yellow solid (0.053 g, 50% yield). Rf (Pet. ether /EtOAc =
5
6
1
80/20): 0.56; H NMR (400 MHz, CDCl3) δ 7.48ꢀ7.47 (m, 2H), 7.43ꢀ7.40 (m, 4H), 7.37ꢀ7.28
7
8
9
(m, 5H) 6.74 (d, J = 16.0 Hz, 1H), 6.45 (dd, J1 = 6.5 Hz, J2 = 15.6 Hz, 1H), 5.42 (d, J = 6.2 Hz,
1H), 2.27 (bs,1H). 13C NMR (100 MHz, CDCl3) δ 142.9, 136.7, 131.7, 130.6, 128.7, 128.7,
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
+
127.9, 126.7, 126.5, 75.2. HRMS (ESI) calculated [MꢀOH] for C15H13: 193.1012, found:
193.1010. FTIR (cm-1) 3422, 1598, 1487, 1216, 1036, 971, 767.
1,3,3-Triphenylprop-2-en-1-ol (3aa):37 Yellow solid, 0.082 g in 0.5 mmol scale, 63% yield. Rf
1
(Pet. ether /EtOAc = 95/05): 0.53; H NMR (400 MHz, CDCl3) δ 7.39ꢀ7.29 (m, 7H), 7.23 (s,
13
8H), 6.27 (d, J = 9.4, 1H), 5.24 (d, J = 9.4, 1H), 2.25 (s, 1H). C NMR (100 MHz, CDCl3) δ
143.5, 143.5, 141.6, 139.2, 130.2, 129.9, 128.7, 128.4, 128.3, 127.8, 127.7, 127.7, 126.3, 71.7.
HRMS (ESI) calculated [MꢀOH] for C17H17OS: 269.1325, found: 269.1327. FTIR (cm-1)
+
3557, 3328, 3057, 3027, 2924, 1596, 1492, 1446, 1362, 1072, 1006.
3,7-Dimethyl-1-phenylocta-2,6-dien-1-ol (3ab): Viscous yellow oil, 0.029 g in 0.25 mmol
scale, 50% yield. Rf (Pet. ether /EtOAc = 80/20): 0.66; 1H NMR (400 MHz, CDCl3) δ 7.42 (d, J
= 7.4 Hz, 2H), 7.34 (t, J = 7.1 Hz, 2H), 7.30ꢀ7.23 (m, 1H), 6.64 (d, J = 16.1 Hz, 1H), 6.32 (d, J =
16.1 Hz, 1H), 5.18ꢀ5.15 (m, 1H), 2.16ꢀ2.05 (m, 2H), 1.70ꢀ1.68 (m, 6H), 1.62ꢀ1.60 (m, 2H), 1.41
13
(s, 3H). C NMR (100 MHz, CDCl3) δ 137.2, 136.8, 132.3, 128.7, 127.5, 127.3, 126.5, 124.5,
+
73.7, 42.7, 28.6, 25.9, 23.1, 17.9. HRMS (ESI) calculated [MꢀOH] for C16H21: 213.1638,
found: 213.1635. FTIR (cm-1) 3444, 1665, 1589, 1460, 1370, 1260, 1215, 1114, 1052, 974, 765.
Benzo[d][1,3]dioxol-5-yl(phenyl)methanol (3ac):38 Yellow oil, 0.031 g in 0.25 mmol scale,
1
48% yield. Rf (Pet. ether /EtOAc = 80/20): 0.41; H NMR (400 MHz, CDCl3) δ 7.31ꢀ7.26 (m,
13
4H), 6.80ꢀ6.74 (m, 3H), 5.92 (s, 2H), 5.68 (s, 1H), 2.49 (s, 1H). C NMR (100 MHz, CDCl3) δ
18
ACS Paragon Plus Environment

Page 19 of 27
The Journal of Organic Chemistry
1
2
3
4
5
148.0, 147.3, 142.3, 137.7, 133.3, 128.7, 127.8, 120.2, 108.3, 107.2, 101.2, 75.4. FTIR (cm-1)
3359, 2956, 2893, 2778, 1603, 1489, 1245, 1038, 929.
6
7
8
(4-Chlorophenyl)(4-methoxyphenyl)methanol (3af):39 Yellow oil, 0.012 g in 0.25 mmol scale,
9
1
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% yield. Rf (Pet. ether /EtOAc = 80/20): 0.49; H NMR (400 MHz, CDCl3) δ 7.30 (s, 4H),
13
7.25 (d, J = 8.7 Hz, 2H), 6.87 (d, J = 8.7 Hz, 2H), 5.77 (s, 1H), 3.79 (s, 3H), 2.25 (s, 1H). C
NMR (100 MHz, CDCl3) δ 159.4, 142.6, 135.9, 133.2, 128.7, 128.1, 127.9, 114.1, 75.3, 55.4.
HRMS (ESI) calculated [MꢀOH]+ for C14H12ClO: 231.0571, found: 231.0578. FTIR (cm-1)
3394, 3002, 2928, 2838, 1609, 1511, 1248, 1173, 1032.
Hydroxy-1-methyl-3-phenylindolin-2-one (11a):40 Pale brown solid, 0.043 g in 0.25 mmol
scale, 73% yield. Rf (Pet. ether /EtOAc = 60/40): 0.36; 1H NMR (400 MHz, CDCl3) δ 7.40ꢀ7.28
(m, 7H), 7.10 (t, J = 7.5 Hz, 1H), 6.91 (d, J = 7.6 Hz, 1H), 3.92 (s, 1H), 3.24 (m, 3H). 13C NMR
(100 MHz, CDCl3) δ 177.7, 143.6, 140.3, 131.8, 129.9, 128.6, 128.3, 125.5, 125.0, 123.7, 108.8,
78.1, 26.6. HRMS (ESI) calculated [M+H] + for C15H14O2N: 240.1019, found: 240.1020. FTIR
(cm-1) 3684, 3386, 3020, 2402, 1718, 1614, 1477, 1369, 1092, 930.
1-Benzyl-3-hydroxy-3-phenylindolin-2-one (11b):41 Pale brown solid, 0.040 g in 0.25 mmol
scale, 51% yield. Rf (Pet. ether /EtOAc = 60/40): 0.53; 1H NMR (400 MHz, CDCl3) δ 7.44ꢀ7.42
(m, 2H), 7.36ꢀ7.22 (m, 10H), 7.06 (t, J = 7.3 Hz, 1H), 6.80 (d, J = 7.8 Hz, 1H), 5.05 (d, J= 15.6
13
Hz, 1H), 4.82 (d, J = 15.6 Hz, 1H), 3.89 (bs, 1H). C NMR (100 MHz, CDCl3) δ 177.8, 142.7,
140.3, 135.5, 131.8, 129.8, 129.0, 128.8, 128.4, 127.9, 127.4, 125.5, 125.1, 123.7, 109.9, 78.1,
44.1. HRMS (ESI) calculated [M+H] + for C21H18O2N: 316.1332, found: 316.1333. FTIR (cm-1)
3387, 3020, 2402, 1718, 1613, 1479, 1367, 1216, 1075, 930.
19
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 20 of 27
1
2
3
4
5
3-Hydroxy-5-methoxy-1-methyl-3-phenylindolin-2-one (11c):42 Pale brown solid, 0.037 g in
0.25 mmol scale, 55% yield. Rf (Pet. ether /EtOAc = 60/40): 0.23; 1H NMR (400 MHz, CDCl3)
6
7
8
13
δ 7.39ꢀ7.28 (m, 5H), 6.90ꢀ6.86 (m, 2H), 6.81 (d, J = 8.3 Hz, 1H), 3.75 (s, 3H), 3.20 (s, 3H). C
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
NMR (100 MHz, CDCl3) δ 177.6, 156.7, 140.3, 136.8, 133.1, 128.6, 128.3, 125.4, 114.7, 111.8,
109.3, 78.5, 55.9, 26.7. HRMS (ESI) calculated [M+Na] + for C16H15O3NNa: 292.0944, found:
292.0947. FTIR (cm-1) 3380, 3020, 2402, 1713, 1609, 1495, 1434, 1366, 1161, 1103, 933.
Supporting Information
1
Details on mechanistic experiments, optimization studies, and the copies of H and 13C NMR
spectra of all products. The Supporting Information is available free of charge on the ACS
Publications website.
Acknowledgement
Generous financial support from the Science and Engineering Research BoardꢀDST, Government
of India (File Number: EMR/2016/007021) is kindly acknowledged. RNG would like to thank
IISc for the fellowship. We thank Mr. Manikandan Thangaraj for the experimental support.
REFERENCES
1. (a) Himeshima, Y.; Sonoda, T.; Kobayashi, H. FluorideꢀInduced 1,2ꢀElimination of Oꢀ
Trimethylsilylphenyl Triflate to Benzyne Under Mild Conditions. Chem. Lett. 1983, 1211ꢀ1214.
See also: (b) Peña, D.; Cobas, A.; Pérez, D.; Guitián, E. An Efficient Procedure for the Synthesis
of OrthoꢀTrialkylsilylaryl Triflates: Easy Access to Precursors of Functionalized Arynes. Synthesis
2002, 1454ꢀ1458.
2. For selected reviews on aryne chemistry, see: (a) Shi, J.; Li, Y.; Li, Y. Aryne Multifunctionalization
with Benzdiyne and Benztriyne Equivalents. Chem. Soc. Rev. 2017, 46, 1707ꢀ1719. (b) Garcíaꢀ
López, J.ꢀA.; Greaney, M. F. Synthesis of Biaryls using Aryne Intermediates. Chem. Soc. Rev.
20
ACS Paragon Plus Environment

Page 21 of 27
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
9
2016, 45, 6766ꢀ6798. (c) Bhojgude, S. S.; Bhunia, A.; Biju, A. T. Employing Arynes in
Diels−Alder Reactions and TransitionꢀMetalꢀFree Multicomponent Coupling and Arylation
Reactions. Acc. Chem. Res. 2016, 49, 1658ꢀ1670. (d) Dubrovskiy, A. V.; Markina, N. A.; Larock,
R. C. Use of Benzynes for The Synthesis of Heterocycles. Org. Biomol. Chem. 2013, 11, 191ꢀ218.
(e) Tadross, P. M.; Stoltz, B. M. A Comprehensive History of Arynes in Natural Product Total
Synthesis. Chem. Rev. 2012, 112, 3550ꢀ3577. (f) Gampe, C. M.; Carreira, E. M. Arynes and
Cyclohexyne in Natural Product Synthesis. Angew. Chem. Int. Ed. 2012, 51, 3766ꢀ3778. (g)
Bhunia, A.; Yetra, S. R.; Biju, A. T. Recent Advances in TransitionꢀMetalꢀFree Carbon–Carbon
and Carbon–Heteroatom BondꢀForming Reactions Using Arynes. Chem. Soc. Rev. 2012, 41,
3140ꢀ3152.
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
3. (a) Wenk, H. H.; Winkler, M.; Sander, W. One Century of Aryne Chemistry. Angew. Chem. Int.
Ed. 2003, 42, 502ꢀ528. (b) Pellissier, H.; Santelli, M. The Use of Arynes in Organic Synthesis.
Tetrahedron 2003, 59, 701ꢀ730.
4. Peña, D.; Pérez, D.; Guitián, E. Insertion of Arynes into σ Bonds. Angew. Chem. Int. Ed. 2006,
45, 3579ꢀ3581, and references therein.
5. (a) Bhojgude, S. S.; Biju, A. T. Arynes in Transition Metal Free Multicomponent Coupling
Reactions. Angew. Chem. Int. Ed. 2012, 51, 1520ꢀ1522, and references cited therein. See also: (b)
Bhunia, A.; Biju, A. T. Employing Arynes in TransitionꢀMetalꢀFree, NꢀHeterocycleꢀInitiated
Multicomponent Reactions. Synlett 2014, 608ꢀ614.
6. For a recent review, see: Roy, T.; Biju, A. T. Recent Advances in Molecular Rearrangements
Involving Aryne Intermediates. Chem. Commun. 2018, 54, 2580ꢀ2594.
7. For a recent review, see: Feng, M.; Jiang, X. Reactions of Arynes Involving TransitionꢀMetal
Catalysis. Synthesis 2017, 49, 4414ꢀ4433.
21
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 22 of 27
1
2
3
4
5
6
7
8
9
8. (a) Dhokale, R. A.; Thakare, P. R.; Mhaske, S. B. TransitionꢀMetalꢀFree CꢀArylation at Room
Temperature by Arynes. Org. Lett. 2012, 14, 3994ꢀ3997. (b) Mohanan, K.; Coquerel, Y.;
Rodriguez, J. TransitionꢀMetalꢀFree αꢀArylation of βꢀKeto Amides via an Interrupted Insertion
Reaction ofArynes. Org. Lett. 2012, 14, 4686ꢀ4689.
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
9. (a) Rémond, E.; Tessier, A.; Leroux, F. R.; Bayardon, J.; Jugé, S. Efficient Synthesis of Quaternary
and PꢀStereogenic Phosphonium Triflates. Org. Lett. 2010, 12, 1568ꢀ1571. For early reports, see:
(b) Wittig, G.; Braun, H. Optisch aktive, vierfach ungleich ligierte TetraarylphosphoniumꢀSalze
Liebigs Ann. Chem. 1971, 751, 27ꢀ31. (c) Wittig, G.; Maturza, H. Quaternierung von
Triarylphosphinen rnit Dehydroaromaten. Liebigs Ann. Chem. 1970, 732, 97ꢀ106. (d) Wittig, G.;
Benz, E. Uber das Verhalten von Dehydrobenzol gegenuber nucleophilen und elektrophilen
Reagenzien. Chem. Ber. 1959, 92, 1999ꢀ2013.
10. (a) Bhunia, A.; Kaicharla, T.; Porwal, D.; Gonnade, R. G.; Biju, A. T. Multicomponent Reactions
Involving Phosphines, Arynes and Aldehydes. Chem. Commun. 2014, 50, 11389ꢀ11392. (b)
Bhunia, A.; Roy, T.; Gonnade, R. G.; Biju, A. T. Rapid Access to Benzoxaphospholes and their
Spiro Analogues by a ThreeꢀComponent Coupling Involving Arynes, Phosphines, and Activated
Ketones. Org. Lett. 2014, 16, 5132ꢀ5135. For the reaction of arynes with aldehydes without
additional reagent, see: (c) Yoshida, H.; Watanabe, M.; Fukushima, H.; Ohshita, J.; Kunai, A. A
2:1 Coupling Reaction of Arynes with Aldehydes via oꢀQuinone Methides:ꢂ Straightforward
Synthesis of 9ꢀArylxanthenes. Org. Lett. 2004, 6, 4049ꢀ4051.
11. For selected recent reports on aryne chemistry, see: (a) Xu, H.; He, J.; Shi, J.; Tan, L.; Qiu, D.;
Luo, X.; Li, Y. Domino Aryne Annulation via a NucleophilicꢀEne Process. J. Am. Chem. Soc.
2018, 140, 3555ꢀ3559. (b) Garg, P.; Singh, A. Unmasking Dipole Character of Acyl Ketene
Dithioacetals via a Cascade Reaction with Arynes: Synthesis of Benzo[b]Thiophenes. Org. Lett.
22
ACS Paragon Plus Environment

Page 23 of 27
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
9
2018, 20, 1320ꢀ1323. (c) Shi, J.; Xu, H.; Qiu, D.; He, J.; Li, Y. Selective Aryne Formation via
Grob Fragmentation from the [2+2] Cycloadducts of 3ꢀTriflyloxyarynes. J. Am. Chem. Soc. 2017,
139, 623ꢀ626. (d) Gupta, E.; Kant, R.; Mohanan, K. Decarbethoxylative Arylation Employing
Arynes: A MetalꢀFree Pathway to Arylfluoroamides. Org. Lett. 2017, 19, 6016ꢀ6019. (e) Ross, S.
P.; Baire, B.; Hoye, T. R. Mechanistic Duality in Tertiary Amine Additions to Thermally
Generated HexadehydroꢀDiels–Alder Benzynes. Org. Lett. 2017, 19, 5705ꢀ5708. (f) Phatake, R.
S.; Mullapudi, V.; Wakchaure, V. C.; Ramana, C. V. FluorideꢀMediated Dephosphonylation of
αꢀDiazoꢀβꢀCarbonyl Phosphonates. Org. Lett. 2017, 19, 372ꢀ375.
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
12. For selected recent aryne threeꢀcomponent coupling developed from our group, see: (a) Bhojgude,
S. S.; Roy, T.; Gonnade, R. G.; Biju, A. T. SubstrateꢀControlled Selectivity Switch in the Threeꢀ
Component Coupling Involving Arynes, Aromatic Tertiary Amines, and CO2. Org. Lett. 2016, 18
5424ꢀ5427. (b) Bhojgude, S. S.; Baviskar, D. R.; Gonnade, R. G.; Biju, A. T. ThreeꢀComponent
Coupling Involving Arynes, Aromatic Tertiary Amines, and Aldehydes via ArylꢀAryl Amino
Group Migration. Org. Lett. 2015, 17, 6270ꢀ6273. (c) Roy, T.; Thangaraj, M.; Gonnade, R. G.;
Biju, A. T. Synthesis of Functionalized Amino Epoxides by a ThreeꢀComponent Coupling
Involving Aziridines, Arynes and Aldehydes. Chem. Commun. 2016, 52, 9044ꢀ9047.
13. (a) Deng, Z.; Lin, J.ꢀH.; Xiao, J.ꢀC. Nucleophilic Arylation with Tetraarylphosphonium Salts. Nat.
Commun. 2016, 7, 10337. For related reports on organometallic reagentꢀfree synthesis of
carbinols, see: (b) Das, M.; O’Shea, D. F. Bu4N+ AlkoxideꢀInitiated/Autocatalytic Addition
Reactions with Organotrimethylsilanes. J. Org. Chem. 2014, 79, 5595ꢀ5607. (c) Suzawa, K.;
Ueno, M.; Wheatley, A. E. H.; Kondo, Y. Phosphazene BaseꢀPromoted Functionalization of
Aryltrimethylsilanes. Chem. Commun. 2006, 4850ꢀ4852. (d) Effenberger, F.; Spiegler, W. Zum
23
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 24 of 27
1
2
3
4
5
6
Mechanismus basekatalysierter Carbodesilylierungen von Aryl und Heteroaryltrimethylsilanen.
Chem. Ber. 1985, 118, 3872ꢀ3899.
7
8
9
14. (a) Koniarczyk, J. L.; Hesk, D.; Overgard, A.; Davies, I. W.; McNally, A. A General Strategy for
SiteꢀSelective Incorporation of Deuterium and Tritium into Pyridines, Diazines, and
Pharmaceuticals. J. Am. Chem. Soc. 2018, 140, 1990ꢀ1993. See also: (b) Hilton, M. C.; Dolewski,
R. D.; McNally, A. Selective Functionalization of Pyridines via Heterocyclic Phosphonium Salts.
J. Am. Chem. Soc. 2016, 138, 13806ꢀ13809.
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. For a review on Cs2CO3, see: Flessner, T.; Doye, S. Cesium Carbonate: A Powerful Inorganic
Base in Organic Synthesis. J. Prakt. Chem. 1999, 341, 186ꢀ190.
16. The benzhydrol formed did not undergo further arylation with arynes under the present conditions.
For the arylation of phenols/alcohols, see: (a) Thangaraj, M.; Bhojgude, S. S.; Mane, M. V.; Biju,
A. T. From Insertion to Multicomponent Coupling: Temperature Dependent Reactions of Arynes
with Aliphatic Alcohols. Chem. Commun. 2016, 52, 1665ꢀ1668. (b) Liu, Z.; Larock, R. C. Facile
OꢀArylation of Phenols and Carboxylic Acids. Org. Lett. 2004, 6, 99ꢀ102. (c) Liu, Z.; Larock, R.
C. Facile NꢀArylation of Amines and Sulfonamides and OꢀArylation of Phenols and
Arenecarboxylic Acids. J. Org. Chem. 2006, 71, 3198ꢀ3209.
17. For details, see the Supporting Information
18. For the threeꢀcomponent coupling of arynes, phosphines and isatins leading to the synthesis of
spirobenzoxaphospholes, see ref. 10b.
19. Sato, Y.; Tamura, T.; Kinbara, A.; Morib, M. Synthesis of Biaryls Via PalladiumꢀCatalyzed
[2+2+2] Cocyclization of Arynes and Diynes: Application to the Synthesis of Arylnaphthalene
Lignans. Adv. Synth. Catal. 2007, 349, 647ꢀ661.
24
ACS Paragon Plus Environment

Page 25 of 27
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
9
20. Karthikeyan, J.; Jeganmohan, M.; Cheng, C.ꢀH. CobaltꢀCatalyzed Addition Reaction of
Organoboronic Acids with Aldehydes: Highly Enantioselective Synthesis of Diarylmethanols.
Chem. Eur. J. 2010, 16, 8989ꢀ8992.
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
21. Zhou, F.; Li, C.ꢀJ. The Barbier–GrignardꢀType Arylation of Aldehydes Using Unactivated Aryl
Iodides in Water. Nat. Commun. 2014, 5, 4254.
22. Kobayashi, S.; Shibukawa, K.; Miyaguchi, Y.; Masuyama, A. Grignard Reactions in Cyclopentyl
Methyl Ether. Asian J. Org. Chem. 2016, 5, 636ꢀ645.
23. Wang, M.ꢀH.; Chen, L.ꢀY. An Efficient Fecl3ꢀMediated Approach for Reduction of Ketones
through NꢀHeterocyclic Carbene Boranes. Tetrahedron Lett. 2017, 58, 732ꢀ735.
24. Kuriyama, M.; Shimazawa, R.; Shirai, R. Efficient 1,2ꢀAddition of Arylꢀ And Alkenylboronic
Acids to Aldehydes Catalyzed by the Palladium/ThioetherꢀImidazolinium Chloride System. J.
Org. Chem. 2008, 73, 1597ꢀ1600.
25. Zou, T.; Pi, S. S.; Li, J. H. Fecl3ꢀCatalyzed 1,2ꢀAddition Reactions of Aryl Aldehydes with
ArylboronicAcids. Org. Lett. 2008, 11, 453ꢀ456.
26. Zheng, L.ꢀS.; Jiang, K.ꢀZ.; Deng, Y.; Bai, X.ꢀF.; Gao, G.; Gu, F.ꢀL.; Xu, L.ꢀW. Synthesis of Arꢀ
BINMOL Ligands by [1,2]ꢀWittig Rearrangement to Probe their Catalytic Activity in 1,2ꢀAddition
Reactions ofAldehydes with Grignard Reagents. Eur. J. Org. Chem. 2013, 748ꢀ755.
27. Zheng, H.; Zhang, Q.; Chen, J.; Liu, M.; Cheng, S.; Ding, J.; Wu, H.; Su, W. Copper(II) Acetateꢀ
Catalyzed Addition of Arylboronic Acids to Aromatic Aldehydes. J. Org. Chem. 2009, 74, 943ꢀ
945.
28. Yang, J.; Chen, X.; Wang, Z. The Carbonyl Group Tuned ElectronꢀDeficient Phosphorus Ligands
and their Application in Rhodium Catalyzed Arylation to Aldehydes. Tetrahedron Lett. 2015, 56,
5673ꢀ5675.
25
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 26 of 27
1
2
3
4
5
6
7
8
9
29. Albrecht, M.; Mirtschin, S.; de Groot, M.; Janser, I.; Runsink, J.; Raabe, G.; Kogej, M.; Schalley,
C. A.; Fröhlich, R. Hierarchical Assembly of HelicateꢀType Dinuclear Titanium(Iv) Complexes. J.
Am. Chem. Soc. 2005, 127, 10371ꢀ10387.
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
30. Vile, J.; Carta, M.; Bezzu, C. G.; McKeown, N. B. TribenzotriquinaceneꢀBased Polymers of
Intrinsic Microporosity. Polym.Chem. 2011, 2, 2257ꢀ2260.
31. Das, T.; Chakraborty, A.; Sarkar, A. Solvent Control of Product Diversity in PalladiumꢀCatalyzed
Addition ofArylboronic Acid to Aryl Aldehydes. Tetrahedron Lett. 2014, 55, 5174ꢀ5178.
32. Kondo, S.ꢀI.; Taguchi, Y.; Bie, Y. Solvent Dependent Intramolecular Excimer Emission of Di(1ꢀ
Pyrenyl)Silane and Di(1ꢀPyrenyl) Methane Derivatives. RSC Adv. 2015, 5, 5846ꢀ5849.
33. Busetto, L.; Cassani, M. C.; Femoni, C.; Mancinelli, M.; Mazzanti, A.; Mazzoni, R.; Solinas, G.
NꢀHeterocyclic CarbeneꢀAmide Rhodium(I) Complexes: Structures, Dynamics, and Catalysis.
Organometallics 2011, 30, 5258ꢀ5272.
34. Li, J.; Liu, Q.; Shen, H.; Huang, R.; Zhang, X.; Xiong, Y.; Chen, C. Ethers as Hydrogen Sources
in BF3.OEt2 Promoted Reduction of Diphenylmethyl Alcohols, Ethers and Esters to
Hydrocarbons. RSC Adv. 2015, 5, 85291ꢀ85295.
35. Yamamoto, T.; Furusawa, T.; Zhumagazin, A.; Yamakawa, T.; Oe, Y.; Ohta, T. Palladiumꢀ
Catalyzed Arylation of Aldehydes with BromoꢀSubstituted 1,3ꢀDiarylꢀImidazoline Carbene
Ligand. Tetrahedron 2015, 71, 19ꢀ26.
36. Zheng, T.; Li, J.; Zhang, S.; Xue, B.; Sun, H.; Li, X.; Fuhr, O.; Fenske, D. Selective C−F and C−H
Activation of Fluoroarenes by Fe(PMe3)4 and Catalytic Performance of Iron Hydride in
Hydrosilylation of Carbonyl Compounds. Organometallics, 2016, 35, 3538ꢀ3545.
26
ACS Paragon Plus Environment

Page 27 of 27
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
9
37. Capdevila, M. G.; Benfatti, F.; Zoli, L.; Stenta, M.; Cozzi, P. G. Merging Organocatalysis with an
Indium(Iii)ꢀMediated Process: A Stereoselective αꢀAlkylation of Aldehydes With Allylic Alcohols.
Chem. Eur. J. 2010, 16, 11237ꢀ11241
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
38. Guay, D.; Hamel, P.; Blouin, M.; Brideau, C.; Chan, C. C.; Chauret, N.; Ducharme, Y.; Huang, Z.;
Girard, M.; Jones, T. R.; Laliberté, F.; Masson, P.; McAuliffe, M.; Piechuta, H.; Silva, J.; Young,
R. N.; Girard, Y. Discovery of Lꢀ791,943: A Potent, Selective, Non Emetic and Orally Active
Phosphodiesteraseꢀ4 Inhibitor. Bioorg. Med. Chem. Lett. 2002, 12, 1457ꢀ1461.
39. Fisher, K. M.; Bolshan, Y. Brønsted AcidꢀCatalyzed Reactions of Trifluoroborate Salts with
Benzhydryl Alcohols. J. Org. Chem. 2015, 80, 12676ꢀ12685.
40. Babu, K.N.; Kinthada, L. K.; Ghosh, S.; Bisai, A. Highly Chemoselective Synthesis of Dimeric 2ꢀ
Oxindoles with A Cꢀ3/Cꢀ5’ Linkage via Friedel–Crafts Alkylations of 2ꢀOxindoles with 3ꢀ
Hydroxyꢀ2ꢀOxindoles. Org. Biomol. Chem. 2015, 13, 10641ꢀ10665.
41. Tan, J.; Kuang, Y.; Wang, Y.; Huang, Q.; Zhu, J.; Wang, Y. Axial TriꢀtertꢀButylphosphane
Coordination to Rh2(OAC)4: Synthesis, Structure, and Catalytic Studies.Organometallics 2016,
35, 3139ꢀ3147.
42. Piemontesi, C.; Wang, Q.; Zhu, J. Synthesis of 3,3ꢀDisubstituted Oxindoles by OneꢀPot Integrated
Brønsted BaseꢀCatalyzed Trichloroacetimidation of 3ꢀHydroxyoxindoles and Brønsted Acidꢀ
Catalyzed Nucleophilic Substitution Reaction. Org. Biomol. Chem. 2013, 11, 1533ꢀ1536.
27
ACS Paragon Plus Environment