Palladium-catalyzed allylic C-H oxidation under simple operation and mild conditions

Article abstract of DOI:10.1039/c9ob00209j

We discovered an effective and simple system (Pd/BQ/air/r.t.) for making allylic alcohols through Pd-catalyzed allylic C-H bond functionalization. This approach exhibits advantages due to its simple operation, mild conditions, and environmentally benign features. By modifying reaction conditions, it can be suitable for preparing unsaturated aldehydes, allylic esters, ethers, and amines.

Full text of DOI:10.1039/c9ob00209j

View Article Online
View Journal
Organic &
Biomolecular
Chemistry
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: Z. Shen and Y.
Guo, Org. Biomol. Chem., 2019, DOI: 10.1039/C9OB00209J.
This is an Accepted Manuscript, which has been through the
Volume 14 Number
1 7 January 2016 Pages 1–372
Royal Society of Chemistry peer review process and has been
accepted for publication.
Organic &
Biomolecular
Chemistry
www.rsc.org/obc
Accepted Manuscripts are published online shortly after
acceptance, before technical editing, formatting and proof reading.
Using this free service, authors can make their results available
to the community, in citable form, before we publish the edited
article. We will replace this Accepted Manuscript with the edited
and formatted Advance Article as soon as it is available.
You can find more information about Accepted Manuscripts in the
author guidelines.
Please note that technical editing may introduce minor changes
to the text and/or graphics, which may alter content. The journal’s
standard Terms & Conditions and the ethical guidelines, outlined
in our author and reviewer resource centre, still apply. In no
event shall the Royal Society of Chemistry be held responsible
for any errors or omissions in this Accepted Manuscript or any
consequences arising from the use of any information it contains.
ISSN 1477-0520
COMMUNICATION
Takeharu Haino et al.
Solvent-induced emission of organogels based on tris(phenylisoxazolyl)
benzene
rsc.li/obc

Please do not adjust margins
Organic & Biomolecular Chemistry
Page 1 of 6
View Article Online
DOI: 10.1039/C9OB00209J
Journal Name
COMMUNICATION
Palladium-catalyzed allylic C–H oxidation under simple operation
and mild conditions
Received 00th January 20xx,
Accepted 00th January 20xx
Yunlong Guo, and Zengming Shen*
DOI: 10.1039/x0xx00000x
www.rsc.org/
the formation of H2CO3 which serves as a nucleophile, resulting in
complicated and potentially dangerous operation (Scheme 1, eqn
(2)).11a Recently, Jiang and co-workers reported Pd-catalyzed
aerobic allylic C‒H oxygenation to synthesize allylic alcohols and
unsaturated aldehydes with high yields, but a stoichiometric
amount of acid and heat were necessary in their system (Scheme 1,
eqn (3)).11b Given the significance of allylic alcohols, devising
effective and green approaches for preparing allylic alcohols
remains highly desirable. To our knowledge, there are no examples
that Pd-catalyzed methods under air atmosphere at room
temperature provide allylic alcohols.
We discovered an effective and simple system (Pd/BQ/air/r.t.) for
making allylic alcohols through Pd-catalyzed allylic C‒H bond
functionalization. This approach exhibits advantages due to its
simple operation, mild conditions, and environmentally benign
features. By modifying reaction conditions, it can be suitable for
preparing unsaturated aldehydes, allylic esters, ethers, and
amines.
Sustainable and practical green chemistry lies at the heart of
current organic synthesis research. This concept features simple
operation, mild conditions, atom economy, and a decrease in
released waste. Allylic C‒H bond functionalization reactions have
the potential to streamline synthetic processes.1 Since White’s
discovery of new systems (Pd/sulfoxide/benzoquinone [BQ]),2 it has
become well-established that Pd(II)/sulfoxide can effectively
Previous work:
catalyst, H2
R1
OH
R1
eq. 1
O
catalyst = [Pt], [Ru], [Fe], etc.
undergo allylic C‒H cleavage to form
a reactive -allylPd(II)
intermediate. Compared with traditional methods,3 this strategy
opens new avenues for providing a series of allylic functional
[Pd(PPh3)4] (5 mol%)
+
R1
R1
OH
OH
H2O
H2O
eq. 2
eq. 3
R1
2,5-tBu2BQ (1.5 equiv.), 40 o
C
compounds
via
the
direct
pathway,
avoiding
the
CO2 (4 MPa)
prefunctionalization of allyl substrates.
PdCl2 (10 mol%)
O2 (balloon)
+
R1
Since then, many methods such as allylic C‒H oxidation,4
dehydrogenation,5 amination,6 alkylation,7 silylation,8 fluorination,9
and borylation10 have emerged. However, to the best of our
knowledge, few examples involve the preparation of allylic alcohols
through allylic C‒H bond activation.11 Allylic alcohols are a class of
versatile building blocks in both medicinal chemistry and natural
product syntheses.12 Traditional hydrogenation methods for
preparing allylic alcohols require prefunctionalization of the
substrates (Scheme 1, eqn (1)).13 In 2014, Tokunaga and co-workers
developed palladium-catalyzed allylic C‒H alcoholization with good
yield. In this case, the high pressure of CO2 (4 MPa) was required for
HCl (1 equiv.) 100 o
C
,
This work:
Pd(TFA)2/BQ
air, r.t.
R1
OH
eq. 4
R1
+
H2O
Other nucleophilic
reagents :
RCH OH
,
2
,
RCOOH
Air
Room temperature
H
N
High regioselectivity and yields
Simple operation
Scheme 1. Synthetic approaches for linear allylic alcohols.
Herein, we report an effective and green protocol of Pd-
catalyzed allylic C‒H functionalization to access allylic alcohols using
water as a nucleophile and readily accessible BQ as an oxidant
under air at room temperature (Scheme 1, eqn (4)). The obvious
advantages of this method are that it is simple to operate, open to
a
Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, School of
Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 800
Dongchuan Road, Shanghai, 200240, China. E-mail: shenzengming@sjtu.edu.cn
Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
Please do not adjust margins

Please do not adjust margins
Organic & Biomolecular Chemistry
Page 2 of 6
COMMUNICATION
Journal Name
the air, and runs at room temperature. By slightly modifying the
Having determined the optimal conditions, weVieewxpAlroticreledOntlhinee
DOI: 10.1039/C9OB00209J
reaction conditions, this protocol can be suitable for the generality and limitations of Pd-catalyzed allylic alcoholization
(Table 2). Notably, a wide range of aromatic and heteroaromatic
substituted allylic compounds smoothly transformed to provide
linear allylic alcohols with high chemo- and regioselectivities
(linear/branched = 100:0). Substrates with electron-rich functional
groups on aromatic rings, such as Me (1b, 1h), OMe (1c), t-Bu (1d),
and Et (1i), gave corresponding allylic alcohols with up to 86% yields.
Notably, when methyl attached at the ortho position of a phenyl
ring, the steric hindrance did not influence benzylic C‒H activation,
resulting in the desired product 2b with an 81% yield. Furthermore,
electron-withdrawing groups also exhibited favorable compatibility
in this system (70%–83% yields for 2e–2g, 2j–2l). Substrate 1j,
containing a pentafluorophenyl ring, performed well to give (E)-3-
(perfluorophenyl)prop-2-en-1-ol (2j) in 82% yield. The compatibility
of this reaction can be extended to benzo[b]thiophene and
thiophene–substituted allylic compounds, which gave the
corresponding linear allyl alcohols with high yields (84% yield of 2q
and 86% yield of 2r). Notably, a series of a-methylstyrenes smoothly
underwent Pd-catalyzed allylic C‒H activation to form the
corresponding products in 71-85% yields under mild, air conditions.
However, the substrate with an unprotected hydroxyl group (1x)
could not work under the standard conditions.
preparation of unsaturated aldehydes, allylic esters, ethers,
and amines.
Initially, 1-allylnaphthalene (1a) was chosen as
a model
substrate. In the presence of Pd(TFA)2 (10 mol%), H2O (10 equiv.) as
a nucleophile, and dimethyl sulfoxide (DMSO) as the solvent under
air atmosphere, we first screened a series of BQ derivatives at 60 °C.
As shown in Table 1, when using 2,6-tBu2BQ (2,6-di-tert-
butylcyclohexa-2,5-diene-1,4-dione) as an oxidant, the desired
linear allylic alcohol 2a was obtained in 86% yield (Table 1, entry 4).
Simply using structural BQ and 2-MeBQ (2-methylcyclohexa-2,5-
diene-1,4-dione) generated moderate yields (Table 1, entries 1–2),
owing to the over-oxidation of the allylic C‒H bond that yielded by-
product 5a ((E)-3-(naphthalen-1-yl)acrylaldehyde). We proposed
that the formation of 5a may be suppressed by decreasing
temperature. As we thought, when this reaction ran at room
temperature, an obvious increase in yield was observed using BQ as
the oxidant (86% yield within 38 h; Table 1, entry 7); 2-MeBQ
provided a similar result (Table 1, entry 8). In examinations of
different catalysts, other palladium catalysts such as Pd(OAc)2,
Pd(PhCN)2Cl2, and PdCl2 were inferior to Pd(TFA)2 (Table 1, entries
8–10). Varying the amounts of BQ and H2O provided no further
increases in the yield (Table 1, entries 11–14). Therefore, the
optimal condition for the formation of linear allylic alcohols is the
use of 10 mol% Pd(TFA)2, BQ (1 equiv.), and H2O (10 equiv.) in
DMSO solvent under air at room temperature (Table 1, entry 7).
This approach has several advantages due to its simple operation,
mild conditions, and environmentally benign features.
Table 2. Substrate scope of Pd-catalyzed allylic C‒H alcoholizationa,b
Pd(TFA)2 (10 mol%), BQ (1 equiv.)
R1
R1
OH
H2O
+
DMSO (1 mL), r.t., air
1
2
2c
R = OMe 77%, 24 h (
)
OH
R = tBu 79%, 23 h (
)
2d
OH
OH
2e
R = CF3 83%, 16 h (
)
R
Table 1. Optimization of the reaction conditions for Pd-catalyzed
allylic alcoholizationa, b
2f
)
R = Cl
R = F
75%, 22 h (
81%, 11 h (
86%, 22 h (
80%, 34 h (
2a
2b
)
86%, 38 h (
F
)
81%, 21 h (
2g
)
2h
2i
R = Me
R = Et
)
F
F
F
Cl
)
OH
OH
)
OH
F
F
[Pd] (10 mol%), ligand, oxidant
+
H2O
OH
DMSO, T
2j
2k
2l
81%, 15 h (
82%, 19 h (
)
70%, 13 h (
80%, 60 h (
)
1a
2a
time (h)
OH
OH
OH
)
OH
T (oC)
yield (%)b
H2O (eq.)
entry cat. (10 mol %)
oxidant (eq. )
60
60
60
60
Pd(TFA)2
1
12
12
34
34
60
69
68
86
BQ (1)
10
10
10
2m
2n
2o
2p
78%, 36 h ( )
85%, 21 h (
S
)
)
76%, 35 h (
Pd(TFA)2
Pd(TFA)2
Pd(TFA)2
2
3
4
2-MeBQ (1)
OH
2-tBuBQ (1)
2,6-tBu2BQ (1)
DDQ (1)
OH
OH
S
OH
10
10
10
Pd(TFA)2
Pd(TFA)2
5
6
60
r.t.
34
48
0
2q
2r
2s
2t
85%, 48 h ( )
84%, 34 h (
)
86%, 22 h (
)
56%, 84 h (
)
87
2-MeBQ(1)
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
Pd(TFA)2
Pd(OAc)2
Pd(PhCN)2Cl2
PdCl2
38
48
48
48
52
52
86
30
7
8
BQ (1)
BQ (1)
BQ (1)
BQ (1)
BQ (0.8)
BQ (0.5)
10
10
10
10
10
10
OH
OH
OH
OH
OH
Cl
F
16
9
trace
63
10
11
12
2u
2v
2w
2x
trace ( )
71%, 58 h (
)
83%, 90 h (
)
72%, 108 h (
)
Pd(TFA)2
Pd(TFA)2
14
r.t.
r.t.
Pd(TFA)2
Pd(TFA)2
48
48
71
82
13
14
BQ (1)
BQ (1)
5
a
Reaction conditions: 1 (0.3 mmol, 1 equiv.), Pd(TFA)2 (10 mol%, 0.03
20
mmol), BQ (0.3 mmol, 1 equiv.), H2O (3 mmol, 10 equiv.), DMSO (1 mL), at
room temperature for given time. b Isolated yield.
a
Reaction conditions: 1-allylnaphthalene (0.30 mmol, 1 equiv.), Palladium
(10 mol%, 0.03 mmol). b Isolated yield.
We further conducted a gram scale reaction. The condition was
slightly different from the aforementioned standard conditions. The
2 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 3 of 6
Organic & Biomolecular Chemistry
Please do not adjust margins
Journal Name
COMMUNICATION
amount of BQ was increased to 1.3 equivalents, and the quantity of
H2O was decreased to 3 equivalents (eqn (5)). The desired linear
allylic alcohol 2a was obtained in good yield (73%).
50%–78% yields. To our surprise, when using 4-(tertV-bieuwtAyrlt)icbleenOznoliniec
acid as a nucleophile, a branched allylic ester 7g was observed with
DOI: 10.1039/C9OB00209J
a yield of 26% after 2 days. Subsequently, we focused on the
etherification of allylbenzenes with ethanol as a nucleophile. By
employing dimethylacetamide (DMA) as the solvent and 1,2-
bis(phenylsulfinyl)ethane as a ligand, Pd-catalyzed etherification of
allylbenzenes with OMe and CF3 substitutions on the aromatic rings
was performed to produce the corresponding linear allylic ethers in
44% and 48% yields, respectively (eqn (6)). Surprisingly, Pd-
catalyzed allylic carbazolization using carbazole as a nucleophile
achieved a low 23% yield (eqn (7)). Notably, this is the first example
of carbazole being used as a nucleophile in Pd-catalyzed allylic C‒H
activation.
Pd(TFA)2 (10 mol%)
BQ (1.3 equiv.)
OH
eq. 5
H O (3 eq.)
DMSO (8 mL),
2
r.t., air, 48 h
1a (1 g)
2a
73% yield
When we slightly modified the reaction conditions by increasing
temperature to 80 oC and adding 4Å molecular sieves without water
under an oxygen atmosphere, by-product (E)-acrylaldehydes 5a
unexpectedly became a major product with an acceptable yield.
Therefore, switching the reaction conditions enabled highly
chemoselective formation of linear allylic alcohols and (E)-
acrylaldehydes. The scope of Pd-catalyzed allylic C‒H
functionalization for making (E)-acrylaldehydes is shown in Table 3.
Aromatic allylic compounds bearing electron-rich and electron-poor
substitutions on aromatic rings were examined under the standard
conditions. Notably, we found that MeO, Et, CF3, pentafluoro, and
Cl atoms were well-tolerated, efficiently giving the corresponding
aryl-substituted (E)-acrylaldehydes with 56%–76% yields.
Table 4. Esterification of allylbenzenesa, b, c
O
Pd(TFA)2 (10 mol%), BQ (1 equiv.)
R1
+
RCOOH
R1
O
R
THF (1 mL), 4Å MS, 50 oC, air, 48 h
6
7
O
O
O
7a
)
7b
)
X = H
X = CF3
63%
53%
(
(
O
7c
)
X = OMe 50%
(
X
7d
78% (
)
tBu
O
O
Table 3. Scope of the formation of (E)-acrylaldehydesa, b
O
O
O
O
O
Pd(TFA)2 (10 mol%), BQ (2.5 equiv.)
R1
H
R1
DMSO (1 mL), 4Å MS, 80 °C, O, 48 h
26%b
(
)
4
5
7e
7f
7g
65% (
)
60% (
)
O
F
F
O
O
H
O
F
F
H
a Reaction conditions: 6 (0.30 mmol, 1 equiv.), Pd(TFA)2 (10 mol%, 0.03
H
H
F
F3C
MeO
mmol), BQ (0.3 mmol, 1 equiv.), 4 Å MS, ROOH (0.5 mL), in 1 mL THF at 50 °C
for 48 h. b ROOH (2 equiv.). c Isolated yield.
5a
5b
5c
5d
56% ( )
60% (
)
62% (
)
73% (
)
O
O
O
O
S
H
H
H
H
ligand =
S
S
O
O
Cl
Et
Cl
Pd(TFA)2 (10 mol%)
5e
5f
5g
5h
65% ( )
76% (
)
69% (
)
62% (
)
BQ (1 equiv.)
ligand (10 mol%)
O
OEt
+
EtOH
eq. 6
DMA (1 mL), 4Å MS
r.t., air, 48 h
X
H
X
X = OMe (8a)
X = CF3 (8b)
X = OMe (9a) 44% yield
X = CF3 (9b) 48% yield
5i
66% (
)
a
Pd(TFA)2 (10 mol%)
BQ (1 equiv.)
Reaction conditions: 4 (0.20 mmol, 1 equiv.), Pd(TFA)2 (10 mol%, 0.02
N
mmol), BQ (0.5 mmol, 2.5 equiv.), 4 Å MS, in 1.5 mL DMSO under O2
atmosphere at 80 °C for 48 h. b Isolated yield.
+
NH
eq. 7
CH2Cl2 (1 mL), 4Å MS
90 °C, air, 48h
Encouraged by the success of the Pd-catalyzed allylic C‒H bond
functionalization using water as a nucleophile, we next focused on
carboxylic acids and alcohols employed as nucleophiles, which can
access allylic esterification and etherification. By slightly changing
the previous conditions for Pd-catalyzed allylic alcoholization, we
found that solvents played a significant role in forming allylic esters
and allylic ethers. Tetrohydrofuran (THF) solvent demonstrated
favorable reactivity in the system of Pd-catalyzed allylic C‒H
esterification, giving the corresponding allylic esters in up to 78%
yields at 50 °C (Table 4). When using aliphatic carboxyl acids as
nucleophiles, the exclusive linear allylic esters could be provided in
10a
23% (10b)
1a
To gain insight into the reaction mechanism, some mechanistic
studies were conducted. First, we observed an intermediate during
the course of the Pd-catalyzed allylic alcoholization reaction. We
isolated it and determined its structure to be (E)-3-(naphthalen-1-
yl)allyl 2,2,2-trifluoroacetate 3a (eqn (8)). Interestingly, we found
that this intermediate disappeared at the end of this reaction. This
phenomenon suggests that the generation of 2a could be provided
through a pathway of the hydrolysis of intermediate 3a. On the
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
Please do not adjust margins

Please do not adjust margins
Organic & Biomolecular Chemistry
Page 4 of 6
COMMUNICATION
Journal Name
basis of this phenomenon, we executed two isotope labelling
experiments: (1) H218O (10 equiv.) was employed in place of H2O
under the standard conditions and resulted in a 73:27 ratio of 18O-
2a/16O-2a (eqn (9); based on the high-resolution mass spectrum;
see ESI). (2) When the reaction of 1a was performed in the
presence of H218O (10 equiv.) and stoichiometric Pd(TFA)2 (1 equiv.)
under air, a 42:58 ratio of 18O-2a/16O-2a was detected (eqn (10)).
These experiments revealed two parallel pathways in this system.
One pathway entails the direct use of H2O as a nucleophile. Another
pathway consists of CF3COO– from Pd(TFA)2 acting as a nucleophile
to form allyl trifluoroacetate intermediate, followed by hydrolysis of
allyl trifluoroacetate intermediate to produce linear allyl alcohol.
-allylPd intermediate A along with releasing aViemwoAlreticcluelOenlionef
–
DOI: 10.1039/C9OB00209J
CF3COO . Then, A reacts with BQ to give intermediate B, which is
activated toward nucleophilic functionalization.14 Subsequently, we
consider two pathways that generate product 2. One pathway
entails H2O acting as
a nucleophile to attack the -allylPd
intermediate B (Path A). Afterwards, CF3COO–, as a base, abstracts a
proton of water to form intermediate C. Finally, intermediate C
provides the linear allylic alcohol 2. In Path B, intermediate B
undertakes reductive elimination to yield the intermediate D in
which the coordinated CF3COO– serves as a nucleophile. After the
disassociation of palladium(0) species from intermediate D,
hydrolysis occurs in the allyl trifluoroacetate intermediate 3 to
provide the linear allylic alcohol 2, which releases a molecule of
CF3COOH to the system again. The palladium (0) species can be
oxidized to Pd(II) once more by BQ with the assistance of CF3COOH.
Pd(TFA)2 (10 mol%)
BQ (1 equiv.) H2O (4 equiv.)
O
CF3
O
eq. 8
DMSO (1 mL), r.t., air, 16 h
1a
1a
1a
7% (3a)
In conclusion, we developed an effective and simple system
(Pd/BQ/air/r.t.) for making linear allylic alcohols through Pd-
catalyzed allyl C‒H bond functionalization. This approach features
several advantages: (1) it uses air as atmosphere, (2) it is conducted
at room temperature, (3) it is simple to operate, and (4) it has high
regioselectivity and yields. Our mechanistic studies suggest two
possible pathways to provide linear allylic alcohols. One pathway
entails water acting as a nucleophile, the other entails CF3COO-
from Pd(TFA)2 serving as a nucleophile. In addition, switching the
reaction conditions enables highly chemoselective formation of (E)-
acrylaldehyde derivatives. When slightly modifying the conditions
for forming linear allylic alcohols, this approach can be suitable for
some other nucleophiles to provide corresponding allylic esters,
ethers, and amines. The synthetic value of our method for
preparing linear allylic alcohols was demonstrated in the gram scale
study, which suggests its value to academia and industry.
Pd(TFA)2 (10 mol%), BQ (1 equiv.)
eq. 9
OH
DMSO (1 mL), H218O (10 equiv. )
r.t., air, 48 h
18O-2a : 16O-2a = 73 : 27
Pd(TFA)2 (100 mol%), BQ (1 equiv.)
DMSO (1 mL), H218O (10 equiv. )
r.t., air, 12 h
OH
eq. 10
18O-2a : 16O-2a
= 42 : 58
Scheme 2. Mechanistic studies on the formation of linear allylic
alcohols.
H
R
OH
OH
CF3COOH + L
1
PdIIOCOCF3
L2PdII(TFA)2
R
A
Conflicts of interest
BQ
2CF3COOH
+
L
There are no conflicts to declare.
(H2O acts as a NuH.)
H2O
Pd(BQ)
OH
CF3COOH
(BQ)PdIIOCOCF3
(BQ)Pd0
R
R
Acknowledgements
C
R
path A
B
This work was supported by the National Natural Sciences
Foundation of China (No. 21672144) and the Shanghai Key
Laboratory for Molecular Engineering of Chiral Drugs (No.
17DZ2260400). We are grateful to the Instrumental Analysis Center
of Shanghai Jiao Tong University for compound analysis.
OH
2
path B
Pd(BQ)
O
R
O
CF3
D
O
H2O
R
OH
R
O
CF3
Notes and references
3
2
CF3COOH
1
(a) J. Tsuji, Acc. Chem. Res., 1969, 2, 144. (b) C. Engelin, T.
Jensen, S. Rodriguez-Rodriguez and P. Fristrup, ACS Catal.,
2013, 3, 294. (c) M. P. Doyle and D. C. Forbes, Chem. Rev.
1998, 98, 911. (d) Z.-H. Zhang and J.-B. Wang, Tetrahedron
2008, 64, 6577. (e) G.-S. Liu and Y.-C. Wu, Top. Curr. Chem.
2009, 292, 195. (f) R. Giri, B.-F. Shi, K.-M. Engle, N. Maugel
and J.-Q. Yu, Chem. Soc. Rev., 2009, 38, 3242. (g) H. Li, B.-J. Li
and Z.-J. Shi, Catal. Sci. Technol. 2011, 1, 191. A. Nakamura
Scheme 3. Postulated mechanism for allylic alcoholization.
On the basis of the aforementioned mechanistic studies and
previous reports,2b a tentative reaction mechanism for Pd-catalyzed
allyl C‒H bond alcoholization is proposed. First, substrate 1 reacts
with catalyst Pd(TFA)2 to undergo allyl C‒H bond activation, giving
4 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 5 of 6
Organic & Biomolecular Chemistry
Please do not adjust margins
Journal Name
COMMUNICATION
and M. Nakada, Synthesis., 2013, 45, 1421. (h) S. E. Mann, L.
Benhamou and T. D. Sheppard, Synthesis., 2015, 47, 3079.
Yamamoto, H. Murayama, T. Ishida, T. Honnma, T. Fujitani
and M. Tokunaga, Appl. Catal. B Environ., 2019,V2ie4w6A1rt0icl0e.Online
DOI: 10.1039/C9OB00209J
2
(a) M.-S. Chen and M.-C. White, J. Am. Chem. Soc., 2004, 12 (a) S.-J. Lee, K.-C. Gray, J.-S. Paek and M.-D. Burke, J. Am.
126, 1346. (b) M.-S. Chen, N. Prabagaran, N.-A. Labenz and
M.-C. White, J. Am. Chem. Soc., 2005, 127, 6970. (c) K.-J.
Fraunhoffer, D.-A. Bachovchin and M.-C. White, Org. Lett.,
2005, 7, 223. (d) J.-H. Delcamp, M.-C. White, J. Am. Chem.
Soc., 2006, 128, 15076. (e) J.-F. Kenneth and M.-C. White, J.
Chem. Soc., 2008, 130, 466. (b) G.-J. McGarvey, J.-M.
Williams, R.-N. Hiner, Y. Matsubara and T. Oh, J. Am. Chem.
Soc., 1986, 108, 4943. (c) S.-D. Rychnovsky and R.-C. Hoye, J.
Am. Chem. Soc., 1994, 116, 1753. (d) D. Brandt, V. Bellosta
and J. Cossy, Org. Lett., 2012, 14, 5594.
Am. Chem. Soc., 2007, 129, 7274. (f) A.-J. Young and M.-C. 13 (a) M.-B. Bhalchandra, I. Yutaka, S. Masayuki and A.
White, J. Am. Chem. Soc., 2008, 130, 14090. (g) S.-A. Reed,
A.-R. Mazzotti and M.-C. White, J. Am. Chem. Soc., 2009, 131,
11701. (h) C. Jiang, D. J. Covell, A. F. Stepan, M. S. Plummer
and M. C. White, Org. Lett., 2012, 14, 1386. (i) A.-J. Young
and M.-C. White, Angew. Chem., Int. Ed. 2011, 50, 6824. (j) T.
J. Osberger and M. C. White, J. Am. Chem. Soc., 2014, 136,
11176.
(a) B.-M. Trost and D.-L. Van Vranken, Chem. Rev., 1996, 96,
395. (b) B.-M. Trost and M.-L. Crawley, Chem. Rev., 2003,
103, 2921. (c) B.-M. Trost, M.-R. Machacek and A.-A.
Aponick, Chem. Res., 2006, 39, 747. (d) F. Ozawa, H.
Okamoto, S. Kawagishi, S. Yamamoto, T. Minami, M.
Yoshifuji, J. Am. Chem. Soc. 2002, 124, 10968. (e) I. Usui, S.
Schmidt and B. Breit, Org. Lett., 2009, 11, 1453. (f) S.-C.
Zheng, M. Zhang and X.-M. Zhao. Chem. Eur. J. 2014, 20,
7216.
(a) E. Thiery, C. Aouf and J. Belloy, J. Org. Chem., 2010, 75,
1771. (b) T. Mitsudome, T. Umetani and N. Nosaka, Angew.
Chem., Int., Ed. 2006, 45, 481. (c) W. H. Henderson, C. T.
Check and N. Proust, Org. Lett., 2010, 12, 824. (d) M. Malik,
G. Witkowski, S. Jarosz, Org. Lett., 2014, 16, 3816. (e) X. Xing,
N.-R. O’Connor and B.-M. Stoltz, Angew. Chem., Int. Ed.,
2015, 54, 11186. (f) H. Kondo, F. Yu, J. Yamaguchi, G.-S. Liu
and K. Itami, Org. Lett. 2014, 16, 4212. (g) H.-J. Chen, C.-B.
Cai. J. Dong, W. Fu and H.-F. Jiang, Org. Lett., 2011, 13, 992.
(h) N.-A. Vermeulen, J.-H. Delcamp and M.-C. White, J. Am.
Chem. Soc., 2010, 132, 11323. (i) C.-H. Li, M. Li, J.-X. Li, J.-H.
Liao, W.-Q. Wu and H.-F. Jiang, J. Org. Chem., 2017, 82,
10912.
Masahiko, Catalysis Letters., 1999, 62, 175. (b) G. Wienhçfer,
F.-A. Westerhaus, K. Junge, R. Ludwig and M. Beller, Chem.
Eur. J., 2013, 19, 7701. (c) W.-J. Liu, K. Tian and H. Jiang,
Green Chem., 2015, 17, 821. (d) R.-X. Liu, H.-Y. Cheng, Q.
Wang, C.-Y. Wu, J. Ming, F.-Y. Zhao and M. Arai, Green
Chem., 2008, 10, 1082.
14 (a) J.-S. Temple, M. Riediker and J. Schwartz, J. Am. Chem.
Soc., 1982, 104, 1310. (b) J.-E. Ba¨ckvall, S.-E. Bystrom and
R.-E. Nordberg, J. Org. Chem., 1984, 49, 4619 (c) H.
Grennberg, A. Gogoll and J.-E. Ba¨ckvall, J. Org. Chem., 1991,
56, 5808. (d) J.-E. Backvall and A. Gogoll, Tetrahedron Lett.,
1988, 29, 2243.
3
4
5
6
E.-M. Stang and M.-C. White, J. Am. Chem. Soc., 2011, 133,
14892.
(a)S.-R. Vemula, D. Kumar and G.-R. Cook, ACS Catal., 2016,
6, 5295. (b) Y. Shimizu, Y. Obora and Y. Ishii, Org. Lett., 2010,
12, 1372. (c) G.-Y. Yin, Y.-C. Wu and G.-S. Liu, J. Am. Chem.
Soc., 2010, 132, 11978. (d) J. Sun, Y. Wang and Yi. Pan, J. Org.
Chem., 2015, 80, 8945. (e) L. Wu, S.-F. Qiu and G.-S. Liu, Org.
Lett., 2009, 11, 2707. (f) S.-A. Reed and M.-C. White, J. Am.
Chem. Soc., 2008, 130, 3316. (g) R. Ma and M.-C. White, J.
Am. Chem. Soc., 2018, 140, 3202.
(a) L. Song, C.-X. Song, G.-X. Cai, W.-H. Wang and Z.-J. Shi, J.
Am. Chem. Soc., 2008, 130, 12901; (b) P.-S. Wang, H.-C. Lin,
X.-L. Zhou and L.-Z. Gong, Org. Lett., 2014, 16, 3332; (c) H.
Zhang, R.-B. Hu, N. Liu, S.-X. Li and S.-D. Yang, Org. Lett.,
2016, 18, 28. (d) G. Hu, J. Xu and P.-F. Li, Org. Lett., 2014, 16,
6036. (e) J. Franzén and J.-E. Bäckvall, J. Am. Chem. Soc.
2003, 125, 6056. (f) A.-K. Persson and J.-E. Bäckvall, Angew.
Chem., Int. Ed., 2010, 49, 4624.
7
8
9
J. M. Larsson, T. S. N. Zhao and K.-J. Szabó, Org. Lett., 2011,
13, 1888.
M.-G. Braun and A.-G. Doyle, J. Am. Chem. Soc., 2013, 135,
12990.
10 (a) Z.-L. Tao, X.-H. Li, Z.-Y. Han and L.-Z. Gong, J. Am. Chem.
Soc. 2015, 137, 4054. (b) H.-P. Deng, L. Eriksson and K.-J.
Szabó, Chem. Commun., 2014, 50, 9207.
11 (a) R. Tomita, K. Mantani, A. Hamasaki, T. Ishida and M.
Tokunaga, Chem. Eur. J., 2014, 20, 9914. (b) C. Li, H. Chen, J.
Li, M. Li, J.-H. Liao, W.-H. Wu and H.-F. Jiang, Adv. Synth.
Catal., 2018, 360, 1600. (c) Z.-Z. Zhang, T. Mamba, E.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 5
Please do not adjust margins

Organic & Biomolecular Chemistry
Page 6 of 6
View Article Online
DOI: 10.1039/C9OB00209J
H
O
Pd(TFA)2 (10 mol%) / BQ
Pd(TFA)2 (10 mol%) / BQ
R
OH
R
R
H
DMSO
DMSO
O2, 80 o
linear : branched = 100 : 0
24 examples
9 examples
up to 76% yield
C
H2O, r.t., air
up to 86% yield
Air
Room temperature
Pd(TFA)2 (10 mol%) / BQ
R
Nu
10 examples
up to 78% yield
solvent, air, T, NuH
High regioselectivity and yields
Simple operation
NuH = RCOOH, EtOH, carbazole