RETRACTED ARTICLE: Palladium-Catalyzed Decarboxylative Selective Acylation of 4H-Benzo[d][1,3]oxazin-4-one Derivatives with α-Oxo Carboxylic acids via Preferential Cyclic Imine-N-Directed Aryl C-H Activation

Article abstract of DOI:10.1002/adsc.201500786

The benzoxazine scaffolds are of much interest as they are found in a large array of natural products and pharmaceutical drugs with diverse activities. We have developed a palladium-catalyzed decarboxylative selective mono- and bis-acylation of 4H-benzo[d

Full text of DOI:10.1002/adsc.201500786

FULL PAPERS
DOI: 10.1002/adsc.201500786
Palladium-Catalyzed Decarboxylative Selective Acylation of 4H-
Benzo[d][1,3]oxazin-4-one Derivatives with a-Oxo Carboxylic
À
acids via Preferential Cyclic Imine-N-Directed Aryl C H
Activation
a
a
a
a,
Biju Majhi, Debasish Kundu, Tubai Ghosh, and Brindaban C. Ranu *
a
Department of Organic Chemistry, Indian Association for the Cultivation of Science, Jadavpur, Kolkata – 700032, India
E-mail: ocbcr@iacs.res.in
Received: August 21, 2015; Revised: October 5, 2015; Published online: January 5, 2016
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201500786.
Abstract: The benzoxazine scaffolds are of much in- ingly when the reaction was performed with silver
terest as they are found in a large array of natural triflate (AgOTf) in place of silver nitrate (AgNO3)
products and pharmaceutical drugs with diverse ac- in the presence of 4 equivalents of glyoxylic acid, the
tivities. We have developed a palladium-catalyzed bis-acylated product was obtained together with
decarboxylative selective mono- and bis-acylation of a small amount of mono-acylated product. This is
4
H-benzo[d][1,3]oxazin-4-one derivatives with a-oxo the first report of acylation of 2-aryl-4H-benzo[d]
carboxylic acids via preferential cyclic imine-N-di- [1,3]oxazin-4-ones via CÀH activation. The notable
rected activation. 2-Aryl-4H-benzo[d] features of this reaction are acylation with more
CÀH
1,3]oxazin-4-one was acylated with a variety of sub- challenging heteroarene-oxo carboxylic acids and
[
stituted phenylglyoxylic acids to produce the corre- alkyl oxo carboxylic acids. This new protocol pro-
sponding products. It was observed that electron-do- vides an easy and efficient access to a variety of o-
nating groups (CH , OCH ) at any position of the ar- acyl-4H-benzo[d][1,3]oxazin-4-one derivatives which
3
3
omatic ring of phenylglyoxylic acid provided good to are of pharmaceutical importance.
excellent yields, whereas phenylglyoxylic acids con-
taining electron-withdrawing groups (COCH , CN, Keywords: acylation; 4H-benzo[d][1,3]oxazin-4-one;
3
NO ) gave the products in moderate yields. Interest- CÀH activation; decarboxylation; palladium
2
Introduction
pharmaceutical drugs with diverse activities such as
[10]
chymotrypsin inhibitor,
HSV-1 protease inhibi-
Transition metal-catalyzed decarboxylative coupling
via CÀH activation has received considerable atten-
tion in recent times as a powerful green tool for
carbon-carbon and carbon-heteroatom bond forma-
tion as it does not require stoichiometric organome-
tallic coupling reagents and it leaves carbon dioxide
[
1]
only in place of toxic metal waste. Since the pio-
[
2]
[3]
neering work of Myers and Goossen this reaction
has been used for CÀH functionalization of various
systems. Recently, decarboxylative acylation using a-
oxo carboxylic acids has been successfully applied for
[
4]
ortho-acylation of acetanilides,
O-phenyl carba-
[
5]
[6]
[7]
mates, indoles, azoxybenzenes, and O-methyl ke-
toximes among others. We became interested in
[
8]
[9]
the functionalization of 4H-benzo[d][1,3]oxazin-4-one
as benzoxazine scaffolds are of much interest. They Figure 1. A few biologically active molecules containing the
are found in a large array of natural products and 4H-benzo[d][1,3]oxazin-4-one moiety.
Adv. Synth. Catal. 2016, 358, 283 – 295
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
283

Biju Majhi et al.
FULL PAPERS
[
11]
[12]
tors, serine proteases inhibitor, and inhibitors of
[
13]
leucocyte clatase. A few representative compounds
are outlined in Figure 1. They also serve as useful
building blocks in organic synthesis.
[
14]
[
15]
To the best of our knowledge there is no report for
functionalization of this system via metal catalyzed
CÀH activation. As a part of our continuing interest
in CÀH functionalization by transition metal-cata-
[
17,18]
lyzed CÀH activation
we report here the hitherto
unreported regioselective CÀH acylation of benzoxa-
Scheme 1. Pd-catalyzed cyclic imine N-directed CÀH acyla-
zine-4-one derivatives by Pd-catalyzed cyclic imine-N-
tion of benzoxazine-4-one derivatives.
directed CÀH activation (Scheme 1). Although a few
[16]
procedures have been reported for their synthesis
by other protocols, some of them are associated with
[a]
Table 1. Optimization of the reaction conditions.
[b]
Entry
Pd Catalyst (mol%)
Oxidant (equiv.)
Co-oxidant (equiv.)
Solvent
Yield [%]
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
Pd(OAc) (10)
AgOAc (1)
AgOAc (1)
AgOAc (1)
AgOAc (1)
AgOAc (1)
AgOAc (1)
Ag CO (1)
–
–
–
–
–
–
–
–
dioxane
xylene
DCE
DMF
diglyme
22
21
27
–
–
–
2
Pd(OAc) (10)
2
Pd(OAc) (10)
2
Pd(OAc) (10)
2
Pd(OAc) (10)
2
Pd(OAc) (10)
CH CN
2
3
Pd(OAc) (10)
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
12
46
trace
52
63
27
43
–
85
83
trace
20
5
69
75
59
84
65
53
–
2
2
3
Pd(OAc) (10)
AgNO (1)
2
3
Pd(OAc) (10)
Ag O (1)
–
2
2
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
Pd(OAc) (10)
AgNO (1)
K S O (1)
(NH ) S O (1)
Na S O (1)
2 2 8
Oxone (1)
TBHP (1)
(NH ) S O (2)
(NH ) S O (3)
(NH ) S O (2)
4 2 2 8
(NH ) S O (2)
(NH ) S O (2)
4 2 2 8
(NH ) S O (2)
(NH ) S O (2)
(NH ) S O (2)
4 2 2 8
(NH ) S O (2)
(NH ) S O (2)
4 2 2 8
(NH ) S O (2)
2
3
2
2
8
Pd(OAc) (10)
AgNO (1)
2
3
4 2 2 8
Pd(OAc) (10)
AgNO (1)
2
3
Pd(OAc) (10)
AgNO (1)
2
3
Pd(OAc) (10)
AgNO (1)
2
3
Pd(OAc) (10)
AgNO (1)
2
3
4
2
2
8
Pd(OAc) (10)
AgNO (1)
2
3
4 2 2 8
Pd(CH CN) Cl (10)
AgNO (1)
3
2
2
3
Pd(acac) (10)
AgNO (1)
2
3
4 2 2 8
Pd(PPh ) Cl (10)
AgNO (1)
3
2
2
3
[
[
[
[
c]
d]
e]
f]
Pd(OAc) (10)
AgNO (1)
2
3
4
2
2
8
Pd(OAc) (10)
AgNO (1)
2
3
4 2 2 8
Pd(OAc) (10)
AgNO (1)
2
3
Pd(OAc) (10)
AgNO (1)
2
3
4 2 2 8
Pd(OAc) (5)
AgNO (1)
2
3
Pd(OAc) (10)
–
2
4 2 2 8
–
AgNO (1)
(NH ) S O (2)
4 2 2 8
3
[a]
Reaction conditions: 2-phenyl-4H-benzo[d][1,3]oxazin-4-one (0.5 mmol), phenylglyoxylic acid (1.5 mmol), oxidant, co-oxi-
dant, solvent, 508C, 18 h.
Isolated yields.
At 408C.
[
[
[
[
[
b]
c]
d]
e]
f]
At 608C.
2
equivalents of phenylglyoxylic acid were used.
For 24 h.
2
84
asc.wiley-vch.de
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2016, 358, 283 – 295

FULL PAPERS
Palladium-Catalyzed Decarboxylative Selective Acylation
Table 2. Pd-catalyzed CÀH acylation of 2-phenyl-4H- Results and Discussion
[
a]
benzo[d][1,3]oxazin-4-one with a-oxo carboxylic acids.
To optimize the reaction conditions a series of experi-
ments were performed with variation of reaction pa-
rameters, such as catalyst, solvent, oxidant, tempera-
ture and time for a representative reaction of 2-
phenyl-4H-benzo[d][1,3]oxazin-4-one and phenyl-
glyoxylic acid. In the presence of Pd(OAc)2
(
1
10 mol%), AgOAc (1 equiv.) as oxidant at 508C in
,4-dioxane, only 22% acylated product, 2-(2-benzoyl-
phenyl)-4H-benzo[d][1,3]oxazin-4-one was isolated
Table 1, entry 1). Dichloroethane was found to be
(
a more effective solvent compared to 1,4-dioxane,
xylene (Table 1, entries 1–3), whereas the reaction did
not proceed at all in DMF, diglyme and CH CN
3
(
Table 1, entries 4–6). Replacement of the oxidant
AgOAc by AgNO3 improved the yield (Table 1,
entry 8). However, use of Ag CO and Ag O led to
2
3
2
lower yields (Table 1, entries 7 and 9). The yield of
product was further improved using K S O as co-oxi-
2
2
8
dant in combination with AgNO3 although
NH ) S O was found to be more efficient compared
(
4
2
2
8
to K S O , Na S O , oxone and TBHP (Table 1, en-
2
2
8
2
2
8
tries 10–14). Thus the best yield was obtained by
using Pd(OAc) (10 mol%) in combination with one
2
equivalent of AgNO3 and two equivalents of
(
(
(
NH ) S O in dichloroethane at 508C for 18 h
4 2 2 8
Table 1, entry 15). An increase of the amount of
NH ) S O beyond 2 equivalents did not improve the
4
2
2
8
outcome of the reaction (Table 1, entry 16). Pd(OAc)2
showed better catalytic activity as compared to
Pd(CH CN) Cl , Pd(acac) , Pd(PPh ) Cl (Table 1, en-
3
2
2
2
3
2
2
tries 15 and 17–19). The reaction temperature at 508C
is just optimum as lower and higher temperatures
(
(
408C and 608C) furnished reduced yields of product
Table 1, entries 20 and 21). The use of 2 equivalents
of phenylglyoxylic acid or 5 mol% of catalyst led to
a lower yield of product (Table 1, entries 22 and 24).
The reaction did not proceed at all in absence of
Pd(OAc) (Table 1, entry 26).
2
2
-Aryl-4H-benzo[d][1,3]oxazin-4-one was subjected
to acylation with a variety of substituted phenylglyox-
ylic acids under the reaction conditions to produce
the corresponding products (Table 2). It was observed
that electron-donating groups (CH , OCH ) at any
3
3
position on the aromatic ring of phenyl glyoxylic acid
provided good to excellent yields (3ab, 3ac and 3bb),
whereas phenylglyoxylic acids containing electron-
withdrawing groups (COCH , CN, NO ) gave the
3
2
[a]
products in moderate yields (3am, 3an and 3ao).
Reaction conditions: 2-aryl-4H-benzo[d][1,3]oxazin-4-one
0.5 mmol), 2-oxo-2-phenylacetic acid (1.5 mmol),
The halogen moieties (F, Cl, Br, I) on phenylglyox-
Pd(OAc)2 (10 mol%), (NH ) S O (1 mmol), AgNO3 ylic acids remained unaffected under the reaction
(
4
2
2
8
(
0.5 mmol), DCE, 508C, 18 h.
conditions affording the corresponding products (3ae,
af, 3ag, 3ah, 3bk and 3al) in good yields although the
Pd-catalyzed decarboxylative acylation of aryl halide
3
[19]
operational drawbacks such as use of high reaction was a possibility.
temperature and generation of waste.
The a- and b-naphthyloxoacetic
Adv. Synth. Catal. 2016, 358, 283 – 295
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
285

Biju Majhi et al.
FULL PAPERS
Table 3. Reaction
of
substituted
2-aryl-4H-benzo[d]
The effect of substituents on the phenyl ring of 2-
aryl-4H-benzo[d][1,3]oxazin-4-one under the reaction
conditions was studied (Table 3). Both electron-donat-
ing (CH , OCH and t-Bu) and electron-withdrawing
[a]
[1,3]oxazin-4-ones with phenylglyoxylic acid.
3
3
groups (F, Cl) on the aromatic ring of 2-aryl-4H-
benzo[d][1,3]oxazin-4-one are compatible with the re-
action conditions. The ortho-substituted 2-aryl-4H-
benzo[d][1,3]oxazin-4-one (1k) was found to produce
a lower yield of product (3ka).
We checked this protocol of decarboxylative CÀH
acylation of benzoxazine-4-ones with heteroarylglyox-
ylic acids. Reactions with thiophenyl- (2p) and furan-
yl- (2q) glyoxylic acids were found to be successful
producing good yields of acylated products
(
Scheme 2, 3ap and 3aq). We have also accomplished
N-directed CÀH acylation in the thiophenyl ring at-
tached with the benzoxazine-4-one moiety (Scheme 2,
3
ra). This type of CÀH acylation in a heteroarene
unit is novel and was not been reported earlier.
[a]
Reaction conditions: 2-aryl-4H-benzo[d][1,3]oxazin-4-one
(
(
0.5 mmol), phenylglyoxylic acid (1.5 mmol), Pd(OAc)2
10 mol%), (NH ) S O (1 mmol), AgNO3 (0.5 mmol),
4
2
2
8
DCE, 508C, 18 h.
acids participated in this reaction efficiently affording Scheme 2. CÀH acylation of benzoxazine-4-ones with heter-
good yield of products (3ai, 3aj, 3bi and 3bj). oarylglyoxylic acids.
2
86
asc.wiley-vch.de
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2016, 358, 283 – 295

FULL PAPERS
Palladium-Catalyzed Decarboxylative Selective Acylation
We have successfully performed the CÀH acylations
with alkylglyoxylic acids (Scheme 3) which is usually
[4,9a,k]
difficult to achieve.
The 2-aryl-4H-benzo[d][1,3]oxazin-4-ones bearing
meta substituents on the aryl ring showed excellent
regioselectivity towards CÀH acylation under these
conditions (Scheme 4). In substrates 1n (F), 1p (CH )
3
and 1q (OCH ), the acylation occurred preferentially
3
at the N-directed positions although O-directed prod-
ucts are also formed in minor amounts. However, in
case of meta-Cl substituted substrate (1o), acylation
occurred exclusively at the N-directed position para
to Cl (3oa). The structure of 3oa was confirmed by X-
[20]
ray crystallography too (Figure 2).
A suitably halo-substituted acyl 2-aryl-4H-benzo[d]
[
1,3]oxazin-4-one may undergo further functionaliza-
tion as outlined in Scheme 5. Thus, the corresponding
acylated product from the reaction of 1h and 2a was
subjected to Suzuki coupling to provide 3hax with in-
corporation of a phenyl ring.
Scheme 3. Pd-catalyzed CÀH acylation of 2-phenyl-4H-
benzo[d][1,3]oxazin-4-one with alkyl a-oxo carboxylic acids.
Scheme 4. CÀH Acylation of meta-substituted 2-aryl-4H-benzo[d][1,3]oxazin-4-ones.
Adv. Synth. Catal. 2016, 358, 283 – 295
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
287

Biju Majhi et al.
FULL PAPERS
Table 4. Pd-catalyzed CÀH bis-acylation of 2-aryl-4H-
benzo[d][1,3]oxazin-4-ones.
[
a]
Figure 2. ORTEP diagram of 2-(2-benzoyl-5-chlorophenyl)-
H-benzo[d][1,3]oxazin-4-one (Scheme 4, 3oa).
4
Scheme 5. Further functionalization of acylated products.
[
a]
Interestingly, when the reaction was performed
Reaction conditions: 2-aryl-4H-benzo[d][1,3]oxazin-4-one
with AgOTf in place of AgNO in the presence of 4
(0.5 mmol), phenylglyoxylic acid (2 mmol), Pd(OAc)2
3
equivalents of glyoxylic acid, the bis-acylated product
accommodating both N- and O-directed functionaliza-
tion was obtained without any considerable amount
(15 mol%), (NH
4
) S
2
2
O
8
(1 mmol), AgOTf (1 mmol),
DCE, 608C, 24 h.
(
3–5%) of mono-acylated product. A series of bis-acy-
Table 5. Mono- vs. bis-acylated products.
-Aryl-4H- Phenylglyoxylic Mono-acylat- Bis-acylat-
lated products were obtained under the reaction con-
ditions (Table 4, Table5). The electron-donating
2
groups, for example, OCH , CH (4ba, 4ca and 4ma) benzo[d][1,3]- acid
ed product
ed product
3
3
and electron-withdrawing groups, for example, Cl, F oxazin-4-one
(
4ea, 4fa) are compatible in this reaction. On close
1
1
1
1
a
b
c
2a
2a
2a
2a
2a
2a
3aa (4%)
3ba (3%)
3ca (5%)
3ea (4%)
3fa (6%)
3ma (3%)
4aa (78%)
4ba (81%)
4ca (79%)
4ea (66%)
4fa (71%)
4ma (61%)
monitoring of the progress of the reaction it was es-
tablished that the bis-acylated product was formed
through the intermediacy of the mono-acylated one
as depicted in Figure 3. The precise role of AgOTf in 1f
leading to bis-acylation is not very clear to us at this 1m
stage.
e
To investigate the mechanism of the reaction, the
reaction was performed in the presence of 1 equiva-
[5–9]
In accordance with the earlier reports
it is as-
lent of TEMPO (a radical-trapping agent) under the sumed that the reaction initiates with the ortho-palla-
standardized conditions. The outcome of the reaction dation of benzoxazine in the presence of Pd(OAc)2
did not change indicating that no free radical inter- forming a 5-membered palladacycle(II) intermediate
mediate was involved in the reaction.
A, which then undergoes a trans-metallation with
2
88
asc.wiley-vch.de
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2016, 358, 283 – 295

FULL PAPERS
Palladium-Catalyzed Decarboxylative Selective Acylation
benzo[d][1,3]oxazin-4-ones has been developed via
a palladium-catalyzed CÀH activation process. To the
best of our knowledge we are not aware of any earlier
report on the acylation of 2-aryl-4H-benzo[d]
[
1,3]oxazin-4-ones via CÀH activation. Significantly,
the mono-acylated product was obtained using
AgNO3 and (NH ) S O whereas replacement of
4
2
2
8
AgNO by AgOTf led to the bis-acylated compound.
3
This is a novel and hitherto unreported observation
and provides a convenient tool for an access to mono-
or bis-acylated product by choice. The other notable
features of this reaction are acylation with more chal-
lenging heteroarene-oxo carboxylic acids and alkyl
oxo-carboxylic acids. This method provides a simple
procedure for the synthesis of a library of acyl-2-aryl-
4H-benzo[d][1,3]oxazin-4-ones which may have much
potential in organic synthesis and the pharma indus-
try.
Figure 3. Monitoring the progress of the diacylated product.
Experimental Section
General Methods
IR spectra were taken as thin films for liquid compounds
and as KBr pellets for solids. NMR spectra were recorded at
1
3
00 and 500 MHz for H spectra and at 75 and 125 MHz for
1
3
C spectra in CDCl solutions.
3
Representative Experimental Procedure for the
Preparation of 2-aryl-4H benzo[d][1,3]oxazin-4-ones
To a solution of anthranilic acid (10 mmol, 1.37 g) in pyri-
dine (30 mL) cooled at 08C in an ice bath was added an
acid chloride (0.02 mol) dropwise slowly and carefully with
proper control. An exothermic reaction occurred. The reac-
tion mixture was stirred for 5 min at 08C. The ice bath was
removed and the reaction mixture was allowed to warm
slowly to room temperature (308C). The reaction mixture
was further stirred for 0.5 h at room temperature. After
completion of the reaction (TLC) the mixture was poured
into ice-cold water (200 mL) and residue was collected by
filtration and washed with cold water (3”60 mL) and dried.
The crude benzoxazin-4-one was recrystallized from ethanol
as white prismatic needles.
Scheme 6. Plausible mechanism of the reaction.
[
9f]
acyl-silver species B formed by the silver-mediated
decarboxylation of phenylglyoxylic acid 2 to generate
the intermediate C. In the next step, intermediate C
undergoes a reductive elimination to provide the de-
sired acylated product 3aa and Pd(0) is reoxidized
Representative Experimental Procedure for the
Mono-acylation of 2-Phenyl-4H-benzo[d][1,3]oxazin-
4
-one to 2-(2-Benzoylphenyl)-4H-benzo[d]
[
1,3]oxazin-4-one
II
To
0.5 mmol, 112 mg) and phenylglyoxylic acid (1.5 mmol,
26 mg) in dichloroethane (3 mL) were added AgNO3
0.5 mmol, 85 mg), (NH ) S O (1 mmol, 228 mg) and
a solution of 2-phenyl-4H-benzo[d][1,3]oxazin-4-one
into Pd by AgNO and (NH ) S O , to start the next
3
4
2
2
8
(
2
cycle (Scheme 6).
(
4
2
2
8
Pd(OAc)2 (0.05 mmol, 11 mg). The resulting mixture was
heated at 508C under air for 18 h (TLC). After the reaction
was complete, the mixture was allowed to cool to room tem-
Conclusions
In summary, an efficient and general protocol for the perature (308C) and was extracted with ethyl acetate (3”
decarboxylative selective acylation of 2-aryl-4H- 20 mL). The extract was washed with water (10 mL) and
Adv. Synth. Catal. 2016, 358, 283 – 295
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
289

Biju Majhi et al.
FULL PAPERS
brine (10 mL). The combined organic layer was dried over
anhydrous Na SO and filtered. After removal of the sol-
116.5, 125.4, 127.0, 128.6, 128.7, 129.5, 129.6, 130.0, 130.5,
131.0, 131.8, 131.9 (2C), 136.5, 136.9, 139.9, 141.9, 146.2,
156.6, 159.0, 198.2; IR (KBr): n=1770, 1747, 1724, 1716,
2
4
vent, the residue (crude product) was purified by column
chromatography over silica gel (hexane/ethyl acetate 92:8)
to afford the pure product, 2-(2-benzoylphenyl)-4H-
benzo[d][1,3]oxazin-4-one (Table 2, 3aa) as a white solid;
À1
1668, 1605, 1487 cm ; HR-MS: m/z=342.1127, calcd. for
+
C H NO [M+H] : 342.1125.
2
2
15
3
2-[2-(3-Methoxybenzoyl)-4-methylphenyl]-4H-benzo[d]
1
yield: 139 mg (85%); mp 176–1788C. H NMR (300 MHz,
[1,3]oxazin-4-one (Table 2, 3bc): off white solid; mp 192–
1
CDCl ): d=7.25 (d, J=7.5 Hz, 1H), 7.34–7.45 (m, 4H),
1948C; H NMR (300 MHz, CDCl ): d=2.41 (s, 3H), 3.72
3
3
7
8
.51–7.54 (m, 1H), 7.64–7.70 (m, 3H), 7.78–7.82 (m, 2H),
(s, 3H), 6.78–6.82 (m, 1H), 7.04 (t, J=1.8 Hz, 1H), 7.11–
7.14 (m, 1H), 7.18–7.25 (m, 2H), 7.32–7.38 (m, 2H), 7.64–
.10 (dd, J =7.8 Hz, J =1.2 Hz, 1H), 8.25–8.28 (m, 1H);
1
2
1
3
C NMR (75 MHz, CDCl ): d=116.6, 126.9, 128.6 (3C),
7.69 (m, 1H), 7.85 (d, J=7.5 Hz, 1H), 7.99 (dd, J =7.8 Hz,
3
1
1
3
1
1
1
28.7 (2C), 129.0, 129.1 (2C), 129.2, 130.1, 132.3, 132.9,
J2 =1.5 Hz, 1H), 8.13–8.16 (m, 1H); C NMR (75 MHz,
36.6, 138.0, 141.3, 146.1, 155.6, 159.0, 197.1; IR (KBr): n=
CDCl ): d=22.1, 55.3, 94.2, 111.7, 114.7, 116.1, 117.9, 121.1,
3
À1
746, 1717, 1679, 1616, 1466, 1359, 1146 cm ; HR-MS: m/
123.9, 124.6, 125.4, 130.4, 130.7, 131.7, 135.8, 136.8, 139.2,
+
z=328.0966, calcd. for C H NO [M+H] : 328.0968.
21
13
3
145.2, 145.5, 160.2, 162.4, 165.8, 196.4; IR (neat): n=2926,
À1
This procedure was followed for all the reactions listed in
Table 2, Table 3, Scheme 2, Scheme 3, Scheme 4, and
Scheme 5.
1
740, 1724, 1691, 1606, 1487, 1365, 1215 cm ; anal. calcd.
ror C H NO : C 74.38, H 4.61, N 3.77; found C 74.36, H
2
3
17
4
4
.65, N 3.79%.
-[4-Methyl-2-(2-methylbenzoyl)phenyl]-4H-benzo[d]
1,3]oxazin-4-one (Table 2, 3bb): white solid; mp 101–
2
[
1
Representative Experimental Procedure for the Bis-
acylation of 2-Phenyl-4H-benzo[d][1,3]oxazin-4-one
to {2-(4-Oxo-4H-benzo[d][1,3]oxazin-2-yl)-1,3-
phenylene}bis(phenylmethanone)
1
038C; H NMR (300 MHz, CDCl ): d=2.48 (s, 3H), 2.74
3
(
4
s, 3H), 7.01–7.06 (m, 1H), 7.17–7.28 (m, 3H), 7.35–7.45 (m,
H), 7.67–7.73 (m, 1H), 8.02–8.10 (m, 2H); C NMR
13
(
75 MHz, CDCl ): d=21.7, 22.0, 116.5, 125.4, 126.9, 127.0,
3
1
1
28.4, 128.5, 129.5, 130.1, 131.0, 131.2, 131.7, 131.9, 136.5,
To
0.5 mmol, 112 mg) and phenylglyoxylic acid (2.0 mmol,
01 mg) in dichloroethane (3 mL) were added AgOTf
1.0 mmol, 257 mg), (NH ) S O (1 mmol, 228 mg) and
a solution of 2-phenyl-4H-benzo[d][1,3]oxazin-4-one
36.9, 139.9, 142.1, 142.9, 146.3, 156.5, 159.1, 198.5; IR
(
3
(
À1
(KBr): n=1774, 1761, 1663, 1601, 1248, 1003 cm ; HR-MS:
+
m/z=356.1283, calcd. for C H NO [M+H] : 356.1281.
23 17
3
4
2
2
8
2
-[2-(4-Fluorobenzoyl)phenyl]-4H-benzo[d][1,3]oxazin-4-
Pd(OAc) (0.075 mmol, 17 mg). The resulting mixture was
2
1
one (Table 2, 3ae): light yellow gummy liquid; H NMR
300 MHz, CDCl ): d=6.97–7.03 (m, 2H), 7.24–7.29 (m,
heated at 608C under air for 24 h (TLC). After the reaction
was complete, the mixture was allowed to cool to room tem-
perature and was extracted with ethyl acetate (3”20 mL).
The extract was washed with water (10 mL) and brine
(
1
3
H), 7.49–7.54 (m, 3H), 7.59–7.65 (m, 2H), 7.67–7.73 (m,
13
1H), 7.98–8.02 (m, 2H), 8.15 (d, J=8.1 Hz, 1H); C NMR
(75 MHz, CDCl ): d=116.2, 116.4, 116.7, 121.3, 123.6, 125.0,
125.8, 127.8, 127.9, 129.3, 130.9, 131.0, 134.3, 136.1, 136.5,
144.9, 161.7, 164.0 (d, JC,F =255.9 Hz, 1C), 196.4; IR (neat):
n=1726, 1691, 1676, 1605, 1485, 1367, 1217 cm ; anal.
(10 mL). The combined organic layer was dried over anhy-
3
drous Na SO and filtered. After removal of the solvent, the
2
4
residue (crude product) was purified by column chromatog-
raphy over silica gel (hexane/ethyl acetate 89:11) to afford
the pure product, [2-(4-oxo-4H-benzo[d][1,3]oxazin-2-yl)-
À1
calcd. for C21
H12FNO : C 73.04, H 3.50, N 4.06, found C
3
1
,3-phenylene}bis(phenylmethanone) (Table 4, 4aa) as
73.06, H 3.55, N 4.05%.
2-[2-(4-Chlorobenzoyl)phenyl]-4H-benzo[d][1,3]oxazin-4-
one (Table 2, 3af): off white solid; mp 132–1348C; H NMR
1
a white solid; yield: 168 mg (78%); mp 258–2608C. H NMR
300 MHz, CDCl ): d=7.29–7.37 (m, 2H), 7.39–7.45 (m,
1
(
3
2
1
1
1
H), 7.50–7.60 (m, 5H), 7.62–7.66 (m, 2H), 7.83–7.85 (m,
(300 MHz, CDCl ): d=7.27–7.31 (m, 3H), 7.45–7.51 (m,
3
H), 7.97–8.05 (m, 4H), 8.18 (dd, J =7.8 Hz, J =1.5 Hz,
3H), 7.60–7.65 (m, 2H), 7.68–7.73 (m, 1H), 7.98–8.02 (m,
1
2
13
13
H); C NMR (75 MHz, CDCl ): d=95.5, 118.4, 123.8,
2H), 8.15 (dd, J =8.1 Hz, J =0.3 Hz, 1H); C NMR
3
1
2
25.1, 125.3, 126.5 (2C), 128.7 (2C), 129.4 (2C), 129.9, 130.6
(75 MHz, CDCl ): d=94.1, 116.1, 121.3, 123.6, 125.0, 125.8,
3
(2C), 130.9, 132.5, 133.0, 133.4, 134.3, 134.4, 135.8, 136.6,
127.2 (2C), 129.3, 129.7 (2C), 130.9, 131.0, 134.4, 136.1,
1
1
36.8, 145.1, 162.0, 165.2, 193.9; IR (neat): n=1752, 1728,
136.2, 136.5, 144.7, 162.2, 165.7, 196.6; IR (neat): n=3020,
À1
À1
673, 1596, 1466, 1216 cm ; HR-MS: m/z=432.1231, calcd.
1724, 1693, 1678, 1606, 1485, 1367, 1217 cm ; HR-MS:
+
+
for C H NO [M+H] : 432.1230.
m/z=362.0577, calcd. Ffor C H ClNO [M+H] : 362.0578.
28
18
4
21 13
3
This procedure was followed for all the reactions listed in
Table 4. All the products were obtained in high purity. All
the products are unknown and characterized properly by
spectroscopic data (IR, H NMR, C NMR, HR-MS and el-
emental analysis).
2-[2-(4-Bromobenzoyl)phenyl]-4H-benzo[d][1,3]oxazin-4-
one (Table 2, 3ag): white solid; mp 142–1448C; H NMR
1
(300 MHz, CDCl ): d=7.22–7.26 (m, 1H), 7.45–7.53 (m,
3
1
13
4H), 7.65–7.70 (m, 5H), 8.13 (dd, J =7.8 Hz, J =1.2 Hz,
1
2
1
3
1H), 8.26–8.29 (m, 1H); C NMR (75 MHz, CDCl ): d=
3
1
1
1
16.7, 126.9, 128.1, 128.5, 128.7, 128.8, 128.9, 129.3, 130.3,
30.6 (2C), 131.9 (2C), 132.4, 136.7, 136.8, 140.8, 145.9,
Characterization Data of all Products
55.4, 158.9, 196.0; IR (KBr): n=1749, 1732, 1716, 1672,
À1
2
-[2-(2-Methylbenzoyl)phenyl]-4H-benzo[d][1,3]oxazin-4-
1601, 1487, 1369 cm ; HR-MS: m/z=406.0078, calcd. for
C
1
+
one (Table 2, 3ab): white solid; mp 98–1008C; H NMR
300 MHz, CDCl ): d=2.69 (s, 3H), 7.04 (t, J=8.1 Hz, 1H),
21
H12BrNO
3
[M+H] : 406.0073.
(
2-[2-(4-Iodobenzoyl)phenyl]-4H-benzo[d][1,3]oxazin-4-
3
1
7
8
.15–7.25 (m, 3H), 7.39–7.46 (m, 2H), 7.57–7.74 (m, 4H),
.07–8.12 (m, 2H); C NMR (75 MHz, CDCl ): d=21.9,
one (Table 2, 3ah): white solid; mp 186–1888C; H NMR
(300 MHz, CDCl ): d=7.24–7.27 (m, 3H), 7.47–7.52 (m,
13
3
3
2
90
asc.wiley-vch.de
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2016, 358, 283 – 295

FULL PAPERS
Palladium-Catalyzed Decarboxylative Selective Acylation
À1
+
2
7
1
1
1
1
H), 7.58–7.72 (m, 5H), 7.96–8.01 (m, 1H), 8.13 (d, J=
1371 cm ; HR-MS: m/z=400.0953, calcd. for C H NO
25
15
3
13
.8 Hz, 1H); C NMR (75 MHz, CDCl ): d=96.0, 116.1,
[M+Na] : 400.0944.
3
21.2, 123.6, 125.0, 125.8, 127.5 (2C), 130.4, 130.9, 131.0,
34.3, 136.1, 137.4, 137.9, 138.5 (2C), 144.5, 162.1, 165.6,
96.2; IR (neat): n=1751, 1732, 1718, 1670, 1602, 1485,
2-[2-(2-Naphthoyl)-4-methylphenyl]-4H-benzo[d]
[1,3]oxazin-4-one (Table 2, 3bi): white solid; mp 121–1238C;
H NMR (300 MHz, CDCl ): d=2.56 (s, 3H), 7.24 (d, J=
8.1 Hz, 1H), 7.39 (d, J=8.4 Hz, 1H), 7.48–7.66 (m, 5H),
1
3
À1
+
369 cm ; HR-MS: m/z=453.9937, calcd. for C H INO
21
12
3
[M+H] : 453.9935.
7.83–7.87 (m, 4H), 7.91–7.97 (m, 1H), 8.08 (dd, J =7.8 Hz,
1
2
-[2-(4-Acetylbenzoyl)phenyl]-4H-benzo[d][1,3]oxazin-4-
J =1.2 Hz, 1H), 8.13–8.18 (m, 2H), 8.26 (d, J=7.8 Hz, 1H);
2
13
1
one (Table 2, 3am): white solid; mp 212–2148C; H NMR
300 MHz, CDCl ): d=2.51 (s, 3H), 7.22–7.27 (m, 1H),
.48–7.51 (m, 1H), 7.60–7.70 (m, 5H), 7.87–7.90 (m, 2H),
.97–8.01 (m, 2H), 8.16 (d, J=7.8 Hz, 1H); C NMR
75 MHz, CDCl ): d=26.7, 116.0, 121.2, 123.6, 125.1, 125.8,
26.1 (2C), 129.3 (2C), 129.4, 130.9, 131.2, 134.4, 136.1,
36.5, 138.1, 142.4, 144.3, 162.1, 165.6, 194.7, 197.1; IR
KBr): n=1732, 1691, 1603, 1483, 1363, 1230 cm ; HR-MS:
m/z=370.1072, calcd. for C H NO [M+H] : 370.1074.
C NMR (75 MHz, CDCl ): d=21.8, 116.6, 124.6, 125.5,
3
(
7
7
(
1
1
126.7, 126.8, 127.9, 128.3, 128.4, 128.5, 128.6, 129.2, 129.3,
129.6, 130.7, 131.0, 132.2, 132.5, 135.5, 136.5, 141.6, 143.3,
146.2, 155.5, 159.1, 197.4; IR (neat): n=2926, 1767, 1740,
3
13
À1
1668, 1626, 1508, 1254 cm ; HR-MS: m/z=392.1284, calcd.
3
+
for C H NO [M+H] : 392.1281.
2
6
18
3
2-[2-(1-Naphthoyl)-4-methylphenyl]-4H-benzo[d]
À1
(
[1,3]oxazin-4-one (Table 2, 3bj): white solid; mp 112–1148C;
+
1
H NMR (300 MHz, CDCl ): d=2.50 (s, 3H), 6.90–6.93 (m,
23
16
4
3
4
-[2-(4-Oxo-4H-benzo[d][1,3]oxazin-2-yl)benzoyl]benzo-
1H), 7.22–7.29 (m, 2H), 7.39–7.48 (m, 4H), 7.51–7.57 (m,
1
nitrile (Table 2, 3an): white solid; mp 144–1468C; H NMR
300 MHz, CDCl ): d=7.25–7.31 (m, 1H), 7.48–7.50 (m,
H), 7.62–7.73 (m, 7H), 7.99–8.03 (m, 2H), 8.16 (d, J=
1H), 7.70–7.84 (m, 3H), 7.96 (dd, J =7.8 Hz, J =1.5 Hz,
1
2
(
1H), 8.08 (d, J=7.8 Hz, 1H), 9.28 (d, J=8.7 Hz, 1H);
3
1
3
1
8
1
1
1
1
C NMR (75 MHz, CDCl ): d=21.7, 116.3, 124.1, 126.6,
3
13
.1 Hz, 1H); C NMR (75 MHz, CDCl ): d=93.7, 113.9,
126.8, 126.9, 127.1, 128.1, 128.2 (2C), 128.5, 129.4, 130.5,
130.6, 131.1 (2C), 133.3, 134.0, 135.0, 136.2, 142.5, 142.9,
145.9, 155.9, 159.1, 198.6; IR (KBr): n=1761, 1716, 1670,
3
15.8, 117.8, 121.3, 123.6, 125.2, 126.0, 126.6 (2C), 129.3,
30.9, 131.4, 133.3 (2C), 134.5, 136.3, 142.8, 143.9, 161.8,
65.5, 197.2; IR (neat): n=2926, 2233, 1751, 1738, 1726,
À1
1620, 1603, 1250 cm ; anal. calcd. for C H NO : C 79.78,
2
6
17
3
À1
711, 1691, 1606, 1485, 1367, 1217 cm ; anal. calcd. for
H 4.38, N 3.58; found C 79.80, H 4.39, N 3.56%.
C H N O : C 74.99, H 3.43, N 7.95; C 74.95, H 3.45, N
2-[2-(2-Fluorobenzoyl)-4-methylphenyl]-4H-benzo[d]
2
2
12
2
3
7
.93%.
[1,3]oxazin-4-one (Table 2, 3bk): colourless gummy liquid;
1
2-[2-(4-Nitrobenzoyl)phenyl]-4H-benzo[d][1,3]oxazin-4-
H NMR (300 MHz, CDCl ): d=2.42 (s, 3H), 6.88–6.95 (m,
3
one (Table 2, 3ao): light yellow solid; mp 241–2438C;
1H), 7.12–7.27 (m, 2H), 7.28–7.33 (m, 2H), 7.38–7.41 (m,
1H), 7.63–7.69 (m, 1H), 7.73–7.79 (m, 1H), 7.87 (d, J=
7.8 Hz, 1H), 8.00 (dd, J =8.1 Hz, J =1.5 Hz, 1H), 8.10–8.12
1
H NMR (300 MHz, CDCl ): d=7.23–7.28 (m, 1H), 7.47–
3
7
.50 (m, 1H), 7.61–7.65 (m, 2H), 7.70–7.76 (m, 3H), 7.97
1
2
13
13
(m, 2H), 8.13–8.18 (m, 3H); C NMR (75 MHz, CDCl ):
(m, 1H); C NMR (75 MHz, CDCl ): d=22.1, 115.8, 117.3
3
3
d=93.7, 115.7, 121.3, 123.6, 124.6 (2C), 125.3, 126.1, 127.0
2C), 129.3, 130.9, 131.4, 134.5, 136.3, 143.7, 144.6, 148.7,
(d, JC,F =21.7 Hz, 1C), 121.1, 123.9, 124.5, 124.7 (d, JC,F =
(
3.7 Hz, 1C), 125.0 (d, JC,F =9 Hz, 1C), 125.4, 127.6, 128.7,
130.6, 131.8 (d, JC,F =8.3 Hz, 1C), 132.0, 136.0, 136.7, 143.8,
145.4, 159.4 (d, JC,F =250.5 Hz, 1C), 162.5, 165.3, 196.6; IR
1
1
61.7, 165.4, 196.8; IR (neat): n=3018, 2928, 1728, 1691,
678, 1606, 1525, 1466, 1360 cm ; anal. calcd. for
À1
À1
C H N O : C 67.74, H 3.25, N 7.52; found : C 67.77, H
(KBr): n=1775, 1730, 1672, 1622, 1598, 1242, 1151 cm ;
2
1
12
2
5
3.27, N 7.49%.
anal. calcd. for C H FNO : C 73.53, H 3.93, N 3.90; found
2
2
14
3
2
-[2-(2-Naphthoyl)phenyl]-4H-benzo[d][1,3]oxazin-4-one
: C 73.55, H 3.96, N 3.88%.
2-[2-(2-Chlorobenzoyl)phenyl]-4H-benzo[d][1,3]oxazin-4-
one (Table 2, 3al): white solid; mp 132–1348C; H NMR
1
(
(
Table 2, 3ai): off white solid; mp 222–2248C; H NMR
300 MHz, CDCl ): d=7.21–7.24 (m, 1H), 7.34–7.39 (m,
1
3
1
2
8
H), 7.46–7.51 (m, 1H), 7.54–7.64 (m, 3H), 7.69–7.73 (m,
(300 MHz, CDCl ): d=7.18–7.27 (m, 3H), 7.33–7.40 (m,
3
H), 7.81 (t, J=7.2 Hz, 2H), 7.88 (d, J=8.4 Hz, 1H), 8.04–
2H), 7.59–7.70 (m, 3H), 7.98–8.01 (m, 2H), 8.05–8.09 (m,
13
13
.12 (m, 3H), 8.30–8.34 (m, 1H); C NMR (75 MHz,
2H); C NMR (75 MHz, CDCl ): d=116.2, 121.4, 123.6,
3
CDCl ): d=116.6, 124.6, 126.8, 127.0, 127.9, 128.51, 128.54,
124.5, 125.8, 127.6, 129.8, 130.4, 131.1, 131.2, 132.5, 133.7,
3
1
1
28.6 (2C), 128.7, 128.9, 129.3, 129.6, 130.1, 131.1, 132.3,
32.5, 135.5, 135.6, 136.5, 141.5, 146.0, 155.5, 159.0, 197.1; IR
134.0, 135.9, 136.3, 142.5, 162.7, 165.9, 191.9; IR (KBr): n=
À1
1751, 1722, 1682, 1604, 1485, 1367 cm ; HR-MS: m/z=
+
(neat): n=3018, 2928, 1745, 1728, 1715, 1693, 1668,
362.0577, calcd. for C H ClNO [M+H] : 362.0578.
2
1
13
3
À1
1
487 cm ; HR-MS: m/z=378.1126, calcd. for C H NO
2-(2-Benzoyl-4-methylphenyl)-4H-benzo[d][1,3]oxazin-4-
2
1
15
3
+
1
[M+H] : 378.1125.
one (Table 3, 3ba): white solid; mp 191–1938C; H NMR
2
-[2-(1-Naphthoyl)phenyl]-4H-benzo[d][1,3]oxazin-4-one
(300 MHz, CDCl ): d=2.45 (s, 3H), 7.18 (d, J=7.8 Hz, 1H),
3
1
(
(
(
(
7
9
1
1
1
2
Table 2, 3aj): light brown solid; mp 132–1348C; H NMR
300 MHz, CDCl ): d=6.99 (d, J=8.1 Hz, 1H), 7.24–7.33
m, 2H), 7.43–7.49 (m, 2H), 7.52–7.57 (m, 1H), 7.68–7.73
7.28–7.43 (m, 6H), 7.60 (t, J=8.1 Hz, 1H), 7.77–7.80 (m,
2H), 8.03 (d, J=7.8 Hz, 1H), 8.12 (d, J=8.1 Hz, 1H);
3
1
3
C NMR (75 MHz, CDCl ): d=21.6, 116.4, 125.9, 126.6,
3
m, 4H), 7.79 (d, J=7.1 Hz, 1H), 7.85 (d, J=8.1 Hz, 1H),
128.30, 128.32, 128.4 (2C), 128.9 (2C), 129.0, 129.1, 130.6,
132.7, 136.4, 137.9, 141.3, 143.2, 146.0, 155.4, 158.9, 197.1; IR
.99 (dd, J =7.8 Hz, J =1.5 Hz, 1H), 8.17–8.20 (m, 1H),
1 2
13
À1
.23 (d, J=8.4 Hz, 1H); C NMR (75 MHz, CDCl ): d=
(KBr): n=1745, 1717, 1680, 1603, 1485, 1360 cm ; HR-MS :
3
+
16.4, 124.1, 126.7, 126.8, 127.2, 128.2, 128.3, 128.4, 128.5,
29.5, 129.9, 130.0, 130.5, 130.6, 131.1, 132.0, 133.4, 134.0,
35.0, 136.3, 142.3, 145.8, 156.0, 159.0, 198.3; IR (neat): n=
926, 2854, 1767, 1732, 1715, 1693, 1651, 1645, 1574,
m/z=342.1124, calcd. for C H NO [M+H] : 342.1125.
2
2
15
3
2-(2-Benzoyl-4-methoxyphenyl)-4H-benzo[d][1,3]oxazin-
1
4-one (Table 3, 3ca): white solid; mp 236–2388C; H NMR
(300 MHz, CDCl ): d=3.83 (s, 3H), 6.94 (s, 1H), 7.04–7.13
3
Adv. Synth. Catal. 2016, 358, 283 – 295
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
291

Biju Majhi et al.
FULL PAPERS
+
(m, 2H), 7.25–7.39 (m, 4H), 7.55 (t, J=7.5 Hz, 1H), 7.78 (d,
HR-MS: m/z=362.0578, calcd. for C H ClNO [M+H] :
21 13 3
J=7.8 Hz, 2H), 7.98 (d, J=7.8 Hz, 1H), 8.16 (d, J=8.7 Hz,
362.0578.
13
1
1
1
1
1
H); C NMR (75 MHz, CDCl ): d=55.7, 114.0, 114.9,
2-(2-Benzoyl-4-methylphenyl)-7-chloro-4H-benzo[d]
3
16.1, 120.5, 126.3, 127.9, 128.2, 128.4 (2C), 128.8 (2C),
30.9, 132.7, 136.3, 137.6, 143.3, 146.1, 155.1, 158.9, 162.6,
96.4; IR (KBr): n=1720, 1682, 1620, 1605, 1487, 1348,
[1,3]oxazin-4-one (Table 3, 3ja): white solid: mp 173–1758C;
1
H NMR (300 MHz, CDCl
): d=2.47 (s, 3H), 7.16 (s, 1H),
3
7.29–7.46 (m, 6H), 7.77–7.80 (m, 2H), 7.97 (dd, J
=8.4 Hz,
C NMR
1
À1
13
209, 1130 cm ; anal. calcd. for C H NO : C 73.94, H 4.23,
J
2
=1.2 Hz, 1H), 8.12 (d, J=8.1 Hz, 1H);
(75 MHz, CDCl ): d=21.7, 114.8, 125.5, 126.4, 128.5 (2C),
128.9, 129.0 (2C), 129.2, 129.3, 129.7, 130.6, 132.9, 137.8,
22
15
4
N 3.92; found: C 73.97, H 4.26, N 3.89%.
-[2-Benzoyl-4-(tert-butyl)phenyl]-4H-benzo[d]
1,3]oxazin-4-one (Table 3, 3da): light yellow solid; mp 203–
3
2
1
1
3
41.5, 142.8, 143.7, 147.1, 156.8, 158.2, 196.9; IR (KBr): n=
755, 1724, 1670, 1595, 1211, 1011 cm ; HR-MS: m/z=
76.0732, calcd. for C H ClNO [M+H] 376.0735.
[
À1
1
2
7
7
1
058C; H NMR (300 MHz, CDCl ): d=1.37(s, 9H), 7.20–
3
+
.23 (m, 1H), 7.28–7.45 (m, 4H), 7.50–7.53 (m, 1H), 7.59–
.67 (m, 2H), 7.79–7.82 (m, 2H), 8.06 (dd, J =8.1 Hz, J =
.2 Hz, 1H), 8.18 (d, J=8.1 Hz, 1H); C NMR (75 MHz,
22 15
3
2-(2-Benzoyl-6-chlorophenyl)-4H-benzo[d][1,3]oxazin-4-
1
2
1
13
one (Table 3, 3ak): white solid; mp 156–1588C, H NMR
(
(
(
300 MHz, CDCl ): d=7.24 (d, J=8.7 Hz, 1H), 7.36–7.45
m, 3H), 7.50–7.53 (m, 1H), 7.63–7.69 (m, 3H), 7.78–7.81
m, 2H), 8.09 (dd, J =8.1 Hz, J =1.5 Hz, 1H), 8.24–8.27
CDCl ): d=31.1 (3C), 35.4, 116.4, 125.6, 126.0, 126.7, 127.0,
3
3
1
1
2
28.3, 128.4, 128.5 (2C), 128.9, 129.0 (2C), 132.7, 136.4,
38.1, 141.1, 146.1, 155.5, 156.2, 159.1, 197.5; IR (neat): n=
1
2
1
3
À1
(m, 1H); C NMR (75 MHz, CDCl ): d=116.6, 126.9, 128.5
(2C), 128.7 (2C), 128.9, 129.1 (2C), 129.2, 129.4, 130.1,
962, 2926, 1747, 1728, 1715, 1693, 1668, 1487, 1362 cm ;
3
+
HR-MS: m/z=384.1592, calcd. for C H NO [M+H] :
25
22
3
132.2, 132.9, 136.5, 137.9, 141.3, 146.0, 155.5, 159.0, 197.0; IR
384.1594.
À1
(KBr): n=1749, 1732, 1699, 1659, 1487, 1360 cm ; HR-MS:
2
-(2-Benzoyl-4-fluorophenyl)-4H-benzo[d][1,3]oxazin-4-
+
1
m/z=362.0577, calcd. for C H ClNO [M+H] : 362.0578.
21 13 3
one (Table 3, 3ea): white solid; mp 138–1408C; H NMR
300 MHz, CDCl ): d=7.18–7.22 (m, 2H), 7.29–7.45 (m,
2-(2-Benzoylphenyl)-6,7-dimethoxy-4H-benzo[d]
(
3
[
1,3]oxazin-4-one (Table 3, 3la): white solid; mp=189–
5
7
H), 7.62–7.67 (m, 1H), 7.77–7.81 (m, 2H), 8.07 (dd, J =
1
1
13
1918C; H NMR (300 MHz, CDCl
): d=3.90 (s, 3H), 3.91
3
.8 Hz, J =1.2 Hz, 1H), 8.27 (q, J=5.4 Hz, 1H); C NMR
2
(s, 3H), 6.62 (s, 1H), 7.31–7.43 (m, 4H), 7.51–7.53 (m, 1H),
(
75 MHz, CDCl ): d=116.2 (d, J =23.3 Hz, 1C), 116.7 (d,
3 C,F
7
.64–7.67 (m, 2H), 7.76–7.79 (m, 2H), 8.20–8.23 (m, 1H);
C NMR (75 MHz, CDCl ): d=56.4, 56.5, 107.5, 107.6,
JC,F =32.3 Hz, 1C), 125.7, 126.8, 128.5, 128.6 (2C), 128.7,
13
3
1
1
29.1 (2C), 129.5, 131.6, 131.7, 133.2, 136.6, 137.3, 145.9,
109.2, 128.5 (2C), 128.7, 128.8, 128.9 (2C), 129.2, 130.1,
54.6, 158.8, 164.8 (d, JC,F =255.7 Hz, 1C), 195.2; IR (KBr):
À1
131.9, 132.8, 138.1, 140.9, 142.4, 150.0, 154.9, 156.3, 158.9,
n=1747, 1730, 1680, 1605, 1485, 1369, 1269 cm ; HR-MS:
m/z=346.0877, calcd. for C H FNO [M+H] : 346.0874.
À1
197.1; IR (KBr): n=1751, 1715, 1668, 1603, 1510, 1288 cm ;
+
21
12
3
anal. calcd. for C H NO : C 71.31, H 4.42, N 3.62; found:
2
3
17
5
2
-(2-Benzoyl-4-chlorophenyl)-4H-benzo[d][1,3]oxazin-4-
C 71.35, H 4.45, N 3.60%.
-(2-Benzoyl-4-methylphenyl)-6,7-dimethoxy-4H-benzo[d]
1,3]oxazin-4-one (Table 3, 3ma): light yellow solid; mp 203–
1
one (Table 3, 3fa): white solid; mp 168–1708C, H NMR
2
(
300 MHz, CDCl ): d=7.22 (dd, J =8.1 Hz, J =0.6 Hz,
3
1
2
[
2
1
2
1
H), 7.38–7.45 (m, 3H), 7.47–7.50 (m, 3H), 7.63–7.71 (m,
1
058C, H NMR (300 MHz, CDCl ): d=2.46 (s, 3H), 3.87 (s,
3
H), 7.80–7.84 (m, 2H), 8.12 (dd, J =8.1 Hz, J =1.5 Hz,
1
2
3
H), 3.89 (s, 3H), 6.58 (s, 1H), 7.30–7.37 (m, 4H), 7.39–7.44
13
H), 8.23 (d, J=8.4 Hz, 1H); C NMR (75 MHz, CDCl ):
3
(m, 2H), 7.76–7.79 (m, 2H), 8.10 (d, J=8.1 Hz, 1H);
d=116.6, 126.9, 127.2, 128.6, 128.7 (2C), 128.8, 128.9, 129.1
2C), 130.2, 130.5, 133.3, 136.7, 137.4, 138.9, 142.9, 145.9,
13
C NMR (75 MHz, CDCl ): d=21.6, 55.4, 56.4, 107.4, 107.5,
3
(
1
1
1
1
09.0, 126.2, 128.4 (2C), 128.7, 128.9 (2C), 129.2, 130.7,
32.7, 138.1, 140.9, 142.5, 142.9, 149.7, 154.9, 156.2, 159.0,
97.3; IR (KBr): n=1747, 1666, 1618, 1603, 1502, 1290,
1
1
54.6, 158.7, 195.3; IR (neat): n=2924, 1728, 1695, 1678,
À1
605, 1487, 1365 cm ; HR-MS: m/z=362.0577, calcd. For
+
C H ClNO [M+H] : 362.057.
À1
2
1
13
3
248, 1026 cm ; HR-MS: m/z=402.1335, calcd. for
2
-(2-Benzoyl-4-bromophenyl)-4H-benzo[d][1,3]oxazin-4-
+
C H NO [M+H] : 402.1336.
2
4
20
5
1
one (Table 3, 3ga): white solid; mp 242–2448C; H NMR
300 MHz, CDCl ): d=7.18–7.21 (m, 1H), 7.35–7.50 (m,
2
-[2-(Thiophene-3-carbonyl)phenyl]-4H-benzo[d]
[1,3]oxazin-4-one (Scheme 2, 3ap): off white gummy liquid;
1
(
3
4
7
H), 7.62–7.65 (m, 2H), 7.76–7.81 (m, 3H), 8.07 (dd, J =
1
H NMR (300 MHz, CDCl ): d=6.91 (dd, J =4.8 Hz, J =
3 1 2
13
.8 Hz, J =1.5 Hz, 1H), 8.12 (d, J=8.4 Hz, 1H); C NMR
2
1.2 Hz, 1H), 7.21–7.29 (m, 2H), 7.55–7.72 (m, 5H), 7.97–
8.05 (m, 2H), 8.12–8.15 (m, 1H); C NMR (75 MHz,
(
(
75 MHz, CDCl ): d=116.5, 126.9, 127.3, 127.6, 128.6, 128.7
2C), 128.9, 129.1 (2C), 130.5, 131.6, 133.1, 133.2, 136.6,
13
3
CDCl ): d=93.0, 116.1, 121.1, 123.6, 124.9, 125.1, 125.7,
3
1
1
4
37.4, 142.8, 145.8, 154.7, 158.6, 195.2; IR (KBr): n=1745,
1
1
28.0, 129.4, 130.8, 131.0, 134.2, 135.9, 136.6, 139.1, 144.3,
62.5, 165.4, 191.5; IR (neat): n=2959, 1726, 1680, 1607,
À1
718, 1676, 1603, 1483, 1360, 1246 cm ; HR-MS: m/z=
+
À1
+
06.0078, calcd. for C H BrNO [M+H] : 406.0073.
21
12
3
1487, 1364, 1253 cm ; HR.MS: m/z=334.0532, calcd. for
2
-(2-Benzoylphenyl)-7-chloro-4H-benzo[d][1,3]oxazin-4-
C H NO S [M+H] : 334.0532.
1
9
12
3
1
one (Table 3, 3ia): white solid; mp 161–1638C; H NMR
2-[2-(Furan-2-carbonyl)phenyl]-4H-benzo[d][1,3]oxazin-
4-one (Scheme 2, 3aq): light yellow gummy liquid; H NMR
(300 MHz, CDCl ): d=6.43 (q, J=1.8 Hz, 1H), 6.99–7.00
(m, 1H), 7.40 (d, J=8.1 Hz, 1H), 7.44–7.51 (m, 2H), 7.57–
7.60 (m, 1H), 7.65–7.75 (m, 3H), 8.15 (dd, J =7.8 Hz, J =
1
(
(
(
300 MHz, CDCl ): d=7.22 (d, J=1.8 Hz, 1H), 7.35–7.41
m, 3H), 7.46–7.52 (m, 2H), 7.65–7.70 (m, 2H), 7.78–7.81
3
3
m, 2H), 8.01 (d, J=8.7 Hz, 1H), 8.23–8.26 (m, 1H);
1
3
C NMR (75 MHz, CDCl ): d=114.9, 125.6, 126.6, 128.6
3
1
2
1
3
(2C), 128.7, 129.1 (2C), 129.2, 129.3, 129.8, 130.1, 132.5,
1.2 Hz, 1H), 8.21–8.24 (m, 1H);
C NMR (75 MHz,
1
33.1, 137.7, 141.5, 142.9, 147.1, 156.9, 158.1, 196.8; IR
CDCl ): d=112.4, 116.6, 118.4, 127.2, 128.6, 128.7, 128.8,
129.3, 129.4, 130.6, 132.1, 136.7, 139.9, 146.2, 146.8, 153.2,
3
À1
(KBr): n=1761, 1732, 1668, 1626, 1597, 1568, 1269 cm ;
2
92
asc.wiley-vch.de
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2016, 358, 283 – 295

FULL PAPERS
Palladium-Catalyzed Decarboxylative Selective Acylation
1
1
55.9, 159.1, 184.3; IR (neat): n=1771, 1723, 1670, 1601,
6.9 Hz, 2H), 7.43–7.46 (m, 3H), 7.61–7.66 (m, 2H), 7.75–
À1
486, 1247 cm ; anal. calcd. for C H NO : C 71.92, H 3.49,
7.78 (m, 2H), 8.07 (d, J=7.8 Hz, 1H), 8.22 (d, J=1.8 Hz,
19
11
4
1
3
N 4.41, found C 71.93, H 3.51, N 4.38%.
-(3-Benzoylthiophen-2-yl)-4H-benzo[d][1,3]oxazin-4-one
1H); C NMR (75 MHz, CDCl ): d=116.5, 126.9, 128.6
3
2
(2C), 129.0 (3C), 129.1, 130.0, 130.6, 132.1, 133.1, 136.3,
1
(Scheme 2, 3ra): colourless gummy liquid; H NMR
136.6, 138.6, 139.4, 145.7, 154.3, 158.5, 195.8; IR (KBr): n=
À1
(300 MHz, CDCl ): d=7.25–7.32 (m, 2H), 7.38–7.45 (m,
1774, 1672, 1622, 1599, 1261 cm ; HR-MS: m/z=362.0578,
3
+
3
2
H), 7.50–7.56 (m, 1H), 7.66–7.69 (m, 2H), 7.87–7.90 (m,
calcd. for C H ClNO [M+H] : 362.0578.
2
1
13
3
13
H), 8.06–8.09 (dd, J =7.8 Hz, J =1.5 Hz, 1H); C NMR
2-(2-Benzoyl-5-methylphenyl)-4H-benzo[d][1,3]oxazin-4-
1
2
1
(75 MHz, CDCl ): d=116.5, 127.0, 128.4, 128.6, 128.7 (2C),
one (Scheme 4, 3pa): white solid; mp 198–2008C; H NMR
3
1
1
1
28.8, 129.4 (3C), 131.4, 133.5, 136.6, 137.6, 144.5, 146.5,
(300 MHz, CDCl ): d=2.47 (s, 3H), 7.23–7.31 (m, 4H),
7.39–7.41 (m, 2H), 7.49–7.52 (m, 2H), 7.65–7.71 (m, 1H),
3
52.5, 158.2, 193.3; IR (KBr): n=1761, 1670, 1601, 1416,
À1
267, 1038 cm ; HR.MS: m/z=334.0534, calcd. for
7.78 (d, J=0.9 Hz, 1H), 7.99 (dd, J =7.8 Hz, J =1.5 Hz,
1
2
+
13
C H NO S [M+H] : 334.0532.
1H), 8.14–8.17 (m, 1H); C NMR (75 MHz, CDCl ): d=
1
9
12
3
3
2
-(2-Acetylphenyl)-4H-benzo[d][1,3]oxazin-4-one
21.6, 94.5, 116.3, 121.2, 123.4, 125.1, 125.5, 125.7 (2C), 129.3
(2C), 129.6, 130.8, 135.1, 135.9, 136.8, 137.8, 141.4, 142.6,
162.7, 166.0, 196.2; IR (neat): n=3020, 2399, 1755, 1724,
1
(
(
Scheme 3, 3ar): white solid; mp 142–1448C; H NMR
300 MHz, CDCl ): d=1.95 (s, 3H), 7.34–7.39 (m, 1H),
.62–7.67 (m, 1H), 7.72–7.79 (m, 3H), 7.95–7.97 (m, 1H),
.10–8.17 (m, 2H); C NMR (75 MHz, CDCl ): d=24.5,
2.7, 115.7, 121.5, 122.7, 124.8, 125.7, 130.8, 131.1, 134.1,
35.9, 136.3, 144.3, 162.1, 164.9, 203.2; IR (KBr): n=1736,
726, 1678, 1605, 1489, 1373, 1240 cm ; anal. calcd. for
3
À1
7
8
9
1
1
1709, 1676, 1661, 1597, 1217 cm ; HR-MS : m/z=342.1124,
13
+
calcd. for C H NO [M+H] : 342.1125.
3
22 15
3
2-(2-Benzoyl-5-methoxyphenyl)-4H-benzo[d][1,3]oxazin-
4-one (Scheme 4, 3qa): white solid; mp 168–1708C;
À1
1
H NMR (300 MHz, CDCl ): d=3.95 (s, 3H), 7.17 (dd, J =
3
1
C H NO : C 72.45, H 4.18, N 5.28; found: C 72.42, H 4.20,
8.4 Hz, J =2.7 Hz, 1H), 7.29–7.34 (m, 3H), 7.37–7.45 (m,
1
6
11
3
2
N 5.30%.
-(2-Isobutyrylphenyl)-4H-benzo[d][1,3]oxazin-4-one
2H), 7.51 (d, J=8.4 Hz, 1H), 7.65–7.68 (m, 2H), 7.75–7.78
1
3
2
(m, 2H), 8.08 (dd, J =7.5 Hz, J =1.2 Hz, 1H); C NMR
1 2
1
(Scheme 3, 3as): colourless gummy liquid; H NMR
(75 MHz, CDCl ): d=55.9, 114.1, 116.5, 117.7, 127.0, 128.4
3
(
300 MHz, CDCl ): d=0.56 (d, J=6.6 Hz, 3H), 1.32 (d, J=
(2C), 128.5, 128.7, 129.1 (2C), 130.9, 131.4, 132.6, 133.3,
3
6
7
.9 Hz, 3H), 2.64–2.73 (m, 1H), 7.29–7.34 (m, 1H), 7.59–
136.5, 138.4, 146.0, 155.9, 158.9, 161.0, 196.5; IR (KBr): n=
1757, 1676, 1595, 1448, 1274, 1215 cm ; anal. calcd. for
À1
.76 (m, 4H), 7.95 (d, J=7.2 Hz, 1H), 8.09–8.16 (m, 2H);
1
3
C NMR (75 MHz, CDCl ): d=16.4, 17.2, 35.0, 97.5, 116.0,
C H NO : C 73.94, H 4.23, N 3.92; found: C 73.96, H 4.20,
3
22 15
4
1
1
1
20.9, 123.9, 124.7, 125.5, 130.6, 130.9, 133.4, 135.9, 136.4,
N 3.95%.
41.3, 161.9, 165.1, 201.3; IR (neat): n=2925, 1725, 1670,
2-(2-Benzoyl-3-methoxyphenyl)-4H-benzo[d][1,3]oxazin-
À1
601, 1449, 1357 cm , anal. calcd. for C H NO : C 73.71,
4-one (Scheme 4, 3qa’): white solid; mp 171–1738C;
18
15
3
1
H 5.15, N 4.78, found: C 73.69, H 5.16, N 4.79%.
-(2-Benzoyl-5-fluorophenyl)-4H-benzo[d][1,3]oxazin-4-
H NMR (300 MHz, CDCl ): d=3.79 (s, 3H), 7.09 (d, J=
3
2
7.8 Hz, 1H), 7.23 (d, J=8.1 Hz, 1H), 7.38–7.45 (m, 3H),
one (Scheme 4, 3na): off white solid; mp 192–1948C;
7.49–7.64 (m, 3H), 7.87–7.94 (m, 3H), 8.11 (dd, J =7.5 Hz,
1
1
13
H NMR (300 MHz, CDCl ): d=7.27 (d, J=8.1 Hz, 1H),
J2 =1.2 Hz, 1H); C NMR (75 MHz, CDCl ): d=55.4,
3
3
7
7
.33–7.39 (m, 3H), 7.41–7.46 (m, 2H), 7.49–7.54 (m, 1H),
115.5, 116.9, 121.3, 126.9, 128.54, 128.57 (2C), 128.6, 128.7
(2C), 129.3, 130.4, 130.5, 132.8, 136.5, 138.5, 146.1, 155.0,
157.5, 159.1, 195.7; IR (KBr): n=2924, 2854, 1759, 1747,
.65–7.71 (m, 1H), 7.76–7.79 (m, 2H), 7.93 (dd, J =9.3 Hz,
1
13
J2 =2.7 Hz, 1H), 8.07–8.10 (m, 1H); C NMR (75 MHz,
CDCl ): d=94.2, 111.8 (d, J =24 Hz, 1C), 116.2, 121.2,
À1
1678, 1603, 1462, 1265 cm ; anal. calcd. for C H NO : C
3
C,F
22 15
4
1
8
1
1
21.7 (d, JC,F =24 Hz, 1C), 125.61 (2C), 125.62 (d, JC,F
.3 Hz, 1C), 129.5 (2C), 129.8, 130.8, 131.8 (d, JC,F =33 Hz,
C), 136.0, 136.4, 137.2, 140.7 (d, JC,F =2.3 Hz, 1C), 162.2,
=
73.94, H 4.23, N 3.92; found: C 73.97, H 4.20, N 3.96%.
2-(3-Benzoyl-[1,1’-biphenyl]-4-yl)-4H-benzo[d]
[1,3]oxazin-4-one (Scheme 5, 3hax): white solid; mp 155–
1
64.2 (d, JC,F =250.5, 1C), 164.5 (d, JC,F =3.8 Hz, 1C), 196.2;
1578C; H NMR (300 MHz, CDCl ): d=7.24 (d, J=8.4 Hz,
3
À1
IR (KBr): n=1746, 1729, 1679, 1606, 1484, 1269 cm ; HR-
MS: m/z=346.0877, calcd. for C H FNO [M+H] :
3
1H), 7.37–7.49 (m, 8H), 7.67 (d, J=7.2 Hz, 3H), 7.74 (d, J=
1.8 Hz, 1H), 7.85–7.89 (m, 3H), 8.33 (d, J=8.4 Hz, 1H);
+
21
12
3
1
3
46.0874.
C NMR (75 MHz, CDCl ): d=116.5, 125.7, 126.8, 127.0,
3
2
-(2-Benzoyl-3-fluorophenyl)-4H-benzo[d][1,3]oxazin-4-
127.3 (2C), 128.2, 128.4, 128.5 (2C), 128.7, 129.0 (2C), 129.1
(2C), 129.4, 129.6, 132.9, 136.4, 137.9, 138.9, 141.9, 145.0,
146.0, 155.3, 158.9, 196.9; IR (KBr): n=1772, 1720, 1670,
one (Scheme 4, 3na’): light yellow solid; mp 186–1888C;
H NMR (300 MHz, CDCl ): d=7.11–7.14 (m, 1H), 7.39–
.48 (m, 4H), 7.52–7.61 (m, 1H), 7.63–7.69 (m, 2H), 7.89–
.91 (m, 2H), 8.11–8.15 (m, 2H); C NMR (75 MHz,
1
3
À1
7
7
1603, 1487, 1366, 1248 cm ; anal. calcd. for C H NO , C
2
7
17
3
13
80.38, H 4.25, N 3.47, found: C 80.41, H 4.27, N 3.44%.
CDCl ): d=116.8, 120.1 (d, J =21.7 Hz, 1C), 125.0 (d,
[5-Methyl-2-(4-oxo-4H-benzo[d][1,3]oxazin-2-yl)-1,3-phe-
3
C,F
JC,F =3 Hz, 1C), 126.9, 128.7, 128.8 (2C), 128.9 (2C), 129.0,
nylene]bis(phenylmethanone) (Table 4, 4ba): white solid;
1
1
1
2
1
29.1, 130.4 (d, JC,F =4.5 Hz, 1C), 131.0 (d, JC,F =8.3 Hz,
C), 133.4, 136.7, 137.9, 145.8, 154.2, 158.7, 159.8 (d, JC,F
mp 260–2628C; H NMR (300 MHz, CDCl ): d=2.39 (s,
3
=
3H), 7.27–7.36 (m, 4H), 7.42 (t, J=7.8 Hz, 2H), 7.54 (t, J=
7.2 Hz, 2H), 7.63 (t, J=7.2 Hz, 2H), 7.71 (d, J=8.1 Hz,
46 Hz, 1C), 192.6; IR (KBr): n=2924, 1776, 1734, 1668,
À1
13
630, 1603, 1454, 1259 cm ; HR-MS: m/z=346.0877, calcd.
1H), 7.97–8.04 (m, 4H), 8.17 (d, J=7.2 Hz, 1H); C NMR
+
for C H FNO [M+H] : 346.0874.
(75 MHz, CDCl ): d=22.2, 95.3, 118.3, 124.2, 124.9, 125.1,
21
12
3
3
2
-(2-Benzoyl-5-chlorophenyl)-4H-benzo[d][1,3]oxazin-4-
126.2, 126.5 (2C), 128.6 (2C), 129.4 (2C), 129.8, 130.6 (2C),
131.8, 132.4, 132.9, 133.4, 134.4, 135.7, 136.6, 136.9, 145.4,
145.6, 162.0, 165.3, 193.9; IR (neat): n=1728, 1672, 1452,
1
one (Scheme 4, 3oa): white solid; mp 171–1738C; H NMR
300 MHz, CDCl ): d=7.22–7.26 (m, 1H), 7.36 (t, J=
(
3
Adv. Synth. Catal. 2016, 358, 283 – 295
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
293

Biju Majhi et al.
FULL PAPERS
À1
1
360, 1215 cm ; HR-MS: m/z=468.1214, calcd. for
to B C R (SR/S2/JCB-11/2008). B. M. and D.K. thank CSIR,
New Delhi for their fellowships.
+
C H NO [M+Na] : 468.1206.
2
9
19
4
{5-Methoxy-2-(4-oxo-4H-benzo[d][1,3]oxazin-2-yl)-1,3-
phenylene}bis(phenylmethanone) (Table 4, 4ca): white solid,
1
mp=251–2538C, H NMR (300 MHz, CDCl ): d=3.82(s,
3
References
3
2
8
H), 6.94–7.02 (m, 2H), 7.27–7.37 (m, 2H), 7.40–7.45 (m,
H), 7.52–7.57 (m, 2H), 7.60–7.65 (m, 2H), 7.75 (d, J=
.4 Hz, 1H), 7.95–7.99 (m, 2H), 8.01–8.04 (m, 2H), 8.17 (dd,
[
1] a) M. Hojo, Y. Murakami, H. Aihara, R. Sakuragi, Y.
Baba, A. Hosomi, Angew. Chem. 2001, 113, 641–643;
Angew. Chem. Int. Ed. 2001, 40, 621–623; b) A. Fürst-
ner, M. Mendez, Angew. Chem. 2003, 115, 5513–5515;
Angew. Chem. Int. Ed. 2003, 42, 5355–5357; c) M. Seck,
X. Franck, R. Hocquemiller, B. Figadere, J.-F. Peyrat,
O. Provot, J.-D. Brion, M. Alami, Tetrahedron Lett.
13
J =7.8 Hz, J =1.5 Hz, 1H); C NMR (75 MHz, CDCl ):
1
2
3
d=56.0, 94.9, 108.5, 117.5, 118.3, 121.0, 124.9, 126.5 (2C),
1
1
2
29.4 (2C), 129.9 (2C), 130.6 (2C), 132.5, 132.9, 133.3, 134.6,
35.7, 136.7, 137.0, 147.6, 162.1, 164.8, 193.9; IR (neat):
À1
926, 1727, 1670, 1492, 1356, 1263 cm ; anal. Calcd. For
C H NO : C 75.48, H 4.15, N 3.04, found C 75.46, H 4.16,
N 3.07%.
5-Fluoro-2-(4-oxo-4H-benzo[d][1,3]oxazin-2-yl)-1,3-phe-
nylene)bis(phenylmethanone) (Table 4, 4ea): white solid;
mp 264–2668C; H NMR (300 MHz, CDCl ): d=7.17–7.23
2
9
19
5
2
004, 45, 1881–1884.
[
2] a) A. G. Myers, D. Tanaka, M. R. Mannion, J. Am.
Chem. Soc. 2002, 124, 11250–11251; b) D. Tanaka,
A. G. Myers, Org. Lett. 2004, 6, 433–436; c) D. Tanaka,
S. P. Romeril, A. G. Myers, J. Am. Chem. Soc. 2005,
(
1
3
(
(
m, 2H), 7.30–7.44 (m, 4H), 7.53–7.58 (m, 2H), 7.62–7.66
m, 2H), 7.81–7.85 (m, 1H), 7.97–8.04 (m, 4H), 8.18 (dd,
127, 10323–10333.
13
[3] L. J. Gooben, F. Rudolphi, C. Oppel, N. Rodriguez,
Angew. Chem. 2008, 120, 3085–3088; Angew. Chem.
Int. Ed. 2008, 47, 3043–3045.
J =7.8 Hz, J =1.5 Hz, 1H); C NMR (75 MHz, CDCl ):
1
2
3
d=94.6, 111.6 (d, JC,F =24.7 Hz, 1C), 118.3, 118.7 (d, JC,F
=
2
1
1
2
3.3 Hz, 1C), 124.8 (d, JC,F =2.3 Hz, 1C), 125.4, 126.4 (2C),
27.4 (d, JC,F =9.7 Hz, 1C), 128.7 (2C), 129.5 (2C), 130.2,
[
4] P. Fang, M. Li, H. Ge, J. Am. Chem. Soc. 2010, 132,
1898–11899.
1
30.6 (2C), 132.4, 133.0, 133.5, 134.2, 135.8, 136.4 (d, JC,F
0.2 Hz, 1C), 147.6 (d, JC,F =9.7 Hz, 1
=
[
5] S. Sharma, A. Kim, E. Park, J. Park, M. Kim, J. H.
Kwak, S. H. Lee, Y. H. Jung, I. S. Kim, Adv. Synth.
Catal. 2013, 355, 667–672.
C), 161.6, 164.1, 166.4 (d, JC,F =255.7 Hz, 1C), 193.8; IR
À1
(neat): n=2926, 1726, 1670, 1602, 1450, 1358 cm , anal.
[
[
6] C. Pan, H. Jin, X. Liu, Y. Cheng, C. Zhu, Chem.
Commun. 2013, 49, 2933–2935.
7] H. Li, P. Li, Q. Zhao, L. Wang, Chem. Commun. 2013,
calcd. for C H FNO : C 74.83, H 3.59, N 3.12; found: C
7
28
16
4
4.86, H 3.62, N 3.09%.
{5-Chloro-2-(4-oxo-4H-benzo[d][1,3]oxazin-2-yl)-1,3-phe-
49, 9170–9172.
nylene}bis(phenylmethanone) (Table 4, 4fa): off white solid;
mp 274–2768C; H NMR (300 MHz, CDCl ): d=7.34–7.50
1
[8] M. Kim, J. Park, S. Sharma, A. Kim, E. Park, J. H.
3
Kwak, Y. H. Jung, I. S. Kim, Chem. Commun. 2013, 49,
(m, 6H), 7.56 (t, J=7.5 Hz, 2H), 7.64–7.69 (m, 2H), 7.76 (d,
925–927.
J=8.4 Hz, 1H), 7.96–8.04 (m, 4H), 8.17–8.20 (m, 1H);
13
[9] a) M. Li, H. Ge, Org. Lett. 2010, 12, 3464–3467; b) H.
Wang, L.-N. Guo, X.-H. Duan, Org. Lett. 2012, 14,
C NMR (75 MHz, CDCl ): d=94.8, 118.4, 124.4, 125.5,
3
1
26.3, 126.5 (2C), 127.3, 128.7 (2C), 129.6 (2C), 130.2, 130.6
4358–4361; c) J. Park, M. Kim, S. Sharma, E. Park, A.
(2C), 131.5, 132.5, 133.0, 133.5, 134.2, 135.8, 136.2, 136.5,
Kim, S. H. Lee, J. H. Kwak, Y. H. Jung, I. S. Kim,
Chem. Commun. 2013, 49, 1654–1656; d) Z. Yang, X.
Chen, J. Liu, Q. Gui, K. Xie, M. Li, Z. Tan, Chem.
Commun. 2013, 49, 1560–1562; e) S. Sharma, I. A.
Khan, A. K. Saxena, Adv. Synth. Catal. 2013, 355, 673–
1
1
40.8, 146.6, 161.6, 164.2, 193.8; IR (neat): n=3020, 2928,
À1
751, 1728, 1672, 1597, 1477, 1215 cm ; anal. calcd. for
C H ClNO : C 72.19, H 3.46, N 3.01; found: C 72.17, H
3
2
8
16
4
.45, N 3.05%.
{2-(6,7-Dimethoxy-4-oxo-4H-benzo[d][1,3]oxazin-2-yl)-5-
6
78; f) J. Miao, H. Ge, Org. Lett. 2013, 15, 2930–2933;
g) H. Li, P. Li, H. Tan, L. Wang, Chem. Eur. J. 2013, 19,
4432–14436; h) Z.-Y. Li, D.-D. Li, G.-W. Wang, J. Org.
methyl-1,3-phenylene}bis(phenylmethanone) (Table 4, 4ma):
light yellow solid; mp 268–2708C; H NMR (300 MHz,
CDCl ): d=2.45 (s, 3H), 3.81 (s, 3H), 3.92 (s, 3H), 7.31–7.37
1
1
3
Chem. 2013, 78, 10414–10420; i) Z. Yao, R. Feng, Z.
Wu, Z. Liu, Y. Zhang, Adv. Synth. Catal. 2013, 355,
(
(
m, 5H), 7.41–7.42 (m, 1H), 7.45–7.60 (m, 6H), 7.87–7.90
m, 2H); C NMR (75 MHz, CDCl ): d=22.1, 56.2, 56.7,
13
3
1517–1522; j) H. Wang, L.-N. Guo, X.-H. Duan, Adv.
9
(
1
4.4, 103.6, 107.9, 111.1, 125.3, 125.7 (2C), 128.8 (2C), 129.4
2C), 129.8, 130.0, 130.1 (2C), 132.1, 134.1, 136.5, 137.4,
38.5, 145.3, 146.0, 147.0, 155.6, 162.4, 164.2, 195.0; IR
Synth. Catal. 2013, 355, 2222–2226; k) M. Kim, N. K.
Mishra, J. Park, S. Han, Y. Shin, S. Sharma, Y. Lee, E.-
K. Lee, J. H. Kwak, I. S. Kim, Chem. Commun. 2014,
50, 14249–14252; l) L. Chen, H. Li, F. Yu, L. Wang,
Chem. Commun. 2014, 50, 14866–14869; m) H. Tan, H.
Li, J. Wang, L. Wang, Chem. Eur. J. 2015, 21, 1904–
(neat): n=2926, 2854, 1713, 1693, 1666, 1610, 1514, 1427,
À1
1
275, 1215 cm ; HR-MS: m/z=506.1595, calcd. for
+
C H NO [M+H] : 506.1598.
3
1
24
6
1907.
[
[
10] P. M. Chandrika, T. Yakaiah, A. R. Rao, B. Narsaiah,
Eur. J. Med. Chem. 2008, 43, 846–852.
11] a) A. M. F. Eissa, R. J. El-Sayed, J. Heterocycl. Chem.
2006, 43, 1161–1168; b) R. L. Jarvest, M. J. Parratt,
C. M. Debouck, J. G. Gorniak, J. L. Jennings, H. T. Ser-
afinowska, J. E. Strickler, Bioorg. Med. Chem. Lett.
1996, 6, 2463–2466.
Acknowledgements
This work has been supported by Department of Science and
Technology, Govt of India with a J C Bose Fellowship grant
2
94
asc.wiley-vch.de
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2016, 358, 283 – 295

FULL PAPERS
Palladium-Catalyzed Decarboxylative Selective Acylation
[
[
[
12] M. Gutschow, U. Neumann, Bioorg. Med. Chem. 1997,
, 1935–1942.
13] U. Neumann, N. M. Schechter, M. Gutschow, Bioorg.
Med. Chem. 2001, 9, 947–954.
14] a) A. Krantz, R. W. Spencer, T. F. Tam, T. J. Liak, L. J.
Copp, E. M. Thomas, S. P. Rafferty, J. Med. Chem.
5918; d) Q.-Z. Zheng, N. Jiao, Tetrahedron Lett. 2014,
55, 1121–1126; e) K. Shin, H. Kim, S. Chang, Acc.
Chem. Res. 2015, 48, 1040–1052; f) X. Chen, K. M.
Engle, D.-H. Wang, J.-Q. Yu, Angew. Chem. 2009, 121,
5196–5217; Angew. Chem. Int. Ed. 2009, 48, 5094–5115;
g) S. D. Sarkar, W. Liu, S. I. Kozhushkov, L. Acker-
mann, Adv. Synth. Catal. 2014, 356, 1461–1479; h) L.
Ackermann, R. Vicente, Top. Curr. Chem. 2010, 292,
5
1
990, 33, 464–479; b) R. Padwal, Curr. Opin. Invest.
Drugs 2008, 9, 414–421.
[
[
15] a) L. Hedstrom, A. R. Moorman, R. H. Abeles, Bio-
chemistry 1984, 23, 1753–1759; b) R. L. Stein, A. M.
Strimpler, B. R. Viscarello, R. A. Wildonger, R. C.
Mauger, D. A. Trainor, Biochemistry 1987, 26, 4126–
2
11–229; i) L. Ackermann, J. Org. Chem. 2014, 79,
8948–8954; j) S. Tain, T. N. Uehara, J. Yamaguchi, K.
Itami, Chem. Sci. 2014, 5, 123–135; k) F. Kakiuchi, T.
Kochi, S. Murai, Synlett 2014, 25, 2390–2414; l) K. Gao,
N. Yashikal, Acc. Chem. Res. 2014, 47, 1208–1219;
m) S. A. Girard, T. Knauber, C.-J. Li, Angew. Chem.
4130; c) J. C. Powers, J. L. Asgian, O. D. Ekici, K. E.
James, Chem. Rev. 2002, 102, 4639–4750; d) M. Pietsch,
M. G. Tschow, J. Med. Chem. 2005, 48, 8270–8288.
2
1
2
014, 126, 76–103; Angew. Chem. Int. Ed. 2014, 53, 74–
00; n) X.-S. Zhang, K. Chen, Z.-J. Shi, Chem. Sci.
014, 5, 2146–2159; o) J. Wencel-Delord, F. Glorius,
16] a) E. C. Taylor, R. I. Knopf, A. L. Borror, J. Am.
Chem. Soc. 1960, 82, 3152–3157; b) T. G. Jackson, S. R.
Morris, R. H. Turner, J. Chem. Soc. Perkin Trans. 1968,
Nat. Chem. 2013, 5, 369–375; p) G. Rouquet, N. Chata-
ni, Angew. Chem. 2013, 125, 11942–11959; Angew.
Chem. Int. Ed. 2013, 52, 11726–11743; q) K. M. Engle,
T.-S. Mei, M. Wasa, J.-Q. Yu, Acc. Chem. Res. 2012, 45,
1592–1593; c) S. Cacchi, G. Fabrizi, F. Marinelli, Synlett
1
996, 997–998; d) R. C. Larock, C. A. Fellows, J. Org.
Chem. 1980, 45, 363–365; e) C. Larksarp, H. Alper,
Org. Lett. 1999, 1, 1619–1622; f) P. Salehi, M. Dabiri,
M. A. Zolfigol, M. Baghbanzadeh, Tetrahedron Lett.
7
4
2
88–802; r) A. J. Hickman, M. S. Sanford, Nature 2012,
84, 177–185; s) T. Satoh, M. Miura, Chem. Eur. J.
010, 16, 11212–11222; t) Y. Wu, L. J. Feng, X. Lu, F. Y.
2
005, 46, 7051–7053; g) D. J. R. OꢁMahony, V. Krchnak,
Tetrahedron Lett. 2002, 43, 939–942; h) R. A. Kumar,
C. Maheswari, S. Ghantasala, C. Jyothi, K. Rajendar
Reddy, Adv. Synth. Catal. 2011, 353, 401–410; i) X. L.
Lian, H. Lei, X. J. Quan, Z. H. Ren, Y. Y. Wang, Z. H.
Guan, Chem. Commun. 2013, 49, 8196–8198; j) Q. Liu,
P. Chen, G. Liu, ACS Catal. 2013, 3, 178–181.
Kwong, H. B. Luo, Chem. Commun. 2014, 50, 15352–
5354.
1
[
[
[
18] For a review on C-H acylation, see: X.-F. Wu, Chem.
Eur. J. 2015, 21, 12252–12265.
19] Y. Ji, X. Yang, W. Mao, Appl. Organomet. Chem. 2014,
28, 678–680.
[
17] a) L. Ackermann, R. Vicente, A. R. Kapdi, Angew.
20] CCDC 1414042 contains the supplementary crystallo-
graphic data for this paper. These data can be obtained
free of charge from The Cambridge Crystallographic
Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
Chem. 2009, 121, 9976–10011; Angew. Chem. Int., Ed.
2
009, 48, 9792–9826; b) C.-L. Sun, B.-J. Li, Z.-J. Shi,
Chem. Rev. 2011, 111, 1293–1314; c) P. B. Arockiam, C.
Bruneau, P. H. Dixneuf, Chem. Rev. 2012, 112, 5879–
Adv. Synth. Catal. 2016, 358, 283 – 295
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
295