Fujiwara-Moritani Reaction of Weinreb Amides using a Ruthenium-Catalyzed C-H Functionalization Reaction

Article abstract of DOI:10.1002/asia.201500343

The ruthenium-catalyzed Fujiwara-Moritani reaction (oxidative-Heck reaction) of Weinreb amides is reported herein. The reaction affords exclusively ortho-C-H olefination products, has excellent substrate scope and tolerates halogen functionalities, which increase the synthetic utility of the method. A variety of activated olefins as well as styrenes can be employed as coupling partners. RU sure? The ruthenium-catalyzed Fujiwara-Moritani reaction (oxidative-Heck reaction) of Weinreb amides has been reported. The reaction affords exclusively ortho-C-H olefination products, has excellent substrate scope and tolerates halogen functionalities; this increases the synthetic utility of the method.

Full text of DOI:10.1002/asia.201500343

DOI: 10.1002/asia.201500343
Full Paper
Heck Reaction
Fujiwara–Moritani Reaction of Weinreb Amides using
a Ruthenium-Catalyzed CÀH Functionalization Reaction
Riki Das and Manmohan Kapur*[a]
Abstract: The ruthenium-catalyzed Fujiwara–Moritani reac-
tion (oxidative-Heck reaction) of Weinreb amides is reported
herein. The reaction affords exclusively ortho-CÀH olefination
products, has excellent substrate scope and tolerates halo-
gen functionalities, which increase the synthetic utility of the
method. A variety of activated olefins as well as styrenes can
be employed as coupling partners.
Introduction
Over the past few years, the Fujiwara–Moritani reaction[1,2] or
the oxidative Heck reaction has become one of the most versa-
tile and widely utilized reactions in the field of CÀH functionali-
zation.[3] Known initially to be catalyzed by palladium, the
scope of this important transformation has been extended suc-
cessfully to catalysis by several other transition metals.[2] The
only notable drawback of the oxidative Heck reaction is the
need to employ electron-deficient (activated) olefins so as to
ensure a good transformation. However, there have been re-
ports in which electron-neutral olefins have successfully been
employed in this transformation. This reaction has been widely
used on a variety of arenes and quite often Lewis-basic direct-
ing groups[4] have been employed to direct the site-selectivity,
invariably involving metallacycles[5] in the process (Scheme 1).
A variety of directing groups have been employed; these in-
clude amides, O-alkylhydroxamic acids, and Weinreb amides.[6]
In the case of O-alkylhydroxamic acids or simple aryl hydroxa-
mic acids, such transformations invariably result in cleavage of
the sensitive NÀO bond. There are very few reports in which
the NÀO bond survives the oxidative-CÀH olefination reaction
conditions, and most of the research groups deliberately sacri-
fice the N-alkoxyl group as an internal oxidant so as to elimi-
nate the need for an external oxidant.[7–9] Wang and co-workers
reported an efficient catalytic system for the rhodium catalyzed
CÀH olefinations of aryl Weinreb amides in which they used
acrylates as the coupling partners.[7c] In continuation to our ef-
forts in the area of site-selective CÀH functionalization,[10] we
report herein, the ortho-selective ruthenium-catalyzed Fuji-
Scheme 1. Directed Fujiwara–Moritani or oxidative-Heck reaction of arenes.
wara–Moritani reaction of aryl Weinreb amides in which we
have successfully employed a variety of activated olefins as
well as styrenes as coupling partners. The reaction worked
very well with both the coupling partners possessing halogen
functionalities, thereby enhancing the synthetic utility of the
method (Scheme 2).
Results and Discussion
Our efforts were initiated with the optimization of different re-
action conditions for the oxidative Heck-reaction. A variety of
catalyst systems were tested. As we were more interested in
styrenes as coupling partners, the optimization reactions were
carried out with styrene as the olefin source. The palladium
catalyzed combinations did not result in any notable reactions.
With the other reaction conditions that were attempted, either
the reaction was unsuccessful or simply resulted in cleavage of
the NÀO bond of the starting material. Only the ruthenium-cat-
alyzed reactions resulted in notable conversions and the best
transformation was obtained with the in situ-generated cation-
ic ruthenium catalyst using the acetate-assisted CÀH function-
[a] R. Das, Dr. M. Kapur
Department of Chemistry
Indian Institute of Science Education and Research Bhopal
Academic Building II, Indore Bypass Road, Bhauri, Bhopal 462066, MP
(India)
E-mail: mk@iiserb.ac.in
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/asia.201500343.
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selectivity was as expected and exclusively, the ortho-
olefinated products. In all the substrates attempted,
the reaction afforded olefinated products with E-ste-
reochemistry and in some of the substrates 2i–j and
2q, the di-olefinated product was the major product.
Barring styrenes, the reaction was unsuccessful
with electron-neutral olefins. In almost all the cases,
the N-alkoxyl group was lost in the product. The ob-
served outcome, however, was not unexpected as
several reports were available in literature where
such catalytic systems resulted in the loss of the NÀO
bond. An exception was observed in 2r where the
Weinreb amide functionality was found to be intact.
At this moment, we are not sure whether the cleav-
age of the NÀO bond is because it acts as an internal
oxidant, as when a control reaction was carried out
without any coupling partner (the olefin), it simply
resulted in the starting material without the N-alkoxyl
group.
Scheme 2. Previously reported methods and our approach.
In an attempt to check whether modifying the
structure of the Weinreb amide would prevent the
NÀO bond cleavage, we synthesized a new Weinreb
amide of the type 3 in which we incorporated a five-
membered cyclic structure (Table 3). The Fujiwara–
Moritani reactions of this cyclic Weinreb amide, how-
ever, were not very different. As shown in Table 3, in
almost all cases, the product obtained was of the
type 4, in which the isoxazolidine ring had opened
up.
Table 1. Attempts towards optimization of the reaction conditions.
Entry Conditions
Yield[a] [%]
1
PdCl2/AcOH/Cu(OAc)2/DCE/908C/23 h
NR
NR
NR
NR
NR
NR
NR
NR
NR
32
2
3
Pd(OAc)2/AgSbF6/Cu(OTf)2/1,4-dioxane/1008C/24 h
Pd(OAc)2/p-TsOH/BQ/AcOH/608C/25 h
An exception was found in the case of 4g, the NÀ
O bond survived the reaction conditions. As depicted
in Table 3, these substrates also resulted in similar
transformations as the acyclic ones with fair substrate
scope and moderate-to-good yields.
4
5
6
7
8
9
Pd(OAc)2/AgOAc/Cu(OTf)2/Toluene/1008C/24 h
Pd(OAc)2/AgOAc/Cu(OAc)2·H2O/Toluene/1008C/30 h
[RuCl2(p-cymene)]2/AgSbF6/KOAc/1,4-dioxane/1008C/15 h
RuCl2(p-cymene)]2/Cu(OAc)2/MeOH/H2O/air/rt/24 h
[RuCl2(p-cymene)]2/AgSbF6/CuBr2/1,4-dioxane/1008C/24 h
[RuCl2(p-cymene)]2/TFA/TFAA/508C/15 h
Similar to that of acyclic Weinreb amides, in this
case too, a control experiment when conducted
under the reaction conditions, without the olefin
partner, resulted in about 50% of the ring-opened
starting material. The products of the type 4 may
have good synthetic utility as a new hydroxyl func-
tionality has been created that can serve as a handle
for further synthetic manipulations.
10
11
12
13
14
15
16
17
18
[RuCl2(p-cymene)]2/AgSbF6/Cu(OAc)2/DCE/908C/25 h
[RuCl2(p-cymene)]2/AgSbF6/Cu(OAc)2·H2O/DCE/908C/25 h
[RuCl2(p-cymene)]2/AgSbF6/Cu(OAc)2·H2O/DME/1108C/21 h
[RuCl2(p-cymene)]2/AgSbF6/Cu(OAc)2·H2O/Toluene/1108C/23 h
[RuCl2(p-cymene)]2/AgSbF6/Cu(OAc)2·H2O/THF/658C/25 h
44
36
26
19
[RuCl2(p-cymene)]2/AgSbF6/Cu(OAc)2·H2O/1,4-dioxane/1008C/15 h 61
[RuCl2(p-cymene)]2/AgSbF6/Cu(OTf)2/1,4-dioxane/1008C/24 h
[RuCl2(p-cymene)]2/AgOAc/Cu(OTf)2/1,4-dioxane/1008C/14 h
[RuCl2(p-cymene)]2/Ag(TFA)/Cu(OTf)2/1,4-dioxane/1008C/24 h
[RuCl2(p-cymene)]2/NaOAc/Cu(OAc)2 (20 mol%)/O2/DCE/
1008C/20 h
[RuCl2(p-cymene)]2/AgSbF6/Cu(OAc)2/DME/1108C/23 h
[RuCl2(p-cymene)]2/AgSbF6/Cu(OAc)2.H2O/1,4-dioxane/MeOH
1008C/15 h
25
52
33
19
20
21
A plausible mechanism for the transformation is
shown in Scheme 3. The initial coordination of the
carbonyl oxygen to the RuII metal is followed by cy-
clometallation via CÀH activation of the ortho CÀH.
This is followed by coordination of the metal to the
olefin and subsequent carbometallation. Syn-b-hy-
dride elimination followed by removal of a proton
leads to Ru0, which is then converted into RuII by the
oxidant CuII.
9
28
31
22
23
24
25
[RuCl2(p-cymene)]2/AgOAc/Cu(OAc)2·H2O/1,4-dioxane/1008C/15 h 39
[RuCl2(p-cymene)]2/Cu(OAc)2·H2O/1,4-dioxane/1008C/24 h
[RuCl2(p-cymene)]2/AgSbF6/PivOH/1,4-dioxane/1008C/17 h
[RuCl2(p-cymene)]2/AgSbF6/Cu(OAc)2·H2O/Diglyme/1508C/15 h
21
13
18
[a] All yields are yields of isolated products; NR=no result (For details of optimization
table, see the Supporting Information). DCE=1,2-dichloroethane; TFA = trifluoroacetic
acid; TFAA = trifluoroacetic anhydride; DME=1,2-dimethoxyethane; BQ=p-benzoqui-
none.
In this particular transformation, it is postulated by
several research groups that this oxidation to regen-
erate the active catalyst is actually carried out by the
alization[11] (Table 1, entry 15). Under these optimized reaction
conditions, the products were obtained in moderate-to-excel-
lent yields with very good substrate scope (Table 2). The site-
N-alkoxyl group, thus resulting in its cleavage. However, our
control experiments show that even in absence of the olefin
coupling partner, this NÀO bond cleavage is feasible and that
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Conclusions
Table 2. Substrate scope for acyclic Weinreb amides.[a]
In summary, we have carried out the directed Fuji-
wara–Moritani or the oxidative-Heck reaction of Wein-
reb amides using an acetate-assisted ruthenium cata-
lyzed CÀH functionalization reaction. The reaction af-
fords exclusively ortho-olefinated products with good
substrate scope and moderate-to-good yields. The
transformation works very well with styrenes as well
as activated olefins and tolerates halogen functionali-
ties in both the coupling partners.
Experimental Section
General Methods: All commercially available compounds
(Acros, Aldrich, Fluka, Merck etc.,) were used without pu-
rification. Unless otherwise noted, all reactions were per-
formed in oven-dried glassware. All reactions were run
under an atmosphere of argon or nitrogen. All solvents
used in the reactions were purified before use. Tetrahy-
drofuran, 1,4-dioxane and toluene were distilled from
sodium and benzophenone, whereas dry dichlorome-
thane, N,N-dimethylformamide (DMF) and triethylamine
were distilled from CaH2. Petroleum ether with a boiling
range of 40–608C was used. Melting points are uncor-
rected. 1H and 13C NMR spectra were recorded on
a Bruker Avance III 400 MHz NMR spectrometer and
a Bruker Avance III 500 MHz NMR spectrometer; spectra
were recorded at 295 K in CDCl3; chemical shifts are cali-
brated to the residual proton and carbon resonance of
the solvent: CDCl3 (1H: d=7.25; 13C: d=77.0). HRMS:
Bruker Daltonics MicroTOF-Q-II with electron spray ioni-
zation (ESI) or atmospheric pressure chemical ionization
(APCI). GC-HRMS: Performed on Agilent 7200 GC-QToF
(with Electron Impact (EI), 70 eV) with 7890 A GC using
DB-5 column. GC-LRMS: Performed on Agilent 7890 A GC
with Agilent 5975C MS (EI 70 eV) using DB-5 column. IR:
PerkinElmer Spectrum BX FTIR, Shimadzu IRAffinity-1 FTIR
and were recorded as thin films between KBr plates.
X-ray structure of 2d[12]
[a] All yields are yields of isolated product.
Table 3. Substrate scope for cyclic 5-membered Weinreb amides.[a]
The acyclic Weinreb amides were prepared according to
procedures reported in the literature.[13] Hydroxamic acids
used for preparation of the 5-membered cyclic Weinreb
amides were also prepared according to procedures re-
ported in the literature.[14]
General Procedures for the Preparation of Cyclic
Weinreb Amides:
Hydroxamic acid (1 equiv) was dissolved in MeOH/H2O
(3:2) and then Cs2CO3 (3 equiv), KI (0.2 equiv), and 1,3-di-
bromopropane (1.2 equiv) were added. The reaction mix-
ture was allowed to stir at room temperature for 48 h.
This was then concentrated under vacuum and extracted
twice with EtOAc. The organic layer was washed with
brine, dried over anhydrous NaSO4, filtered, and concen-
trated under vacuum. The crude mixture was purified by
silica-gel column chromatography.
[a] All yields are yields of isolated product.
the NÀO bond reduction might actually be proceeding by an
alternative mechanism. It is quite possible that the [RuIIÀH]+
species formed after the b-hydride elimination could play
a role in this NÀO bond reduction. At this moment though, we
do not have conclusive proof for this.
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GCMS or by TLC. Upon completion of the reaction and subsequent
cooling to room temperature, the reaction mixture was diluted
with EtOAc and filtered through a short pad of Celite. The filtrate
was concentrated under reduced pressure and the crude product
was purified by silica-gel column chromatography.
(E)-2-(4-chlorostyryl)-N-methylbenzamide (2a):
Yield: 95%, yellowish-white solid, m.p. 148–1508C, TLC Rf 0.30 (3:2,
1
Petroleum ether/EtOAc); H NMR (400 MHz, CDCl3): d=7.67 (d, J=
8.1 Hz, 1H), 7.47–7.39 (m, 5H), 7.31–7.24 (m, 3H), 6.98 (d, J=
16.2 Hz, 1H), 5.82 (bs, 1H), 2.99 ppm (d, J=5.0 Hz, 3H); 13C NMR
(100 MHz, CDCl3): d=170.14, 135.67, 135.64, 135.29, 133.57, 130.24,
129.92, 128.87, 127.98, 127.67, 127.52, 126.56, 126.16, 26.87 ppm;
IR (KBr): n˜ =3598, 3342, 2354, 2328, 1638, 1535, 1169, 959, 850,
748, 672 cmÀ1
;
ESI-HRMS: Calculated for C16H14ClNO [M+H]+
272.0837, found 272.0842.
(E)-2-(4-bromostyryl)-N-methylbenzamide (2b):
Yield: 82%, white solid, m.p. 139–1428C; TLC Rf 0.30 (3:2, Petrole-
1
um ether/EtOAc); H NMR (400 MHz, CDCl3): d=7.71 (d, J=7.9 Hz,
Scheme 3. Plausible mechanism for the transformation.
1H), 7.53–7.42 (m, 5H), 7.41–7.36 (m, 2H), 7.32 (t, J=7.6 Hz, 1H),
7.01 (d, J=16.3 Hz, 1H), 5.83 (bs, 1H), 3.04 ppm (s, 3H); 13C NMR
(100 MHz, CDCl3): d=170.15, 136.08, 135.65, 135.26, 131.81, 130.24,
129.92, 128.29, 127.69, 127.52, 126.67, 126.14, 121.73, 26.87 ppm;
IR (KBr): n˜ =3593, 2848, 2355, 2337, 1658, 1520, 1167, 801, 751,
687 cmÀ1; ESI-HRMS: Calculated for C16H14BrNO [M+H]+ 316.0332
and 318.0312, found 316.0349 and 318.0330.
Oxazolidin-2-yl(phenyl)methanone (3a):[15]
Prepared according to the general procedure and the title com-
pound was isolated a colourless gel (43% yield). H NMR (400 MHz,
1
CDCl3): d=7.74 (d, J=7.2 Hz, 2H), 7.43 (t, J=7.3 Hz, 1H), 7.36 (t,
J=7.4 Hz, 2H), 3.92 (t, J=6.8 Hz, 2H), 3.84 (t, J=7.3 Hz, 2H),
2.29 ppm (q, J=7.2 Hz, 2H). 13C NMR (100 MHz, CDCl3): d=169.56,
133.49, 131.19, 128.99, 127.90, 69.48, 44.89, 27.37 ppm; ESI-HRMS:
Calculated for C10H11NO2 [M+H]+ 178.0863, found 178.0862.
(E)-N-methyl-2-(4-methylstyryl)benzamide (2c):
Yield: 75%, white solid, m.p. 156–1588C, TLC Rf 0.30 (3:2, Petrole-
1
um ether/EtOAc); H NMR (400 MHz, CDCl3): d=7.71 (d, J=7.9 Hz,
Oxazolidin-2-yl(p-tolyl)methanone (3b):
1H), 7.50 (dd, J=7.6, 1.1 Hz, 1H), 7.45–7.42 (m, 4H), 7.31 (dd, J=
7.5, 1.1 Hz, 1H), 7.20 (d, J=7.9 Hz, 2H), 7.06 (d, J=16.3 Hz, 1H),
5.83 (bs, 1H), 3.04 (d, J=4.9 Hz, 3H), 2.30 ppm (s, 3H); 13C NMR
(100 MHz, CDCl3): d=170.26, 138.00, 135.62, 135.55, 134.31, 131.39,
130.16, 129.43, 127.66, 127.30, 126.73, 126.14, 124.89, 26.85,
21.28 ppm; IR (KBr): n˜ =3231, 2367, 2343, 1674, 1522, 1053, 744,
670 cmÀ1; ESI-HRMS: Calculated for C17H17NO [M+H]+ 252.1383,
found 252.1389.
Prepared according to the general procedure and the title com-
pound was isolated as a yellow gel (64% yield). H NMR (400 MHz,
1
CDCl3): d=7.68 (d, J=8.1 Hz, 2H), 7.19 (d, J=8.0 Hz, 2H), 3.93 (t,
J=6.9 Hz, 2H), 3.86 (t, J=7.4 Hz, 2H), 2.36 (s, 3H), 2.30 ppm (q, J=
7.37 Hz, 2H). 13C NMR (100 MHz, CDCl3): d=170.04, 141.68, 130.55,
129.16, 128.59, 69.42, 44.86, 27.40, 21.52 ppm; ESI-HRMS: Calculat-
ed for C11H13NO2 [M+H]+ 192.1019, found 192.1039.
(E)-N-methyl-2-styrylbenzamide (2d):
Oxazolidin-2-yl(4-methoxyphenyl)methanone (3c):
Yield: 68%, white solid, m.p. 133–1368C, TLC Rf 0.30 (3:2, Petrole-
um ether/EtOAc); H NMR (400 MHz, CDCl3): d=7.67 (d, J=7.87 Hz,
Prepared according to the general procedure and the title com-
pound was isolated as a yellow gel (64% yield). H NMR (400 MHz,
1
1
1H), 7.50–7.46 (m, 3H), 7.45–7.38 (m, 2H), 7.34 (t, J=7.3 Hz, 2H),
7.29–7.25 (m, 2H), 7.04 (d, J=16.3 Hz, 1H), 5.82 (s, 1H), 2.97 ppm
(d, J=4.0 Hz, 3H); 13C NMR (100 MHz, CDCl3): d=170.23, 137.08,
135.65, 135.48, 131.39, 130.19, 128.72, 128.00, 127.62, 127.49,
126.81, 126.20, 125.93, 26.86 ppm; IR (KBr): n˜ =3592, 3310, 2355,
2325, 1649, 1632, 1539, 1315, 1154, 962, 761, 691 cmÀ1; ESI-HRMS:
Calculated for C16H15NO [M+H]+ 238.1226, found 238.1212.
CDCl3): d=7.80 (d, J=8.9 Hz, 2H), 6.89 (d, J=8.9 Hz, 2H), 3.93 (t,
J=6.9 Hz, 2H), 3.87 (t, J=7.6 Hz, 2H), 3.82 (s, 3H), 2.30 ppm (q, J=
7.4 Hz, 2H); 13C NMR (100 MHz, CDCl3): d=169.77, 162.03, 131.29,
125.46, 113.16, 69.43, 55.36, 44.91, 27.36 ppm; ESI-HRMS: Calculat-
ed for C11H13NO3 [M+H]+ 208.0968, found 208.0991.
General Procedure for the Ru-Catalyzed Oxidative Olefina-
tion Reaction:
(E)-2-(4-methoxystyryl)-N-methylbenzamide (2e):
In a pressure tube equipped with a stirrer bar, Weinreb amide
(0.303 mmol) was dissolved in dry 1,4-dioxane (1.5 mL). The reac-
tion mixture was degassed with argon for about 10 min, followed
by the addition of [RuCl2(p-cymene)]2 (4 mol%), AgSbF6 (20%
mmol), Cu(OAc)2·H2O (0.666 mmol), and the olefin partner
(0.909 mmol). The tube was fitted with a Teflon screw cap under
an argon flow. The reaction mixture was heated to 1008C and
stirred at that temperature. The reaction was followed either by
Yield: 61%, white solid, m.p. 102–1058C; TLC Rf 0.30 (3:2, Petrole-
1
um ether/EtOAc); H NMR (400 MHz, CDCl3): d=7.79–7.68 (m, 1H),
7.53–7.42 (m, 4H), 7.34 (d, J=16.8 Hz, 1H), 7.31–7.28 (m, 1H), 7.03
(d, J=16.8 Hz, 1H), 6.92 (d, J=8.4 Hz, 2H), 5.84 (bs, 1H), 3.86 (s,
3H), 3.50 ppm (d, J=4.8 Hz, 3H); 13C NMR (100 MHz, CDCl3): d=
170.34, 159.60, 135.75, 135.42, 131.34, 130.94, 130.14, 129.92
128.55, 128.07, 127.63, 127.10, 126.82, 125.99, 123.74, 114.16, 55.35,
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26.84 ppm; IR (KBr): n˜ =3352, 3063, 2953, 2843, 2357, 2334, 1648,
1633, 1555, 1537, 1517,1414, 1303, 1251, 1176, 1112, 1032, 964,
853, 821, 751, 702, 668 cmÀ1; ESI-HRMS: Calculated for C17H17NO2
[M+H]+ 268.1332, found 268.1343.
1H), 3.88 (s, 3H), 2.98 ppm (3H, s); 13C NMR (100 MHz, CDCl3): d=
169.77, 160.96, 137.43, 136.00, 131.82, 130.09, 129.38, 128.33,
127.02, 121.80, 113.19, 111.38, 55.44, 26.90 ppm; IR (KBr): n˜ =3565,
2354, 2320, 1620, 1520, 1395, 1286, 1217, 1170, 1039, 961, 854,
803, 703 cmÀ1 ESI-HRMS: Calculated for C17H16BrNO2 [M+H]+
;
346.0437 and 348.0417, found 346.0457 and 348.0436.
(E)-N-methyl-2-(2-(naphthalene-1-yl)vinyl)benzamide (2 f):
Yield: 57%, white solid, M.p. 195–1978C; TLC Rf 0.30 (3:2, Petrole-
(E)-2-(4-chlorostyryl)-4-methoxy-N-methylbenzamide (2l):
Yield: 78%, white solid, m.p. 183–1878C; TLC Rf 0.20 (3:2, Petrole-
1
um ether/EtOAc); H NMR (400 MHz, CDCl3): d=8.23 (d, J=8.3 Hz,
1H), 7.91–7.89 (m, 1H), 7.86–7.85 (m, 3H), 7.79 (d, J=7.2 Hz, 1H),
7.57–7.49 (m, 6H), 7.36 (td, J=7.5, 1.1 Hz, 1H), 5.87 (bs, 1H),
3.03 ppm (d, J=4.9 Hz, 3H); 13C NMR ( 100 MHz, CDCl3): d=170.26,
135.82, 135.75, 134.62, 133.70, 131.35, 130.28, 128.89, 128.49,
128.40, 127.68, 126.55, 126.20, 125.87, 125.78, 124.10, 123.64,
26.90 ppm; IR (KBr): n˜ =3665, 3606, 2355, 2325, 1629, 1538, 1164,
1
um ether/EtOAc); H NMR (400 MHz, CDCl3): d=7.52 (d, J=16.1 Hz,
1H), 7.44–7.41 (m, 3H), 7.30 (d, J=8.6 Hz, 2H), 7.14 (d, J=2.2 Hz,
1H), 6.95 (d, J=16.3 Hz, 1H), 6.81 (dd, J=8.4, 2.3 Hz, 1H), 5.75 (bs,
1H), 3.85 (s, 3H), 2.98 ppm (3H, s); 13C NMR (100 MHz, CDCl3): d=
169.78, 160.96, 137.45, 135.56, 133.63, 130.04, 129.38, 128.88,
128.28, 128.02, 126.91 113.15, 111.38, 55.44, 26.90 ppm; IR (KBr):
n˜ =3393, 2359, 2334, 1638, 1525, 1040, 956, 849, 803, 687,
667 cmÀ1; ESI-HRMS: Calculated for C17H16ClNO2 [M+H]+ 302.0942,
found 302.0961.
950, 779, 762, 665 cmÀ1
; ESI-HRMS: Calculated for C20H17NO
[M+Na]+ 310.1202, found 310.1214.
(E)-2-(4-fluorostyryl)-N-methylbenzamide (2g):
Yield: 54%, yellowish white solid, m.p. 118–1208C, TLC Rf 0.30 (3:2,
Petroleum ether/EtOAc); H NMR (400 MHz, CDCl3): d=7.69 (d, J=
(E)-4-Methoxy-N-methyl-2-styrylbenzamide (2m):
1
7.9 Hz, 1H), 7.51–7.40 (m, 5H), 7.31–7.28 (m, 1H), 7.09–7.01 (m,
3H), 5.93 (bs, 1H), 3.02 ppm (d, J=4.8 Hz, 3H); 13C NMR (100 MHz,
CDCl3): d=170.24, 162.53 (d, J=247.8 Hz, 1C), 135.49 (d, J=
18.6 Hz, 2C), 133.33, 130.22, 130.03, 128.35 (d, J=8.1 Hz, 2C),
127.53, 127.50, 126.09, 125.72, 125.70, 115.66 (d, J=21.8 Hz, 2C),
26.87 ppm; IR (KBr): n˜ =3575, 2865, 2391, 2334, 1661, 1542, 1186,
973, 863, 693 cmÀ1; ESI-HRMS: Calculated for C16H14FNO [M+H]+
256.1132, found 256.1152.
Yield: 74%, white solid, m.p. 120–1238C, TLC Rf 0.30 (3:2, Petrole-
um ether/EtOAc); H NMR (400 MHz, CDCl3): d=7.57–7.53 (m, 3H),
1
7.49 (d, J=8.4 Hz, 1H), 7.39 (t, J=7.6 Hz, 2H), 7.31 (d, J=7.6 Hz,
1H), 7.18 (d, J=2.3 Hz, 1H), 7.05 (d, J=16.0 Hz, 1H), 6.85 (dd, J=
8.4 Hz, 2.8 Hz, 1H), 5.8 (bs, 1H), 3.88 (s, 3H), 3.02 ppm (s, 3H);
13C NMR (100 MHz, CDCl3): d=169.87, 160.91, 137.60, 136.99,
131.49, 129.53, 128.73, 128.29, 128.05, 126.85, 126.27, 113.02,
111.36, 55.41, 26.88 ppm; IR (KBr): n˜ =3567, 2362, 2342, 1521, 1149,
1162, 1037, 952, 827, 748, 682 cmÀ1; ESI-HRMS: Calculated for
C17H17NNaO2 [M+Na]+ 290.1151, found 290.1166.
(2E, 2’E)-dibenzyl-3,3,-(2-(methylcarbamoyl)-1,3-phenylene)
diacrylate (2i):
(E)-4-methoxy-N-methyl-2-(2-(naphthalene-1-yl)vinyl)benza-
mide (2n):
Yield: 87%, white solid, M.p. 85–878C, TLC Rf 0.30 (3:2, Petroleum
ether/EtOAc); 1H NMR (400 MHz, CDCl3): d=7.72 (d, J=15.9 Hz,
2H), 7.58 (d, J=7.9 Hz, 2H), 7.38–7.30 (m, 11 H), 6.42 (d, J=15.9 Hz,
2H), 5.92 (d, J=4.8 Hz, 1H), 5.20 (s, 2H), 2.99 ppm (d, J=4.8 Hz,
3H); 13C NMR (100 MHz, CDCl3): d=168.05, 166.00, 141.19, 138.51,
135.86, 132.39, 129.62, 128.61, 128.33, 128.24, 127.85, 121.16,
66.51, 26.86 ppm; IR (KBr): n˜ =3591, 3306, 3063, 2949, 2355, 2329,
1713, 1697, 1647, 1555, 1539, 1454, 1414, 1375, 1314, 1264, 1164,
Yield: 71%, white solid, m.p. 185–1868C; TLC Rf 0.30 (3:2, Petrole-
1
um ether/EtOAc); H NMR (400 MHz, CDCl3): d=8.19 (d, J=8.1 Hz,
1H), 7.87–7.74 (m, 4H), 7.55–7.45 (m, 5H), 7.26–7.24 (m, 1H), 6.85
(dd, J=8.6 Hz, 2.15, 1H), 5.83 (bs, 1H), 3.89 (s, 3H), 2.96 ppm (d,
J=4.7 Hz, 3H); 13C NMR (100 MHz, CDCl3): d=169.86, 160.98,
137.86, 134.50, 133.71, 131.34, 129.60, 129.21, 128.69, 128.59,
128.46, 128.44, 126.21, 125.87, 125.77, 124.17,123.61, 112.97,
111.92, 55.48, 26.90 ppm; IR (KBr): n˜ =3566, 2355, 2325, 1618, 1539,
1285, 1157, 1112, 1040, 950, 768 cmÀ1; ESI-HRMS: Calculated for
C21H19NO2 [M+H]+ 318.1489, found 318.1486.
1013, 976, 805, 751, 697 cmÀ1
;
ESI-HRMS: Calculated for
C28H25NNaO5 [M+Na]+ 478.1625, found 478.1626.
(2E,2E’)-diethyl- 3,3’-(2-methylcarbamoyl)-1,3-phenylene)dia-
crylate (2j):
(E)-4-methoxy-N-methyl-2-(4-methylstyryl)benzamide (2o):
Yield: 58%, white solid, m.p. 138–1408C; TLC Rf 0.30 (3:2, Petrole-
Yield: 67%, white solid, m.p. 127–1298C, TLC Rf 0.30 (3:2, Petrole-
um ether/EtOAc); H NMR (400 MHz, CDCl3): d=7.70 (d, J=15.9 Hz,
1
1
um ether/EtOAc); H NMR (400 MHz, CDCl3): d=7.45 (d, J=3.2 Hz,
2H), 7.62 (d, J=7.9 Hz, 2H), 7.41(t, J=7.9 Hz, 1H), 6.42 (d, J=
15.9 Hz, 2H), 5.73 (bs, 1H), 4.23 (q, J=7.1 Hz, 4H), 3.06 (d, J=
4.9 Hz, 3H), 1.31 ppm (t, J=7.1 Hz, 3H); 13C NMR (100 MHz, CDCl3):
d=168.18, 166.22, 140.58, 138.25, 132.58, 129.65, 127.79, 121.72,
60.74, 26.89, 14.27 ppm; IR (KBr): n˜ =3361, 2354, 1713, 1644, 1367,
1315, 1264, 1174, 1037, 982, 869, 802 cmÀ1; ESI-HRMS: Calculated
for C18H21NO5 [M+H]+ 332.1492, found 332.1503.
1H), 7.42 (d, J=4.4 Hz, 1H), 7.39 (d, J=8.0 Hz, 2H), 7.16–7.12 (m,
3H), 6.97 (d, J=16.2 Hz, 1H), 6.79 (dd, J=8.5, 2.5 Hz, 1H), 5.76 (bs,
1H), 3.84 (s, 3H), 2.96 (d, J=4.9 Hz, 3H), 2.34 ppm (s, 3H); 13C NMR
(100 MHz, CDCl3): d=169.91, 160.91, 138.06, 137.73, 134.21, 131.51,
129.58, 129.45, 128.20, 126.77, 125.22, 112.90, 111.25, 55.40, 26.87,
21.28 ppm; IR (KBr): n˜ =3548, 2364, 2342, 1656, 1523, 1158, 1138,
1048, 942, 826, 758, 686 cmÀ1; ESI-HRMS: Calculated for C18H19NO2
[M+H]+ 282.1489, found 282.1489.
(E)-2-(4-Bromostyryl)-4-methoxy-N-methylbenzamide (2k):
Yield: 82%, white solid, m.p. 186–1888C; TLC Rf 0.20 (3:2, Petrole-
(E)-2-(4-fluorostyryl)-4-methoxy-N-methylbenzamide (2p):
Yield: 53%, white solid, m.p. 135–1408C; TLC Rf 0.30 (3:2, Petrole-
1
um ether/EtOAc); H NMR (400 MHz, CDCl3): d=7.53 (d, J=16.4 Hz,
1H), 7.47–7.42 (m, 3H), 7.36 (d, J=9.3 Hz, 2H), 7.14 (d, J=2.4 Hz,
1H), 6.94 (d, J=16.2 Hz, 1H), 6.81 (dd, J=8.6, 2.4 Hz, 1H), 5.75 (bs,
1
um ether/EtOAc); H NMR (400 MHz, CDCl3): d=7.52–7.46 (m, 4H),
Chem. Asian J. 2015, 10, 1505 – 1512
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7.17 (d, J=2.6 Hz, 1H), 7.07 (t, J=8.6 Hz, 2H), 7.00 (d, J=16.1 Hz,
1H), 6.84 (dd, J=8.6, 2.6 Hz, 1H), 5.84 (bs, 1H), 3.89 (s, 3H),
3.02 ppm (d, J=5.4 Hz, 3H); 13C NMR (100 MHz, CDCl3): d=169.88,
162.25 (d, J=261.7 Hz, 1C), 137.58, 133.23 (d, J=25.0 Hz, 2C),
130.18, 129.41, 128.41(d, J=64 Hz, 2C), 128.19, 126.06, 126.05,
115.68 (d, J=17.3 Hz, 2C), 112.99, 111.32, 55.43, 26.90 ppm; IR
(KBr): n˜ =3276, 2364, 2338, 1654, 1515, 1224, 1035, 952, 842, 680,
667 cmÀ1; ESI-HRMS: Calculated for C17H16FNO2 [M+H]+ 286.1238,
found 286.1263.
(E)-N,2-dimethyl-6-(2-(naphthalene-1-yl)vinyl)benzamide
(2u):
Yield: 54%, white solid, m.p. 210–2138C; TLC Rf 0.30 (3:2, Petrole-
1
um ether/EtOAc); H NMR (400 MHz, CDCl3): d=8.17 (d, J=8.1 Hz,
1H), 7.87–7.78 (m, 3H), 7.68 (d, J=7.1 Hz, 1H), 7.61 (d, J=7.8 Hz,
1H), 7.54–7.44 (m, 3H), 7.31(t, J=7.6 Hz, 1H), 7.18–7.12 (m, 2H),
5.7 (bs, 1H), 2.99 (d, J=5.2 Hz, 3H), 2.36 ppm (s, 3H); 13C NMR
(100 MHz, CDCl3): d=170.68, 136.78, 135.08, 134.74, 134.68, 133.67,
131.33, 129.49, 129.10, 128.67, 128.66, 128.33, 128.26, 126.20,
125.88, 125.74, 123.97, 123.69, 123.12, 26.63, 19.27 ppm; IR (KBr):
n˜ =3366, 2358, 2338, 1649, 1517, 1031, 796, 770, 739, 667 cmÀ1
ESI-HRMS: Calculated for C21H19NNaO [M+Na]+ 324.1359, found
;
Dimethyl 4,4’-((1E,1E’)-(2-(methylcarbamoyl)-1,3-phenylene)-
bis (ethane-2,1-diyl))dibenzoate (2q):
324.1347.
Yield: 86%, white solid, m.p. 127–1298C; TLC Rf 0.30 (3:2, Petrole-
um ether/EtOAc); H NMR (400 MHz, CDCl3): d=8.04 (d, J=8.4 Hz,
1
(E)-benzyl 3-(2-((3-hydroxypropyl)carbamoyl)-5-methoxy-
phenyl) acrylate (4a):
4H), 7.66 (d, J=7.3 Hz, 2H), 7.55 (d, J=7.9 Hz, 4H), 7.44 (t, J=
8.6 Hz, 1H), 7.30 (d, J=16.0 Hz, 2H), 7.12 (d, J=16.0 Hz, 2H), 5.87
(bm, 1H), 3.94 (s, 6H), 3.10 ppm (d, J=5.2 Hz, 3H); 13C NMR
(100 MHz, CDCl3): d=169.77, 166.83, 141.32, 136.20, 134.49, 130.42,
130.05, 129.47, 129.32, 127.64, 126.65, 125.08, 52.17, 26.82 ppm; IR
(KBr): n˜ =3402, 2359, 2356, 2331, 1647, 1540, 1278, 1174, 955, 693,
Yield: 72%, white solid, m.p. 109–1108C, TLC Rf 0.20 (3:2, Petrole-
1
um ether/EtOAc); H NMR (400 MHz, CDCl3): d=8.09 (d, J=15.9 Hz,
1H), 7.48 (d, J=8.5 Hz, 1H), 7.45–7.31 (m, 5H), 7.06 (d, J=2.5 Hz,
1H), 6.91 (dd, J=8.5, 2.5 Hz, 1H), 6.47 (bs, 1H), 6.40 (d, J=15.9 Hz,
1H), 5.25 (s, 2H), 3.72 (t, J=5.6 Hz, 2H), 3.59 (q, J=6.0 Hz, 2H),
1.76 ppm (qt, J=5.8 Hz, 2H); 13C NMR (100 MHz, CDCl3): d=169.10,
166.50, 160.96, 142.82, 135.82, 134.40, 129.79, 129.44, 128.70,
128.63, 128.38, 120.43, 115.63, 111.88, 66.61, 60.12, 55.47, 37.59,
31.97 ppm; IR (KBr): n˜ =3428, 3318, 2334, 2355, 1866, 1731, 1714,
1696, 1647, 1539, 1455, 1315 cmÀ1; ESI-HRMS: Calculated for
C21H23NO5 [M+H]+ 370.1649, found 370.1665.
666 cmÀ1
;
ESI-HRMS: Calculated for C28H25NNaO5 [M+Na]+
478.1625, found 478.1629.
(E)-2-(2-cyanovinyl)-N-methoxy-N-methylbenzamide (2r):
Yield: 69%, white solid, m.p. 70–748C, TLC Rf 0.30 (3:2, Petroleum
1
ether/EtOAc); H NMR (400 MHz, CDCl3): d=7.56–7.54 (m, 1H), 7.47
(d, J=16.6 Hz, 1H), 7.43–7.40 (m, 2H), 7.38–7.36 (m, 1H), 5.87 (d,
J=16.6 Hz, 1H), 3.40–3.33 ppm (m, 6H); 13C NMR (100 MHz, CDCl3):
d=168.86, 147.62, 135.53, 130.86, 130.52, 129.87, 127.53, 125.65,
117.83, 98.60, 61.27, 32.64 ppm; IR (KBr): n˜ =3545, 3022, 2219,
1644, 1487, 1447, 980, 774, 639, 570 cmÀ1; ESI-HRMS: Calculated
for C12H12N2O2 [M+H]+ 217.0972, found 217.0987.
(2E,2’E)-dibenzyl 3,3’-(2-((3-hydroxypropyl)carbamoyl)-5-
methyl-1,3-phenylene)diacrylate (4b):
Yield: 73%, white solid, m.p. 113–1148C, TLC Rf 0.20 (3:2, Petroleum
ether/EtOAc); 1H NMR (400 MHz, CDCl3): d=7.80 (d, J=15.9 Hz,
2H), 7.44 (s, 2H), 7.45–7.33 (m, 10H), 6.46 (d, J=15.9 Hz, 2H), 6.33
(t, J=5.9 Hz, 1H), 5.24 (s, 4H), 3.70 (t, J=5.8 Hz, 2H), 3.62 (q, J=
5.9 Hz, 2H), 2.38 (s, 3H), 1.80 ppm (qt, J=5.8 Hz, 2H); 13C NMR
(100 MHz, CDCl3): d=168.04, 166.36, 141.54, 139.57, 136.06, 135.77,
132.20, 128.63, 128.49, 128.38, 128.36, 120.67, 66.63, 60.46, 37.78,
31.74, 21.32 ppm; IR (KBr): n˜ =3441, 2355, 2329, 1712, 1634, 1596,
1539, 1454, 1376, 1314, 1264, 1167, 1070, 974, 856, 751, 699,
(E)-Benzyl 3-(5-bromo-2-(methylcarbamoyl)phenyl)acrylate
(2s):
Yield: 66%, white solid, m.p. 123–1268C; TLC Rf 0.30 (3:2, Petrole-
1
um ether/EtOAc); H NMR (400 MHz, CDCl3): d=7.99 (d, J=16.0 Hz,
1H), 7.77 (d, J=2 Hz, 1H), 7.64–7.55 (m, 1H), 7.42–7.34 (m, 6H),
6.45 (d, J=16.2 Hz, 1H), 5.79 (bs, 1H), 5.26 (s, 2H), 3.02 ppm (s,
3H); 13C NMR ( 100 MHz, CDCl3): d=168.30, 165.84, 140.99, 135.84,
134.72, 132.70, 131.78, 130.07, 129.18, 128.61, 128.47, 128.28,
124.62, 121.67, 66.56, 26.96 ppm; IR (KBr): n˜ =3295, 2364, 2343,
1693, 1652, 1555, 1313, 1167, 1007, 974, 748 cmÀ1; ESI-HRMS: Cal-
culated for C18H16BrNO3 [M+H]+ 374.0386 and 376.0367, found
374.0387 and 376.0370.
575 cmÀ1
;
ESI-HRMS: Calculated for C31H31NNaO6 [M+Na]+
536.2044, found 536.2070.
(E)-methyl-3-(2-((3-hydroxypropyl)carbamoyl)-3-methylphen-
yl) acrylate (4c):
Yield: 68%, viscous pale yellow gel, TLC Rf 0.20 (3:2, Petroleum
ether/EtOAc); 1H NMR (400 MHz, CDCl3): d=7.72 (d, J=15.9 Hz,
1H), 7.41 (d, J=7.7 Hz, 1H), 7.25 (t, J=8.1 Hz, 1H), 7.18 (d, J=
7.5 Hz, 1H), 6.38 (d, J=15.9 Hz, 1H), 6.37 (bs, 1H), 3.85–3.70 (m,
5H), 3.63–3.53 (m, 2H), 2.31 (s, 3H) 1.81 ppm (qt, J=6.1 Hz, 2H);
13C NMR (100 MHz, CDCl3): d=169.57, 167.32, 141.99, 138.03,
135.42, 131.99, 131.21, 129.18, 123.65, 119.82, 60.17, 51.85, 37.27,
31.94, 19.18 ppm; IR (KBr): n˜ =3434, 2334, 2318, 1742, 1714, 1685,
1643, 1539, 1456, 1317, 1064, 965, 864, 782, 658 cmÀ1; ESI-HRMS:
Calculated for C15H19NNaO4 [M+Na]+ 300.1206, found 300.1209.
(E)-benzyl 3-(3-methyl-2-(methylcarbomyl)phenyl)acrylate
(2t):
Yield: 61%, white solid, m.p. 78–808C; TLC Rf 0.30 (3:2, Petroleum
ether/EtOAc); 1H NMR (400 MHz, CDCl3): d=7.74 (d, J=16.0 Hz,
1H), 7.44–7.33 (m, 6H), 7.29–7.26 (m, 1H), 7.21 (d, J=7.8 Hz, 1H),
6.43 (d, J=15.9 Hz, 1H), 5.91 (bs, 1H), 5.22 (s, 2H), 3.01 (d, J=
5.2 Hz, 3H), 2.33 ppm (s, 3H); 13C NMR (100 MHz, CDCl3): d=
169.58, 166.33, 142.17, 138.23, 135.98, 135.42, 131.92, 131.33,
129.11, 128.58, 128.25, 128.19, 123.80, 120.04, 66.35, 26.55,
19.13 ppm; IR (KBr): n˜ =3289, 3067, 2949, 2365, 2343, 1716, 1650,
1591, 1542, 1458, 1409, 1376, 1313, 1262, 1233, 1164, 1088, 979,
(2E,2’E)-diethyl 3,3’-(2-((3-hydroxypropyl)carbomoyl)-5-me-
thoxy-1,3-phenylene)diacrylate (4d):
866, 791, 739, 648 cmÀ1
;
ESI-HRMS: Calculated for C19H19NO3
Yield: 63%, white solid, m.p. 102–1088C, TLC Rf 0.20 (3:2, Petrole-
[M+H]+ 310.1438, found 310.1447.
um ether/EtOAc); H NMR (400 MHz, CDCl3): d=7.76 (d, J=15.9 Hz,
1
Chem. Asian J. 2015, 10, 1505 – 1512
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ꢀ 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

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2H), 7.13 (s, 2H), 6.40 (d, J=15.9 Hz, 2H), 6.34 (t, J=5.9 Hz, 1H),
4.27 (q, J=7.1 Hz, 4H), 3.88 (s, 3H), 3.82 (t, J=5.8 Hz, 2H), 3.67 (q,
J=6.8 Hz, 2H), 1.89 (quintet, J=5.8 Hz, 2H), 1.75 (bs, 1H),
1.34 ppm (t, J=7.1 Hz, 6H); 13C NMR (100 MHz, CDCl3): d=168.07,
166.42, 159.77, 140.84, 133.79, 131.60, 121.26, 112.89, 60.84, 60.11,
55.51, 37.48, 31.83, 14.21 ppm; IR (KBr): n˜ =3356, 2982, 2940, 2359,
1714, 1646, 1596, 1541, 1458, 1368, 1272, 1178, 1038, 974,
Keywords: amides
Moritani · oxidative Heck · ruthenium
·
CÀH functionalization
·
Fujiwara–
[1] a) I. Moritanl, Y. Fujiwara, Tetrahedron Lett. 1967, 8, 1119–1122; b) Y. Fuji-
wara, I. Moritani, S. Danno, R. Asano, S. Teranishi, J. Am. Chem. Soc.
1969, 91, 7166–7169.
859 cmÀ1
;
ESI-HRMS: Calculated for C21H27NNaO7 [M+Na]+
428.1680, found 428.1654.
[2] For reviews related to this topic see a) J. Le Bras, J. Muzart, Chem. Rev.
2011, 111, 1170–1214; b) C. S. Yeung, V. M. Dong, Chem. Rev. 2011, 111,
1215–1292. See also: c) S. Kozhushkov, L. Ackermann, Chem. Sci. 2013,
4, 886–896; d) X. Shang, Z.-Q. Liu, Chem. Soc. Rev. 2013, 42, 3253–
3260; e) T. Kitamura, Y. Fujiwara, in From C-H to C-C bonds: Cross-Dehy-
drogenative-Coupling (Ed.: C.-J. Li), RSC Green Chemistry Series 2015, 26,
pp 33–54f) L. Zhou, W. Lu, Chem. Eur. J. 2014, 20, 634–642; g) J.
Le Bras, J. Muzart, Synthesis 2014, 1555–1572; h) W. Rauf, J. M. Brown,
Chem. Commun. 2013, 49, 8430–8440. For a new dimension in oxida-
tive Heck reactions, see i) J. Wang, C. Liu, J. Yuan, A. Lie, Angew. Chem.
Int. Ed. 2013, 52, 2256–2259; Angew. Chem. 2013, 125, 2312–2315; j) C.
Liu, D. Liu, A. Lie, Acc. Chem. Res. 2014, 47, 3459–3470; k) L. Meng, C.
Liu, W. Zhang, C. Zhou, A. Lie, Chem. Commun. 2014, 50, 1110–1112;
l) D. Liu, C. Liu, H. Li, A. Lie, Chem Commun. 2014, 50, 3623–3626; m) S.
Tang, Y. Wu, W. Liao, R. Bai, C. Liu, A. Lie, Chem. Commun. 2014, 50,
4496–4499; n) D. Liu, C. Liu, A. Lie, Pure Appl. Chem. 2014, 86, 321–
328; o) H. Cao, D. Liu, C. Liu, X. Hu, A. Lie, Org. Biomol. Chem. 2015, 13,
2264–2266; p) S. Tang, K, Liu, C. Liu, A. Lie, Chem. Soc. Rev. 2015, 44,
1070–1082.
(2E,2’E)-diethyl-3,3’-(2-((3-hydroxypropyl)carbamoyl)-5-
methyl-1,3-phenylene)diacrylate (4e):
Yield: 61%, white solid, m.p. 149–1548C, TLC Rf 0.20 (3:2, Petrole-
1
um ether/EtOAc); H NMR (400 MHz, CDCl3): d=7.74 (d, J=15.9 Hz,
2H), 7.44 (s, 2H), 6.45 (t, J=6.0 Hz, 1H), 6.40 (d, J=15.9 Hz, 2H),
4.25 (q, J=7.1 Hz, 4H), 3.80 (t, J=5.8 Hz, 2H), 3.66 (q, J=5.9 Hz,
2H), 2.40 (s, 3H), 1.88 (qt, J=5.9 Hz, 2H), 1.33 (t, J=7.1 Hz, 6H),
1.27 ppm (bs, 1H); 13C NMR (100 MHz, CDCl3): d=168.21, 166.62,
140.96, 139.47, 135.94, 132.25, 128.34, 121.00, 60.83, 60.35, 37.67,
31.84, 21.34, 14.26 ppm; IR (KBr): n˜ =3361, 3296, 2359, 2334, 1699,
1635, 1557, 1541, 1368, 1316, 1268, 1181, 1040, 985, 864, 693 cmÀ1
ESI-HRMS: Calculated for C21H27NO6 [M+H]+ 390.1911, found
;
390.1920.
[3] For some selected reviews on CÀH Functionalization a) A. E. Shilov, G. B.
Shul’pin, Chem. Rev. 1997, 97, 2879–2932; b) J. A. Labinger, J. E. Bercaw,
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(E)-2-(4-chlorostyryl)-N-(3-hydroxypropyl)-4-methylbenza-
mide (4 f):
Yield: 58%, white solid, m.p. 124–1278C, TLC Rf 0.20 (3:2, Petrole-
1
um ether/EtOAc); H NMR (400 MHz, CDCl3): d=7.55–7.47 (m, 2H),
7.45 (d, J=8.5 Hz, 2H), 7.40 (d, J=7.8 Hz, 1H), 7.34 (d, J=8.5 Hz,
2H), 7.13 (d, J=7.8 Hz, 1H), 6.99 (d, J=16.3 Hz, 1H), 6.26 (bs, 1H),
3.74 (t, J=5.3 Hz, 2H), 3.63 (q, J=6.3 Hz, 2H), 2.42 (s, 3H), 1.79 (qt,
J=5.8 Hz, 2H), 1.68 ppm (bs, 1H); 13C NMR (100 MHz, CDCl3): d=
170.75, 140.62, 135.62, 135.42, 133.55, 132.42, 129.84, 128.94,
128.51, 127.90, 127.66, 126.87, 126.61, 59.47, 36.87, 32.34,
21.48 ppm; IR (KBr): n˜ =3670, 3593, 2918, 2852, 2650, 2549, 2354,
2325, 1673, 1515, 1153, 1044, 958, 812, 684, 663 cmÀ1; ESI-HRMS:
Calculated for C19H20ClNNaO2 [M+Na]+ 352.1075, found 352.1047.
(E)-isoxazolidin-2-yl(4-methyl-2-(2-(phenylsulfonyl)vinyl)-
phenyl) methanone (4g):
Yield: 48%, white solid, m.p. 158–1608C, TLC Rf 0.30 (2:3, Petrole-
1
um ether/EtOAc); H NMR (400 MHz, CDCl3): d=7.92–7.90 (m, 2H),
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7.82 (d, J=15.4 Hz, 1H), 7.60–7.56 (m, 1H), 7.53–7.49 (m, 2H), 7.36
(d, J=7.9 Hz, 1H), 7.32 (s, 1H), 7.24–7.21 (m, 1H), 6.82 (d, J=
15.4 Hz, 1H), 4.91–3.68 (m, 4H), 2.73–2.15 ppm (m, 5H); 13C NMR
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21.30 ppm; IR (KBr): n˜ =3430, 3054, 3021, 2351, 1631, 1447, 1305,
1147, 1081, 974, 838, 746, 627 cmÀ1; ESI-HRMS: Calculated for
C19H19SNO4 [M+K]+ 396.0666, found 396.0687.
Acknowledgements
Funding from DST-India (SB/S1/OC-10/2014) and CSIR-India
(02(205)/14/EMR-II) is gratefully acknowledged. R.D. thanks
UGC-India for a Research Fellowship. We thank CIF, IISERB for
the analytical data and Ms. Anusha Upadhyay, IISERB for the X-
ray data. We also acknowledge the Director, IISERB, for funding
and the infrastructure facilities.
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Manuscript received: April 3, 2015
Final article published: May 29, 2015
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