Copper(I) bromide-catalyzed carbonylative coupling of aryl halides with phenols, alcohols and amines using sodium cyanide as C1 source: A synthesis of carboxylic acid derivatives

Article abstract of DOI:10.1002/adsc.201301155

A new carbon monoxide-free synthesis of carboxylate derivatives via carbonylative coupling of aryl bromides with phenols, alcohols, amines and acids in the presence of copper(I) bromide as catalyst and sodium cyanide in a stoichiometric amount has been developed. Its intramolecular version provides for the preparation of lactones (e.g., isochroman-1-ones and isobenzfuranones), imides, anhydrides and lactams in excellent yields (73-96%).

Full text of DOI:10.1002/adsc.201301155

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DOI: 10.1002/adsc.201301155
Copper(I) Bromide-Catalyzed Carbonylative Coupling of
Aryl Halides with Phenols, Alcohols and Amines using
Sodium Cyanide as C1 Source: A Synthesis of Carboxylic Acid
Derivatives
Pragati K Prasada and Arumugam Sudalaia,*
a
Chemical Engineering and Process Development Division, National Chemical Laboratory, Pashan Road, Pune – 411 008,
India
Fax : (+91)-20-2590-2676; phone: (+91)-20-2590-2174; e-mail: a.sudalai@ncl.res.in
Received: December 20, 2013; Revised: March 5, 2014; Published online: && &&, 0000
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201301155.
Abstract: A new “carbon monoxide-free” synthesis
of carboxylate derivatives via carbonylative cou-
pling of aryl bromides with phenols, alcohols,
amines and acids in the presence of copper(I) bro-
mide as catalyst and sodium cyanide in a stoichio-
metric amount has been developed. Its intramolecu-
lar version provides for the preparation of lactones
(e.g., isochroman-1-ones and isobenzfuranones),
imides, anhydrides and lactams in excellent yields
(73–96%).
liquids.[6] Still, there is continuing interest in easier
and cost-effective alternative methods that avoid the
use of CO gas and organometallic reagents.
The classical reaction of bromobenzene derivatives
with a stoichiometric amount of CuCN in DMF at
reflux temperature (Rosenmund–Von Braun reac-
tion)[7] generally affords the corresponding cyanoben-
zene derivatives. Subsequently, nickel[8,9] and palladi-
um[10] complexes as catalysts in the cyanation of aryl
bromides using KCN and NaCN[11] as CN source were
introduced. Many other variants followed later includ-
ing zinc cyanide,[12] trimethylsilyl cyanide,[13] tributyl-
tin cyanide,[14] dialkylcyanoboronates,[15] potassium
hexacyanoferrate(II)[16] and acetone cyanohydrin.[17]
However, the high cost of these metals/reagents and
the need to use expensive and toxic phosphines as li-
gands necessitated the development of other methods.
Keywords: anhydrides; C1 building blocks; isochro-
man-1-ones; lactams; lactones
Aromatic and heteroaromatic carboxylate derivatives The copper-catalyzed cyanation of aryl and heteroaryl
such as esters, amides, lactones, lactams, anhydrides, bromides in toluene at around 110–1308C has also
etc. are versatile raw materials in the manufacture of been reported.[18] However, this method requires the
agrochemicals, dyes, pharmaceuticals, photosensitizers use of a ten-fold amount of the rather expensive
and other industrial products.[1] Their preparation di- ligand N,N’-dimethylethylenediamine relative to the
rectly from aryl halides begins with halogen-metal ex- copper salt. This feature is thus less attractive for
change by alkyllithium or Grignard reagents followed large-scale applications. As a consequence, the search
by reaction with CO2 to produce carboxylic acids, for more practical methods involving copper catalysis
which can subsequently be condensed with phenols, appears necessary to meet the demands of contempo-
alcohols or amines.[2] Alternatively, an efficient and rary chemical synthesis, that is, less waste and the use
complementary methodology is the emergence of Pd- of catalytic processes wherever possible.
catalyzed Heck carbonylation of aryl halides with al-
Recently, we have reported a new method for the
cohols or amines, which is highly attractive due to its CuCN-mediated one-pot cyclization of 4-(2-bromo-
high atom economy.[3] However, the use of highly spe- phenyl)-2-butenoates that provides for an efficient
cialized equipment capable of withstanding elevated synthesis of substituted naphthalene amino esters.[19]
pressure has often been necessary to enable safe han- In analogy with this, we reasoned that subjecting 2-
dling of CO in the standard laboratory equipment. bromobenzylic alcohol (2w) to the same reaction con-
Recent improvements[4] in this strategy focus on ditions should afford the corresponding aryl cyanide,
alkoxy/aryloxy carbonylation, oxidative esterification which can be elaborated after hydrolysis, to construct
via NHC catalysis[5] and aminocarbonylation in ionic the corresponding butylphthalide (3w), an anticonvul-
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Pragati K Prasad and Arumugam Sudalai
sponding phenyl ester 3a in 28% yield. The yield of
3a was significantly improved to 45% when the
CuCN quantity was increased (2 equiv.) under other-
wise the same reaction conditions. However, a remark-
able increase in yield of 3a (74%) was realized when
the CuCN concentration was further increased
(3 equiv.). On lowering the temperature (1208C), the
product yield was reduced (46%). A brief evaluation
of solvents showed that DMF was the most suitable
one. In order to provide a catalytic process, we have
carried out the carbonylative coupling with CuBr as
the catalyst and NaCN, a relatively easy to handle
solid as the CN source. Thus, by using CuBr
(10 mol%) along with NaCN (1.1 equiv.), 3a was ob-
tained in low yield (24%, entry 4). In order to im-
prove the yield, a series of N-based ligands was
screened along with CuBr (10 mol%) and NaCN
(1.1 equiv.), which allowed the reaction to proceed at
1208C giving 3a in reasonably good yields (entries 5–
10). After several experimentations, it was thus found
that a combination of bromobenzene, phenol, NaCN
(1.1 equiv.), CuBr (10 mol%), and 1,10-phenanthro-
Scheme 1. CuBr-catalyzed synthesis of butylphthalide from
2-bromobenzyl alcohol.
Scheme 2. CuBr-catalyzed carbonylative coupling of aryl
halides with NaCN and nucleophiles.
sant drug for the treatment of stroke. Gratifyingly, line (10 mol%) in DMF at 1208C for 12 h represented
phthalide 3w (85%) was isolated in a single step di- the optimised conditions for achieving 3a in high
rectly from bromo alcohol 2w (Scheme 1).
yields (74%, entry 6). The observed ligand-based ac-
In this communication, we wish to describe a new celeration can be rationalized by the fact that Cu(I) is
Cu-catalyzed one-pot methodology for the prepara- electronically enriched when associated to bipyridine-
tion of several carboxylate derivatives directly from type ligands thus facilitating oxidative addition of
aryl halides (1) with phenols, alcohols, amines and ArX onto Cu(I).[20] Lowering the CuBr concentration
H2O as the nucleophiles (2) using NaCN as C1 source (5 mol%) afforded 3a in low yields (37%). Employing
under neutral reaction conditions (Scheme 2).
For determining the optimal conditions (Table 1), either.
K4[Fe(CN)6][20e,21] as the cyanide source was not useful
bromobenzene and phenol were treated with CuCN
With the optimized reaction conditions in hand,
(1 equiv.) in DMF at 1508C, which gave the corre- next we sought to examine the scope and limitations
Table 1. CuBr-catalyzed carbonylative coupling of bromobenzene with phenol using NaCN as C1 source: optimization stud-
ACHTUNGTRENNUNG
ies.[a]
No.
Catalyst (10 mol%)
Ligand/Additive (10 mol%)
CN source (equiv.)
Temp. [8C]
Yield of 3a [%][b]
1
2
3
4
5
6
7
8
–
–
–
–
–
–
CuCN (3)
CuCN (3)
150
120
120
120
120
120
120
120
120
120
150
74 (28,[c] 45[d])
46
19
24
CuCN
CuBr
CuBr
CuBr
CuI
CuBr
CuBr
CuBr
NaCN (1.1)
NaCN (1.1)
NaCN (1.1)
NaCN (1.1)
NaCN (1.1)
NaCN (1.1)
NaCN (1.1)
NaCN (1.1)
K4[Fe(CN)6] (0.5)
l-proline
70
1,10-phenanthroline
1,10-phenanthroline
ethylenediamine
N,N-dimethylethylenediamine
N,N-diisopropylethylenediamine
KI
74 (37,[e] trace[f])
76
38
32
9
10
11
27
Cu
G
trace[g]
[a]
PhBr (3 mmol), PhOH (3 mmol), DMF, 12 h.
Isolated yield after column chromatographic purification.
1 equiv. of CuCN used.
2 equiv. of CuCN used.
5 mol% of CuBr used.
[b]
[c]
[d]
[e]
[f]
Toluene used.
DMF+H2O (1:1) used.
[g]
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Copper(I) Bromide-Catalyzed Carbonylative Coupling of Aryl Halides
Table 2. CuBr-catalyzed carbonylative coupling of haloaromatics with nucleophiles.[a]
No.
Substrate (1) (ArX)
Nucleophiles (2a–k) (RYH)
Product (3a–k)
Yields [%][b]
a
b
c
d
e
f
g
h
i
bromobenzene
bromobenzene
bromobenzene
bromobenzene
bromobenzene
bromobenzene
bromobenzene
bromobenzene
3-bromotoluene
4-methoxybromobenzene
4-nitroiodobenzene
phenol
phenyl benzoate
74
71
76
68
70
63
71
70
68
71
71
4-nitrophenol
4-methoxybenzyl alcohol
aniline
2-chloroaniline
4-methoxyaniline
2-chlorobenzylamine
water
phenol
phenol
phenol
4-nitrophenyl benzoate
4-methoxybenzyl benzoate
benzanilide
2-chlorobenzanilide
4-methoxybenzanilide
2-chlorobenzylbenzamide
benzoic acid
3-methylphenyl benzoate
4-methoxyphenyl benzoate
4-nitrophenyl benzoate
j
k
[a]
Reaction conditions: NaCN (3.3 mmol), CuBr (10 mol%), substrate (3 mmol), nucleophile (3 mmol), 1,10-phenanthroline
(10 mol%), DMF, 1208C, 12 h.
Isolated yield after column chromatographic purification.
[b]
À
of the reaction with various bromides and amine nu- catalyst. Mechanistically, Ar X on oxidative addition
cleophiles. Table 2 illustrates a number of representa- with CuX forms arylCuX, which subsequently under-
tive aryl halides that have been coupled with a variety goes nucleophilic displacement with NaCN to gener-
of phenols and amines, indicative of considerable gen- ate ArCuCN (I).[18,25] Reductive elimination of
erality. Noteworthy among these are the aryl halides ArCuCN produces ArCN (II) (isolated and character-
bearing NO2 and OMe groups that were successful ized) which on s-bond metathesis with nucleophiles
under these conditions. Electron-rich and electron-de- (e.g., alcohols, phenols and amines) gives imine
ficient nucleophiles such as phenols, alcohols, anilines, (III),[26] hydrolysis of which affords 3a–z (Figure 1).
benzylamine, etc. gave good yields of the correspond-
In summary, we have developed a simple Cu-cata-
ing carboxylic esters and amides (63–76%). Other lyzed protocol for the carbonylative coupling of aryl
minor products isolated in these cases were the corre- halides with a variety of nucleophiles and NaCN as
sponding aryl nitriles, unreacted nucleophiles (alcohol C1 source using 1,10-phenanthroline as ligand that
or amine) and traces of benzoic acid. Also, benzoic provides for the synthesis of carboxylic acid deriva-
acid was obtained (70%) when water was used. How- tives in high yields. Incorporation of the carbonyl
ever, in the case of 1-bromooctane, only 1-cyanooc- moiety into organic molecules using a three-compo-
tane (80%) was obtained under reaction conditions nent matrix with CN, an organic halide and a nucleo-
while long-chain aliphatic alcohols (C8 and C16) when philic component constitutes a simple and diverse ap-
reacted with bromobenzene, gave benzoic acid as the proach to the formation of benzoic acid derivatives.
sole product, which may be a limitation of the catalyt- This transformation is very practical, as it could be
ic process.
conducted under air. We believe that this “CO-free”
Next, its intramolecular versions were examined, catalytic process will find tremendous applications in
which allowed for the synthesis of lactones, lactams,[24] the commercial production of large volume chemicals
anhydrides and other heterocycles. As can be seen such as aromatic carboxylic acids, esters, amides, lac-
from Table 3, several substituted 2-bromophenethyl tones, anhydrides, coumarins, etc.
alcohol derivatives (2l–q), were subjected to Cu-cata-
lyzed intramolecular coupling with NaCN (1.1 equiv.)
that afforded the corresponding isochroman-1-ones Experimental Section
(3l–q) in excellent yields (84–88%). Similarly, 2-bro-
NB: Sodium cyanide is “highly toxic” and must be handled
with due care.
mobenzylic alcohol derivatives (2s–w) gave the corre-
sponding isobenzfuranones (phthalides), (3s–w) in 78–
92% yields. Interestingly, phthalic anhydride (3x) was
also obtained in 96% yields from 2-iodobenzoic acid.
Simple coumarin (entry 3r) was also obtained in 81%
yield from vinylic dibromophenol 2r.[23,24] The dicarbo-
nylative coupling of ortho-dibromobenzene into
phthalimide 3y[24] in a single step is remarkable.
General Experimental Procedure for the Preparation
of 1-(2-bromophenyl)alkenols (2l–q) and (2s–u)
To a stirred solution of substituted 2-bromobenzaldehyde or
2-(2-bromophenyl)acetaldehyde[8] (5 mmol) in CH3CN:H2O
(40 mL:10 mL) at 08C were added allyl bromide (6 mmol),
activated Zn dust (6 mmol) and saturated NH4Cl solution
(10 mL). The reaction mixture was allowed to stir at room
Also, aryl nitriles can be employed instead of aryl
halides as substrates giving the desired products (3),
although the reaction fails in the absence of a Cu(I) temperature for 2–3 h (monitored by TLC). The reaction
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Table 3. CuBr-catalyzed intramolecular carbonylative coupling: substrate scope.[a]
Substrate (2l–z)[b]
Product (3l–z), Yield
R1 =H, R2 =H; (2l)
R1 =H, R2 =Me; (2m)
R1 =OMe, R2 =H; (2n)
R1 =F, R2 =H; (2o)
R1 =H, R2 =H; (3l), 84%
R1 =H, R2 =Me; (3m), 86%
R1 =OMe, R2 =H; (3n), 87%
R1 =F, R2 =H; (3o), 88%
(2p)
(2q)
(3p), 84%
(3q), 84%
(3r), 81%
AHCTUNGTERG(NNUN 2r)
R1 =F, R2 =allyl; (2s)
R1 =OMe, R2 =allyl; (2t)
R1 =Br, R2 =allyl; (2u)
R1 =H, R2 =heptyl; (2v)
R1 =F, R2 =allyl; (3s), 92%
R1 =OMe, R2 =allyl; (3t), 85%
R1 =Br, R2 =allyl; (3u), 78%
R1 =H, R2 =heptyl; (3), 91%
(2x)
(3x), 96%
(2y)
(2z)
(3y), 73%
(3z), 81%
[a]
For reaction conditions, see footnote under Table 2.
[b]
The corresponding aldehydes were trapped with allyl bromide under Barbier allylation[22] conditions (see Experimental
Section).
[c]
[d]
Concomitant reduction of one of the Br atoms to H takes place.[23]
2 equiv.of NaCN used, 1 equiv. of benzylamine used as nucleophile.
mixture was then cooled to 08C and excess Zn was
quenched with aqueous NH4Cl. Solvent was evaporated
under reduced pressure and aqueous layer was diluted with
EtOAc. The organic layer was separated and the aqueous
layer was extracted with EtOAc (3ꢁ20 mL). The combined
organic extracts were dried over anhydrous Na2SO4 and con-
centrated under reduced pressure to give crude products
which were purified by column chromatography [silica gel
(230–400 mesh) and petroleum ether:EtOAc (7:3) as an
eluent] to afford the corresponding 1-(2-bromophenyl)alk-
AHCTUNGTRENNeGUN nols (2k–p) and (2r–t); yield: 80–92%.
General Experimental Procedure for the Preparation
of Carboxylic Acid Derivatives (3a-3k) via an
Intermolecular Reaction
To a stirred solution of haloarenes 1a–k (3 mmol) and nucle-
ophiles 2a–k (3 mmol) in dry DMF (15 mL) were added
NaCN (3.3 mmol), CuBr (0.3 mmol) and 1,10-phenanthro-
line (0.3 mmol). The entire reaction mixture was heated to
Figure 1. Proposed catalytic cycle for CuBr-catalyzed car-
bonylative coupling of aryl halides with NaCN and nucleo-
philes.
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Copper(I) Bromide-Catalyzed Carbonylative Coupling of Aryl Halides
1208C while being stirred under N2 for 12 h (monitored by
TLC). The reaction mixture was then cooled to room tem-
perature and excess cyanide was quenched with aqueous
NaClO2, diluted with water (10 mL) and EtOAc (15 mL).
The organic layer was separated and the aqueous layer was
extracted with EtOAc (3ꢁ20 mL). The aqueous layer after
extraction was poured into aqueous KMnO4 solution and
then disposed of. The combined organic extracts were
washed with brine, dried over anhydrous Na2SO4 and con-
centrated under reduced pressure to give crude products
which were purified by column chromatography [silica gel
(230–400 mesh) and petroleum ether:EtOAc (7:3) as an
eluent] to afford the corresponding esters and amides (3a–
k); yield: 63–74%.
130.0, 130.3, 132.8, 159.6, 166.2; analysis: C15H14O3 requires
C 74.36, H 5.82, O 19.81; found: C 74.35, H 5.78, O 19.87%.
N-Phenylbenzamide (3d): Yield: 0.402 (2.040 mmol,
68%); colorless solid; mp 1638C; IR (CHCl3): umax =690,
780, 1305, 1430, 1530, 1600, 1670, 3330 cmÀ1 1H NMR
;
(200 MHz, CDCl3): d=6.63–6.77 (m, 2H), 7.13 (tt, J=1.6
and 8.4 Hz, 2H), 7.32–7.65 (m, 5H), 7.86 (td, J=1.6 and
6.4 Hz, 2H); 13C NMR(100 MHz, CDCl3): d=115.1, 118.6,
120.2, 124.6, 127.1, 128.8, 129.1, 129.3, 131.8, 135.1, 138.0,
146.3, 165.5; analysis: C13H11NO requires C 79.17, H 5.62, N
7.10, O 8.11; found: C 79.95, H 5.54, N 7.13, O 7.38%.
N-(2-Chlorophenyl)benzamide (3e): Yield: 0.486 g
(2.099 mmol, 70%); colorless solid; mp 1018C; IR (CHCl3):
umax =690, 788, 1310, 1415, 1510, 1600, 1680, 3310 cmÀ1
;
1H NMR (200 MHz, CDCl3): d=7.07 (dt, J=1.3 and 7.4 Hz,
1H), 7.29–7.59 (m, 5H), 7.93 (td, J=1.3 and 6.1 Hz, 2H),
8.45 (br. s., 1H), 8.58 (dd, J=1.6 and 8.3 Hz, 1H); 13C NMR
(100 MHz, CDCl3): d=121.5, 122.9, 124.6, 127.1, 127.9,
128.9, 128.9, 132.1, 134.6, 134.8, 165.0; analysis: C13H10ClNO
requires C 67.40, H 4.35, Cl 15.30, N 6.05, O 6.91; found: C
67.87, H 4.23, Cl 15.18, N 6.20, O 6.52%.
General Experimental Procedure for the Preparation
of Carboxylic Acid Derivatives (3l–3z) via an
Intramolecular Reaction
To a stirred solution of haloarenes 2k–y (3 mmol) in dry
DMF (15 mL) were added NaCN (3.3 mmol), CuBr
(0.3 mmol) and 1,10-phenanthroline (0.3 mmol). The entire
reaction mixture was heated to 1208C while being stirred
under N2 for 12 h (monitored by TLC). The reaction mix-
ture was then cooled to room temperature and excess cya-
nide was quenched with aqueous NaClO2, diluted with
water (10 mL) and EtOAc (15 mL). The organic layer was
separated and the aqueous layer was extracted with EtOAc
(3ꢁ20 mL). The aqueous layer after extraction was poured
into aqueous KMnO4 solution and then disposed of. The
combined organic extracts were washed with brine, dried
over anhydrous Na2SO4 and concentrated under reduced
pressure to give crude products which was purified by
column chromatography [silica gel (230–400 mesh) and pe-
troleum ether:EtOAc (7:3) as an eluent] to afford the corre-
sponding esters and imides (3l–z); yield: 73–96%.
N-(2-Chlorobenzyl)benzamide
(3g):
Yield:
0.523 g
(2.130 mmol, 71%); colorless solid; mp 998C; IR (CHCl3):
umax =688, 785, 1316, 1400, 1520, 1678, 3320 cmÀ1; H NMR
1
(200 MHz, CDCl3): d=4.70 (d, J=5.4 Hz, 2H), 6.73 (br. s.,
1H) 7.20–7.26 (m, 2H) 7.35–7.52 (m, 5H) 7.77 (dd, J=1.6
and 8.2 Hz, 2H); 13C NMR (100 MHz, CDCl3): d=42.0,
127.0, 127.1, 128.6, 128.9, 129.6, 130.4, 131.5, 133.7, 134.3,
135.7, 167.2; analysis: C14H12ClNO requires C 68.44, H 4.92,
Cl 14.43, N 5.70, O 6.51; found: C 68.87, H 4.23, Cl 14.78, N
5.20, O 6.92%.
Benzoic acid (3h): Yield: 0.256 g (2.098 mmol, 70%); col-
orless solid; mp 1238C; IR (CHCl3): umax =700, 1280, 1320,
1
1410, 1690, 3200 cmÀ1; H NMR (400 MHz, acetone-d6): d=
7.43–7.48 (m, 2H), 7.50–7.55 (m, 1H), 7.93–7.96 (m, 2H);
13C NMR (50 MHz, acetone-d6): d=30.2, 128.3, 129.1, 132.1,
135.3, 169.1; analysis: C7H6O2 requires C 68.85, H 4.95, O
26.20; found: C 68.82, H 4.97, O 26.21%.
Phenyl benzoate (3a): Yield: 0.440 g (2.222 mmol, 74%);
colorless solid; mp 708C; IR (CHCl3): umax =690, 1080, 1260,
Phenyl 3-methylbenzoate (3i): Yield: 0.433 g (2.041 mmol,
1
1500, 1718, 2980 cmÀ1 1H NMR (200 MHz, CDCl3): d=
;
68%); colorless oil; H NMR (200 MHz, CDCl3): d=2.45 (s,
3H), 7.16 À7.30 (m, 3H), 7.34–7.46 (m, 4H), 7.98–8.01 (m,
2H); 13C NMR (50 MHz, CDCl3): d=21.0, 121.5, 125.5,
127.0, 128.2, 129.1, 129.2, 130.4, 134.0, 137.9, 150.8, 164.7;
analysis: C14H12O2 requires C 79.23, H 5.70, O 15.08; found:
C 79.12, H 5.97, O 14.91%.
7.18–7.30 (m, 3H) 7.39–7.53 (m, 4H) 7.58–7.67 (m, 1H),
8.20 (td, J=1.7 and 6.9 Hz, 2H); 13C NMR (50 MHz,
CDCl3): d=121.7, 125.8, 128.5, 129.4, 129.7, 130.2, 133.5,
151.0, 164.9; Aanalysis: C13H10O2 requires C 78.77, H 5.09,
O 16.14; found: C 78.56, H 5.34, O 16.10%.
Phenyl
4-methoxybenzoate
(3j):
Yield:
0.485 g
4-Nitrophenyl benzoate (3b): Yield: 0.517 g (2.127 mmol,
71%); colorless solid; mp 1418C; IR (CHCl3): umax= 695,
(2.130 mmol, 71%); colorless solid; mp 708C; 1H NMR
(200 MHz, CDCl3): d=3.89 (s, 3H), 6.97 (td, J=3.5 Hz and
9.1 Hz, 2H), 7.15–7.29 (m, 3H), 7.35–7.46 (m, 2H);
13C NMR (125 MHz, CDCl3): d=55.4, 113.8, 121.8, 123.2,
125.7, 129.4, 132.3, 151.1, 163.9, 164.7; analysis: C14H12O3 re-
quires C 73.67, H 5.30, O 21.03; found: C 73.75, H 5.13, O
21.12%.
1
1060, 1206, 1340, 1530,1740, 3010 cmÀ1; H NMR (200 MHz,
CDCl3): d=7.43 (td, J=3.2 and 8.9 Hz, 2H) 7.50–7.61 (m,
2H) 7.55 (dt, J=1.6 and 7.6 Hz, 1H) 7.70 (tt, J=1.6 and
7.6 Hz, 1H), 8.19–8.24 (m, 2H), 8.34 (td, J=3.2 and 8.9 Hz,
2H); 13C NMR (50 MHz, CDCl3): d=122.6, 125.2, 128.6,
128.8, 130.3, 134.2, 145.4, 155.7, 164.0; analysis: C13H9NO4
requires C 64.20, H 3.73, N 5.76, O 26.31; found: C 64.46, H
3.54, N 5.67, O 26.33%.
Phenyl 4-nitrobenzoate (3k): Yield: 0.518 g (2.130 mmol,
71%); colorless solid; mp 1288C; 1H NMR (200 MHz,
CDCl3): d=7.16–7.50 (m, 5H), 8.36 (s, 4H); 13C NMR
(125 MHz, CDCl3): d=122.8, 123.8, 129.8, 131.3, 131.9,
134.6, 148.9, 151.0, 162.9; analysis: C13H9NO4 requires C
64.20, H 3.73, N 5.76, O 26.31; found: C 64.38, H 3.52, N
5.81, O 26.29%.
4-Methoxybenzyl
(2.280 mmol, 76%); colorless solid; mp 918C; IR (CHCl3):
umax =693, 1075, 1270, 1500, 1720, 2990 cmÀ1 1H NMR
benzoate
(3c):
Yield:
0.552 g
;
(200 MHz, CDCl3): d=3.80 (s, 3H), 5.28 (s, 2H), 6.89 (td,
J=2.9 and 8.6 Hz, 2H), 7.35–7.45 (m, 4H), 7.53 (tt, J=1.7
and 7.1 Hz, 1H), 8.04 (td, J=1.7 and 7.1 Hz, 2H); 13C NMR
(50 MHz, CDCl3): d=55.1, 66.4, 113.9, 128.2, 129.5, 129.6,
3-Allylisochroman-1-one (3l): Yield: 0.474 g (2.521 mmol
(86%); colorless oil; IR (CHCl3): umax =745, 917, 1118, 1281,
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COMMUNICATIONS
Pragati K Prasad and Arumugam Sudalai
1
1723, 2918, 3077 ; H NMR (200 MHz, CDCl3): d=2.45–2.72
analysis: C9H6O2 requires C 73.97, H 4.14, O 21.89; found:
C 73.94, H 4.17, O 21.89%.
(m, 2H) 2.87–3.07 (m, 2H) 4.51–4.62 (m, 1H), 5.13–5.24 (m,
2H), 5.79–5.97 (m, 1H) 7.21–7.56 (m, 3H), 8.07 (dd, J=0.8
and 7.7 Hz, 1H); 13C NMR (125 MHz,) CDCl3: d=32.5,
39.2, 77.6, 118.8, 125.2, 127.3, 127.6, 130.3, 132.3, 133.6,
138.9, 164.9; HR-MS (ESI+): m/z=211.0730, calcd. for
(C12H12O2)+ [(M+Na)+]: 211.0727; analysis: C12H12O2 re-
quires C 76.57, H 6.43, O 17.00; found: C 76.58, H 6.33, O
17.09%.
2H-Chromen-2-one (3r): Yield: 0.355 g (2.430 mmol,
81%); colorless liquid; IR (CHCl3): umax =820, 1104, 1180,
1
1610, 1710, 3030 cmÀ1; H NMR (200 MHz, CDCl3): d=6.43
(d, J=9.4 Hz, 1H), 7.28–7.57 (m, 4H), 7.77 (d, J=9.4 Hz,
1H); 13C NMR (50 MHz, CDCl3) d 116.7, 116.9, 118.8,
124.4, 127.8, 131.8, 143.5, 154.0, 160.8; analysis: C9H6O2 re-
quires C 73.97, H 4.14, O 21.89; found: C 73.94, H 4.17, O
21.89%.
3-Allyl-7-methylisochroman-1-one (3m): Yield: 0.521 g
(2.579 mmol, 86%); colorless oil; IR (CHCl3): umax =774,
3-Allyl-5-fluoroisobenzofuran-1(3H)-one
(3s):
Yield:
921, 1082, 1194, 1723, 2923, 3078 cmÀ1; H NMR (200 MHz,
0.530 g (2.760 mmol, 92%); colorless oil; IR (CHCl3): umax
=
1
1
CDCl3): d=2.39 (s, 3H), 2.51–2.68 (m, 2H), 2.82–2.94 (m,
2H), 4.48–4.61 (m, 1H), 5.12–5.23 (m, 2H), 5.77–6.00 (m,
1H) 7.10 (d, J=7.7 Hz, 1H) 7.32 (d, J=7.7 Hz, 1H), 7.90 (s,
1H); 13C NMR (50 MHz, CDCl3): d=20.9, 32.1, 39.2, 77.7,
118.7, 124.8, 127.2, 130.4, 132.4, 134.4, 135.9, 137.3, 165.2;
HR-MS (ESI+): m/z=225.0886, calcd. for (C13H14O2)+ [(M+
Na)+]: 225.0884; analysis: C13H14O2 requires C 77.20, H 6.98,
O 15.82; found: C 77.38, H 6.83, O 15.79%.
988, 1100, 1247, 1483, 1604, 1624, 1766, 3100 cmÀ1; H NMR
(200 MHz, CDCl3): d=2.62–2.78 (m, 2H), 5.12–5.25 (m,
2H), 5.48 (t, J=6.1 Hz, 1H), 5.65–5.86 (m, 1H), 7.12–7.28
(m, 2H), 7.89 (dd, J=4.8 and 8.1 Hz, 1H); 13C NMR
(50 MHz, CDCl3): d=38.2, 79.2, 109.3, 117.2, 119.8, 122.2,
127.8, 130.6, 151.9, 163.6, 168.7; analysis: C11H9FO2 requires
C 68.75, H 4.72, F 9.89, O 16.65; found: C 68.82, H 4.97, O,
26.21%.
3-Allyl-6-methoxyisochroman-1-one (3n): Yield: 0.569 g
(2.610 mmol, 87%); colorless oil; IR (CHCl3): umax =778,
3-Allyl-5-methoxyisobenzofuran-1(3H)-one (3t): Yield:
0.518 g (2.551 mmol, 85%); colorless oil; IR (CHCl3): umax
=
917, 1027, 1260, 1606, 1716, 2920, 3076 cmÀ1
;
1H NMR
692, 1073, 1103, 1259, 1605, 1744, 2997 cmÀ1 1H NMR
;
(200 MHz, CDCl3): d=2.48–3.04 (m, 4H), 3.86 (s, 3H),
4.49–4.60 (m, 1H), 5.16–5.24 (m, 2H), 5.83–6.00 (m, 1H),
6.70 (d, J=2.4 Hz, 1H), 6.87 (dd, J=2.4 and 8.3 Hz, 1H),
8.02 (d, J=8.3 Hz, 1H); 13C NMR (50 MHz, CDCl3): d=
32.7, 39.1, 55.4, 77.4, 112.0 113.4, 117.5, 118.7, 132.3, 132.4,
141.2, 163.7, 165.3; HR-MS (ESI+): m/z=241.0835, calcd.
for (C13H14O3)+ [(M+Na)+]: 241.0831; analysis: C13H14O3 re-
quires C 71.54, H 6.47, O 21.99; found: C 71.58, H 6.53, O
21.89%.
(200 MHz, CDCl3): d=2.56–2.81 (m, 2H), 3.91 (s, 3H),
5.15–5.25 (m, 2H), 5.42 (t, J=6.1 Hz, 1H), 5.68- 5.89 (m,
1H), 6.87 (d, J=1.6 Hz, 1H), 7.02 (dd, J=1.6 and 8.5 Hz,
1H), 7.80 (d, J=8.5 Hz, 1H); 13C NMR (50 MHz, CDCl3):
d=38.8, 55.7, 79.3, 106.1, 116.2, 118.7, 119.6, 127.2, 131.3,
152.0, 164.5, 169.8; analysis: C12H12O3 requires C 70.58, H
5.92, O 23.50; found: C 70.61, H 5.67, O 23.72%.
5-Bromoisobenzofuran-1(3H)-one (3u): Yield: 0.498 g
(2.338 mmol (78%); colorless solid; mp 1628C; 1H NMR
(200 MHz, CDCl3): d=5.30 (s, 2H), 7.68 (t, J=3.7 Hz, 2H),
7.77–7.81 (m, 1H); 13C NMR (50 MHz, CDCl3): d=68.8,
124.9, 125.6, 127.1, 129.2, 132.7, 148.2, 169.7; analysis:
C8H5BrO2 requires C 45.11, H 2.37, Br 37.51, O 15.02;
found: C 45.65, H 2.24, Br 38.13, O 13.98%.
3-Allyl-6-fluoroisochroman-1-one (3o): Yield: 0.536 g
(2.640 mmol, 88%); colorless oil; IR (CHCl3): umax =667,
755, 1107, 1267, 1615, 1725, 2919, 3079 cmÀ1 1H NMR
;
(200 MHz, CDCl3): d=2.45–2.72 (m, 2H) 2.84–3.08 (m,
2H), 4.51- 4.65 (m, 1H), 5.16–5.25 (m, 2H), 5.78–5.99 (m,
1H), 6.93 (dd, J=2.3 and 8.1 Hz, 1H), 7.06 (dt, J=2.3 and
8.1 Hz, 1H), 8.10 (dd, J=5.6 and 8.6 Hz, 1H); 13C NMR
(125 MHz, CDCl3): d=32.6, 39.1, 77.5, 114.3, 115.3, 119.1,
121.5, 132.1, 133.3, 141.9, 164.0, 166.8; HR-MS (ESI+):
m/z=229.0635, calcd. for (C12H11O2F)+ [(M+Na)+]:
229.0632; analysis: C12H11O2F requires C 69.89, H 5.38, F
9.21, O 15.52; found: C 69.95, H 5.54, F 9.13, O 15.38%.
3-Heptylisobenzofuran-1(3H)-one (3v): Yield: 0.633 g
(2.728 mmol, 91%); colorless oil; 1H NMR (200 MHz,
CDCl3): d=0.88 (t, J=3.5 Hz, 3H), 1.27–1.47 (m, 10H),
1.66–1.82 (m, 1H), 1.96–2.12 (m, 1H), 5.46 (dd, J=4.0 and
7.4 Hz, 1H), 7.41–7.55 (m, 2H), 7.66 (dt, J=1.6 and 7.6 Hz,
1H). 7.88 (d, J=7.6 Hz, 1H); 13C NMR (50 MHz, CDCl3):
d=14.0, 22.5, 24.8, 29.0, 29.3, 31.7, 34.7, 81.2, 121.6, 125.6,
126.2 128.9, 133.8, 150.0, 170.3; analysis: C15H20O2 requires
C 77.55, H 8.68, O 13.77; found: C 77.58, H 8.71, O 13.71%.
3-Butylisobenzofuran-1(3H)-one (3w): Yield: 0.496 g
(2.610 mmol, 87%); colorless oil; 1H NMR (200 MHz,
CDCl3): d=0.91 (t, J=6.3 Hz, 3H), 1.26–1.52 (m, 4H),
1.71–1.82 (m, 1H), 1.98–2.12 (m, 1H), 5.46 (dd, J=4.1 and
7.2 Hz, 1H), 7.50 (dd, J=7.2 and 9.8 Hz, 2H), 7.67 (t, J=
7.2 Hz, 1H), 7.88 (d, J=7.8 Hz, 1H); 13C NMR (50 MHz,
CDCl3): d=13.8, 22.4, 26.8, 34.4, 81.1, 121.6, 125.6, 126.2,
128.9, 133.8,150.0, 170.2; analysis: C12H14O2 requires C
75.76, H 7.42, O 16.82; found: C 75.54, H 7.57, O 16.89%.
Isobenzofuran-1,3-dione (3x): Yield: 0.426 g (2.878 mmol,
96%); colorless solid; mp 1318C; IR (CHCl3): umax =667,
6,7,8-Trimethoxy-1-oxoisochromane-5-carbonitrile
(3p):
Yield: 0.663 g (2.520 mmol, 84%); yellowish solid; mp
1078C; IR (CHCl3): umax =802, 1036, 1130, 1579, 1677, 1713,
2922, 2949 cmÀ1 1H NMR (200 MHz, CDCl3): d=3.31 (t,
;
J=8.5 Hz, 2H), 3.85 (s, 3H), 3.95 (s, 3H), 4.04 (s, 3H), 4.65
(t, J=8.5 Hz, 2H); 13C NMR (125 MHz, CDCl3): d=27.4,
61.4, 61.8, 62.2, 65.7, 100.3, 113.8, 115.2, 141.2, 145.1, 159.6,
159.7, 161.2; HR-MS (ESI+): m/z=286.0693, calcd. for
(C13H13NO5)+ [(M+Na)+]: 286.0691; analysis: C13H13NO5 re-
quires C 59.31, H 4.98, N 5.32, O 30.39; found: C 58.95, H
4.57, N 5.27, O 31.21%.
6-Allyl-5,6-dihydro-8H-pyranoACTHNUGTRNEUNG[3,4-b]pyridin-8-one (3q):
Yield: 0.476 g (2.518 mmol, 84%); yellow oil; 1H NMR
(200 MHz, CDCl3): d=2.29–2.73 (m, 4H), 5.05–5.19 (m,
2H), 5.23 (s, 1H), 5.79–5.96 (m, 1H), 7.27 (dd, J=4.9 and
7.6 Hz, 1H), 7.92 (dd, J=1.5 Hz and 7.6 Hz, 1H), 8.28 (dd,
J=1.5 and 4.9 Hz, 1H); 13C NMR (125 MHz, CDCl3): d=
40.4, 42.0, 69.3, 118.9, 122.4, 133.3, 134.0, 140.4, 147.7, 151.5;
758, 1052, 1307, 1604, 1748, 1772, 2924 cmÀ1 1H NMR
;
(200 MHz, CDCl3): d=7.77 (dd, J=2.0 and 6.0 Hz, 2H),
7.89 (dd, J=2.0 and 6.0 Hz, 2H); 13C NMR (100 MHz,
CDCl3): d=123.6, 132.7, 134.3, 167.7; HR-MS (ESI+): m/z=
149.0233, calcd. for (C8H5O3)+: 149.0232; analysis: C8H4O3
6
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ÝÝ
These are not the final page numbers!

COMMUNICATIONS
Copper(I) Bromide-Catalyzed Carbonylative Coupling of Aryl Halides
requires C 64.87, H 2.72, O 32.40; found: C 64.82, H 2.77, O
32.41%.
[7] C. F. Koelsch, A. G. Whitney, J. Org. Chem. 1941, 6,
795–803.
2-Benzylisoindoline-1,3-dione
(2.187 mmol, 73%); colorless solid; mp 1158C; IR (CHCl3):
(3y):
Yield:
0.396 g
[8] a) L. Cassar, J. Organomet. Chem. 1973, 54, C57–C58;
b) L. Cassar, M. Fo, F. Montanari, G. P. Mainelli, J. Or-
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[10] M. Sundermeier, A. Zapf, M. Beller, Eur. J. Inorg.
Chem. 2003, 3513–3526, and references cited therein.
[11] a) B. A. Anderson, E. C. Bell, F. O. Ginah, K. Harn,
L. M. Pagh, J. P. Wepsiec, J. Org. Chem. 1998, 63, 8224–
8228; b) M. Sundermeier, A. Zapf, M. Beller, J. Sans,
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ier, A. Zapf, S. Mutyala, W. Baumann, J. Sans, S. Weiss,
M. Beller, Chem. Eur. J. 2003, 9, 1828–1836.
umax =717, 1062, 1331, 1391, 1453, 1715, 1764, 2853,
2924 cmÀ1 1H NMR (200 MHz, CDCl3): d=4.84 (s, 2H),
;
7.24–7.45 (m, 5H), 7.69 (dd, J=2.9 and 5.6 Hz, 2H), 7.84
(dd, J=2.9 and 5.6 Hz, 2H); 13C NMR (50 MHz, CDCl3):
d=41.6, 123.3, 127.8, 128.7, 132.2, 133.9, 136.4, 167.9; HR-
MS (ESI+): m/z=260.0682, calcd. for (C15H11O2NNa)+
[(M+Na)+]: 260.0678; analysis: C15H11NO2 requires C 75.94,
H 4.67, N 5.90, O 13.49; found: C 75.87, H 4.33, N 5.98, O
13.82%.
Acknowledgements
PKP thanks CSIR, New Delhi and Tap Clean Coal Technol-
ogy (CSC 0102). The authors are also thankful to Dr. V.V.
Ranade, Head, Chem. Engg. & Process Develop. for his con-
stant encouragement.
[12] a) D. M. Tschaen, R. Desmond, A. O. King, M. C.
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Pragati K Prasad and Arumugam Sudalai
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COMMUNICATIONS
Copper(I) Bromide-Catalyzed Carbonylative Coupling of
Aryl Halides with Phenols, Alcohols and Amines using
Sodium Cyanide as C1 Source: A Synthesis of Carboxylic
Acid Derivatives
9
Adv. Synth. Catal. 2014, 356, 1 – 9
Pragati K Prasad, Arumugam Sudalai*
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ÞÞ
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