Oxidative coupling of NH isoquinolones with olefins catalyzed by Rh(III)

Article abstract of DOI:10.1021/jo2002209

Rh(III)-catalyzed oxidative coupling reactions between isoquinolones with 3-aryl groups and activated olefins have been achieved using anhydrous Cu(OAc)₂ as an oxidant to give tetracyclic products. The nitrogen atom acts as a directing group to

Full text of DOI:10.1021/jo2002209

NOTE
pubs.acs.org/joc
Oxidative Coupling of NH Isoquinolones with Olefins Catalyzed by
Rh(III)
Fen Wang,†,‡ Guoyong Song,† Zhengyin Du,*,‡ and Xingwei Li*,†
†Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China
‡College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou 730070, China
S Supporting Information
b
ABSTRACT: Rh(III)-catalyzed oxidative coupling reactions be-
tween isoquinolones with 3-aryl groups and activated olefins have
been achieved using anhydrous Cu(OAc)2 as an oxidant to give
tetracyclic products. The nitrogen atom acts as a directing group
to facilitate ortho CꢀH activation. This reaction can be one-pot
starting from methyl benzohydroxamates, without the necessity of
the isolation of isoquinolone products. A broad scope of substrates
has been demonstrated, and both terminal and internal activated
olefins can be applied. In the coupling of N-methylmaleimide, a Wacker-like mechanism was proposed, where backside attack of the
NH group in isoquinolones is suggested as a key step. Selective CꢀH activation has also been achieved at the 8-position of
1-naphthol, leading to an olefination product.
n the past decade, oxidative functionalization of CꢀH bonds,
particularly sp2 CꢀH bonds, that proceeds via a CꢀH activa-
synthetic utility of Rh(III)-catalyzed coupling reactions. We have
also reported17a that either the N or the O atom in NH
isoquinolones (tautomers of 1-hydroxyisoquinolones) can act
as an efficient directing group to achieve activation of proximal
CꢀH bonds and subsequent oxidative functionalization with
alkynes (eq 2). Given functional similarities between alkynes and
alkenes, we anticipate that NH isoquinolones, together with
structurally related 1-naphthols, can undergo oxidative olefina-
tion with activated alkenes such as acrylates. Notably, three types
of products (AꢀC) as given in eq 3 can be envisioned, as a result
of chemoselectivity of CꢀH activation and regioselectivity of
olefin insertion. In fact, products of the types A and B are
reported in this work.
I
tion pathway has attracted increasing attention, and synthetic
methods based on these strategies provide powerful tools to
construct complex structures.1 Metal-catalyzed direct CꢀH
activation followed by oxidative functionalization with alkenes
(the oxidative Heck-type reaction2) has emerged as an attractive
and atom-economic alternative to the traditional Heck coupling3
because each partner is minimally functionalized and no prior
activation of the coupling partner is necessary. It is well-known
that palladium catalysts have been predominantly used for this
type of transformation,4,5 although other metals such as ruthe-
nium have also been reported.6
Rhodium catalysts stand out in the area of CꢀH functionaliza-
tion via CꢀH activation pathway either in redox or redox-neutral
reactions.1d,j,7 The wide applications of rhodium catalysts in CꢀH
activation is due to their wide functional group tolerance, high
selectivity, and compatibility with oxidants. Despite the rather
limited examples of rhodium-catalyzed oxidative Heck reactions,8
there is rapidly increasing interest in using low loading of Rh(III)
complexes that give high selectivity and broad substrate scope
(Scheme 1). Recently, Miura and Satoh,9ꢀ11 Glorius,12,13 Ellman
and Bergman,14 and we15,16 have made some progress in rhodium-
catalyzed cross-coupling between olefins and arenes under chela-
tion assistance. We now report the oxidative olefination of NH
isoquinolone and 1-naphthol.
We recently reported Rh(III)-catalyzed oxidative coupling of
benzamides with activated olefins leading to γ-lactams, with the
olefination product proposed as an intermediate (eq 1).16 Here
the role of amide as a directing group is significant.17 Under-
standing, designing, and exploring other readily installable direct-
ing groups should be an important task that serves to expand the
Received: February 4, 2011
Published: March 17, 2011
r
2011 American Chemical Society
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NOTE
Scheme 1. Rh(III)-Catalyzed Oxidative Olefination
methyl benzohydroxamate. Indeed, when methanol solvent
was evacuated after the completion of the reaction between
methyl benzohydroxamate and alkyne, addition of Cu(OAc)2,
benzyl acrylate (115 °C), and MeCN provided a suitable set
of conditions for oxidative olefination (conditions B). Under
these conditions, 3a was obtained in an overall yield of 78%.
This also suggests that the presence of a catalytic amount of
CsOAc has essentially no detrimental effect on the oxidative
olefination step.
We initiated our exploration with an attempt to oxidatively
couple benzyl acrylate with NH isoquinolone 1a. Importantly,
novel synthesis of 1a and its analogues was recently reported18
by Fagnou and co-workers under redox-neutral conditions
using a combination of [RhCp*Cl2]2 (2.5 mol %) and CsOAc
(30 mol %) starting from readily available methyl benzohydrox-
amate [PhC(O)NH(OMe)] and an alkyne (MeOH, 60 °C).
This important synthetic method allows easy access to a variety
of NH isoquinolones. We found that our previously reported
conditions for the coupling of benzamides with benzyl acrylate
(eq 1, 4 mol % of [RhCp*Cl2]2, 2.1 equiv of Ag2CO3, MeCN,
115 °C) proved successful, and 3a was isolated as the only
product in 83% yield. The structure of this product was eluci-
dated on the basis of NMR spectroscopy and mass spectrometry.
In particular, 13C NMR spectroscopy revealed that two CH2
groups are present. This reaction possibly proceeds via an oxida-
tive olefinationꢀhydroamination cascade.5d The efficiency of
this reaction was further improved when Cu(OAc)2 (2.2 equiv)
was used as an inexpensive oxidant, where the catalyst loading
can be reduced to 2 mol %. Under these improved conditions
(conditions A), product 3a was isolated in comparably high yield
(eq 4). In contrast, no coupling reaction was observed when the
olefin was replaced by styrene.
With the optimized conditions in hand, we explored a series of
substrates under both one-pot and stepwise conditions. Isolated
NH isoquinolone 1a readily coupled with a few acrylates to give
3aꢀe in isolated yields ranging from 55 to 86% (Table 1). Other
activated alkenes such as an acrylamide and an acrylonitrile can be
applied, although relatively lower yields of 3f (50%) and 3g (58%)
were obtained under conditions B. In these cases, the reactions are
quite selective, and most of the unreacted 1a was recovered. The
scope of isoquinolones was further defined in the coupling with
benzyl acrylate under conditions A. Isolated isoquinolones bearing
electron-donating (see 3i, 3j, and 3m) and -withdrawing groups
(see 3h, 3k, 3k0, and 3l) in the phenyl ring are applicable, although
introduction of a highly withdrawing m-CF3 group tends to slow
down this coupling reaction (3h). When an m-methyl-substituted
methyl benzohydroxamate was used under either conditions A or
B, 3i was isolated as the only product. In contrast, when an m-
fluoro-substituted methyl benzohydroxamate was allowed to react
with benzyl acrylate under the one-pot conditions, two regioi-
somers were isolated as analytically pure products in similar yields
(41% for 3k and 45% for 3k0). The low regioselectivity of CꢀH
activation in the first step is most likely ascribed to the reduced
steric bulk of a fluoro group and/or its directing effect.16
Using isolated isoquinolones synthesized from other symmetri-
cally substituted alkynes (ArCꢁCAr) for oxidative olefination also
proved successful, and both electron-donating and -withdrawing
groups in the Ar group can be tolerated. Thus 3o and 3p were
isolated in high yield. In addition, an isoquinolone derived from
an unsymmetrically substituted alkyne (MeCꢁCPh) under-
went smooth coupling with benzyl acrylate to give 3n in high
yield, with the methyl group oriented distal to the nitrogen,
which is consistent with previous reports.17a,19 In contrast to
the above success, (isolated) NH isoquinolone 4 obtained from
the reaction of 4-octyne and PhC(O)NH217a failed to give any
desired coupling with benzyl acrylate (eq 5) even with 4 mol %
loading of the catalyst, indicating that neither the CꢀH bond in
Since the same catalyst [RhCp*Cl2]2 was used both in the
redox-neutral preparation of NH isoquinolines and in their
oxidative functionalization with alkynes, we reasoned that an
overall one-pot synthesis of products 3 could be achievable from
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NOTE
Table 1. Rh(III)-Catalyzed Oxidative Coupling of NH Isoquinolones and Alkenesaꢀc
a Isolated yield. b Conditions indicated in parentheses after the yield. c Conditions A: isoqunolone (0.5 mmol), olefin (1.0 mmol), Cu(OAc)2 (1.1 mmol),
[RhCp*Cl2]2 (0.01 mmol), MeCN (4 mL) 115 °C, 16 h, sealed tube under N2. Conditions B: PhC(O)NH(OMe) (0.5 mmol), alkyne (0.51 mmol),
[RhCp*Cl2]2 (0.015 mmol), CsOAc (0.15 mmol), MeOH (3 mL), 60°, 14 h, then evacuated, olefin (1.0 mmol), Cu(OAc)2 (1.1 mmol), MeCN (4 mL),
115 °C, sealed tube under N2, 16 h.
the alkyl chain nor the CꢀH bond ortho to the carbonyl group
The alkene substrate is not limited to a terminal one.
Internal alkenes bearing vicinal withdrawing groups also
underwent CꢀH activation. This is in contrast to the observed
oxidative coupling of 4 and analogues with alkynes, where
CꢀH activation occurred at the position ortho to the carbonyl
group.17a
coupled with 1a under the standard conditions A to give
analogous products. Thus 3r was isolated in 40% yield when
N-methylmaleimide was used, and product 3s was obtained in
similar yields starting from either diethyl maleate or fumarate.
In all of these cases, unreacted starting material 1a was
essentially fully recovered.
We reasoned that the olefination intermediate given in
eq 4 cannot be a reasonable one in the reaction of 1a and
N-methylmaleimide if this coupling follows a cyclometalationꢀolefin
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NOTE
Scheme 2. Plausible Mechanism of the Coupling of an Internal Olefin with an NH Isoquinolone
insertionꢀβ-H elimination process (the Heck-like mechanism)
(Scheme 2). This is because both olefin insertion and β-H
elimination occur via a syn-coplanar, four-membered ring transi-
tion state, and the cyclic character of this olefin obviates the
possibility of β-H elimination. A plausible Wacker-like mechan-
ism to account for the observed reaction is proposed in Scheme 2.
Coordination of the olefin on Rh(III) center serves to activate
the CdC bond toward nucleophiles. Backside attack of the NH
group in 1a at the activated olefin is proposed to give a trans
hydroamination (amidorodation) product (D).20 β-Hydride
elimination of D is proposed and is followed by reinsertion into
olefin intermediate E, which gives rise to the isomerization of the
intermediate D to a Rh(III) species F.21 Subsequent cyclometa-
lation of F is proposed to give a rhodacycle G, from which CꢀC
reductive elimination occurs to afford the final product. In
contrast to the proposed cyclometalation of intermediate F, no
such process is suggested for intermediate D which eventually
gives product C (eq 3). This is likely because intermediate F can
lead to a favorable six-membered ring rhodacyclic intermediate
instead of a seven-membered one for D, although the rhodium
center is in a sterically more hindered environment in F. This
catalytic cycle is completed when the resulting Rh(I) species is
oxidized by Cu(II) to regenerate the Rh(III) species.
oxidative coupling with internal alkynes.22 However, no oxidative
coupling with any olefin has been reported. Gratifyingly, the
coupling of 1-naphthol and benzyl acrylate gave two expected
products 5 and 6 in 5 and 38% isolated yield, respectively,
although this reaction suffers from moderate selectivity (eq 6).
Here the major isolated product 6 is derived from intramolecular
hydroalkoxylation of the olefination product 5. Heating (115 °C)
a CD3CN solution of product 5 gave essentially no formation of
6, indicating that this intramolecular hydroalkoxylation process is
metal-catalyzed. Importantly, when the reaction solvent was
changed to DMF (100 °C), the reaction is much more efficient
and selective, and product 5 was isolated as the only product in
81% yield, highlighting significant solvent effect in the oxidative
coupling between 1-naphthol and an acrylate.
Although in principle NH isoquinolones can be regarded as
special phenols, where the OH can act as a directing group and
although we have observed17a that oxidative olefination did occur
between simple 1-hydroxyisoquinoline and acrylates at the
8-position, no CꢀH activation at the 8-position of compound
4 could be achieved under our optimized conditions (eq 5).
These big differences between simple 1-hydroxisoquinoline and
4 may be ascribed to steric effects, and this inspired us to explore
structurally related 1-naphthols as possible substrates. Indeed,
1-naphthols have been successfully employed as a partner in
In conclusion, we have successfully developed Rh(III)-cata-
lyzed oxidative coupling between functionalized NH isoquino-
lones and activated olefins using Cu(OAc)2 as an oxidant to give
tetracyclic products. The N atom acts as a directing group for
ortho CꢀH activation in the 3-aryl group of NH isoquinolones.
Significantly this reaction can be one-pot starting from methyl
benzohydroxamates without the isolation of isoquinolones. A
broad scope of substrates has been demonstrated, and both
activated terminal and internal olefins are an efficient coupling
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NOTE
partner. In the coupling of N-methylmaleimide, a Wacker-like
mechanism was proposed, where backside attack of the NH
group in isoquinolones is proposed to give an intermediate that
isomerizes and subsequently leads to cyclometalation. When no
3-aryl group is present in NH isoquinolone substrates, neither
the N nor the OH group can act as an efficient directing group for
CꢀH activation. Selective CꢀH activation was successfully
achieved at the 8-position of 1-naphthol, leading to an olefination
product under similar conditions. The broad selection of the two
coupling partners and the diversity of the coupling products
should make this method a useful one in the synthesis of complex
structures.
133.5, 132.1, 131.2, 131.0, 129.5, 128.5, 128.4, 127 0.4, 126.4, 125.2,
124.8, 124.0, 122.8, 114.5, 60.0, 51.8, 36.6; IR 1742, 1646, 1616, 1477,
1364, 1163, 764, 704 cmꢀ1; HRMS (ESI) calcd for [C25H19NO3 þ H]þ
382.1438; found 382.1423.
1
Compound 3c: Yield 65% (conditions A); H NMR (400 MHz,
CDCl3) δ 8.54 (d, J = 7.6 Hz, 1H), 7.44ꢀ7.63 (m, 7H), 7.31ꢀ7.36 (m,
2H), 7.21 (d, J = 8.0, 1H), 7.09 (t, J = 7.6 Hz, 1H), 6.39 (d, J = 8.0 Hz,
1H), 6.02 (dd, J = 7.6, 3.6 Hz, 1H), 4.14 (d, J = 4.0 Hz, 1H), 4.10 (d, J =
8.0 Hz, 1H), 3.74 (dd, J = 16.1, 4.0 Hz, 1H), 3.07 (dd, J = 16.0, 8.0 Hz,
1H), 1.15 (t, J = 8.0 Hz, 3H, CH3); 13C NMR (125 MHz, CDCl3) δ
170.3, 160.9, 141.6, 138.7, 137.9, 135.2, 133.5, 132.1, 131.1, 131.0, 129.5,
129.43, 129.39, 128.41, 128.36, 127.3, 126.3, 125.2, 124.8, 123.9, 122.9,
114.4, 60.6, 60.0, 36.6, 14.0; IR 1737, 1645, 1620, 1476, 1375, 1180, 762,
705 cmꢀ1; HRMS (ESI) calcd for [C26H21NO3 þ H]þ 396.1594; found
396.1601.
’ EXPERIMENTAL SECTION
1
Compound 3d: Yield 81% (conditions A); H NMR (400 MHz,
CDCl3) δ 8.53 (d, J = 7.6 Hz, 1H),7.43ꢀ7.62 (m, 7H), 7.30ꢀ7.36 (m,
2H), 7.18 (d, J = 8.4 Hz, 1H), 7.09 (t, J = 8.0 Hz, 1H), 6.38 (d, J = 4.0 Hz,
1H), 6.00 (dd, J = 7.6, 3.6 Hz, 1H), 4.05 (t, J = 8.0 Hz, CH2, 2H), 3.74
(dd, J = 16.0, 4.0 Hz, 1H), 3.10 (dd, J = 16.0, 8.0 Hz, 1H), 1.45ꢀ1.53 (m,
General Considerations. All rhodium-catalyzed reactions were
carried out using standard Schlenk techniques or in a nitrogen-filled
1
drybox. All solvents were distilled under N2 prior to use. H and 13C
NMR spectra were recorded using CDCl3 as a solvent on a 400 or 500
MHz spectrometer at 298 K. The chemical shift is given in dimensionless
δ values and is referenced relative to TMS in 1H and 13C NMR
spectroscopy. High-resolution mass spectra were obtained on a LC-Q-
TOF-MS spectrometer. All other reagents were obtained from com-
mercial sources. Anhydrous Cu(OAc)2 was used throughout this work.
NH isoquinolones18 and compound 417a were synthesized according to
literature reports.
2H, CH2), 1.22ꢀ1.27 (m, 2H, CH2), 0.83 (t, J = 8.0 Hz, 3H, CH3); 13
C
NMR (125 MHz, CDCl3) δ 170.4, 160.9, 141.7, 138.7, 138.0, 135.2,
133.6, 132.1, 131.2, 131.0, 129.50, 129.45, 129.43, 128.5, 128.4, 127.3,
126.4, 125.2, 124.9, 124.0, 122.9, 114.5, 64.6, 60.1, 36.6, 30.5, 19.0, 13.6;
IR 1736, 1645, 1621, 1472, 1176, 764, 701 cmꢀ1; HRMS (ESI) calcd for
[C28H25NO3 þ H]þ 424.1907; found 424.1901.
1
Compound 3e: Yield 80% (conditions A); H NMR (400 MHz,
Representative Procedure of the Synthesis of 3aꢀs. Con-
ditions A: NH isoquinolone 1a (148.7 mg, 0.50 mmol), Cu(OAc)2
(119.8 mg, 1.10 mmol, 2.2 equiv), and [RhCp*Cl2]2 (6.2 mg, 2 mol %)
were weighed into a 25 mL pressure tube, to which acetonitrile (4 mL)
was added. After purged with nitrogen, benzyl acrylate (162.2 mg, 1.00
mmol, 2 equiv) was added via a syringe. The reaction tube was sealed,
and the mixture was stirred at 115 °C for 16 h. The mixture was diluted
with CH2Cl2 (10 mL) and was filtered through Celite, followed by
removal of volatiles under reduced pressure. Purification was performed
by flash column chromatography on silica gel using EtOAc and
petroleum ether. Yield: 86% (197 mg, 0.43 mmol).
CDCl3) δ 8.54 (d, J = 7.6 Hz, 1H), 7.51ꢀ7.62 (m, 6H), 7.42ꢀ7.45 (m,
1H), 7.33ꢀ7.37 (m, 2H), 7.21 (d, J = 8.4 Hz, 1H), 7.10 (t, J = 7.6 Hz,
1H), 6.39 (d, J = 8.0 Hz, 1H), 5.98 (dd, J = 7.2, 3.2 Hz, 1H), 3.56 (dd, J =
12.0, 4.1 Hz, 1H), 3.22 (dd, J = 16.1, 8.0 Hz, 1H), 1.26 (s, 9H, 3CH3);
13C NMR (125 MHz, CDCl3) δ 169.4, 160.9, 141.6, 138.7, 138.1, 135.3,
133.6, 132.1, 131.1, 130.9, 129.5, 129.4, 129.39, 128.4, 128.3, 127.3,
126.3, 125.2, 124.9, 123.9, 123.0, 114.3, 80.8, 60.4, 37.4, 27.8; IR 1720,
1648, 1619, 1476, 1367, 1150, 765, 698 cmꢀ1; HRMS (ESI) calcd for
[C28H25NO3 þ H]þ 424.1907; found 424.1912.
1
Compound 3f: Yield 50% (conditions B); H NMR (400 MHz,
CDCl3) δ 8.52 (d, J = 8.0 Hz, 1H), 7.60ꢀ7.66 (m, 5H), 7.48ꢀ7.55 (m,
2H), 7.39 (t, J = 8.0 Hz, 1H), 7.34 (d, J = 4.4 Hz, 1H), 7.24 (d, J = 8.0 Hz,
1H), 7.18 (t, J = 8.7 Hz, 1H), 6.43 (d, J = 7.6 Hz, 1H), 5.82 (dd, J = 6.0,
4.0 Hz, 1H), 3.55ꢀ3.67 (m, 2H, CH2); 13C NMR (125 MHz, CDCl3) δ
161.1, 138.84, 138.79, 137.3, 134.7, 133.8, 132.6, 131.2, 130.7, 129.8,
129.6, 129.5, 129.4, 128.6, 127.4, 126.8, 125.5, 124.7, 124.4, 122.7, 115.9,
Conditions B: PhC(O)NH(OMe) (76 mg, 0.5 mmol), diphenylace-
tylene (89 mg, 0.5 mmol), [RhCp*Cl2]2 (9.3 mg, 3 mol %), and CsOAc
(29 mg, 30 mol %) were weighed into a pressure tube. Methanol (4 mL)
was added, and the mixture was stirred at 60 °C for 14 h. After removal of
methanol under reduced pressure, Cu(OAc)2 (181 mg, 1.0 mmol) and
acetonitrile (4 mL) were added. The tube was sealed, and the mixture
was stirred at 115 °C for 12 h. The mixture was then diluted with CH2Cl2
(10 mL) and was filtered through Celite. All volatiles were then removed
under reduced pressure. Purification was performed by flash column
chromatography on silica gel using EtOAc and petroleum ether: yield
78% (178 mg, 0.39 mmol); 1H NMR (400 MHz, CDCl3) δ 8.53 (d, J =
4.0 Hz, 1H), 7.57ꢀ7.60 (m, 4H), 7.52 (t, J = 7.2 Hz, 1H), 7.44 (d, J = 7.6
Hz, 1H), 7.19ꢀ7.34 (m, 9H), 7.07 (t, J = 7.6 Hz, 1H), 6.35 (d, J = 8 Hz,
1H), 6.03 (dd, J = 7.2, 3.6 Hz, 1H), 5.06ꢀ5.13 (m, 2H), 3.77 (dd, J = 16,
3.6 Hz, 1H), 3.19 (dd, J = 16, 7.8 Hz, 1H); 13C NMR (100 MHz,
CDCl3) δ 170.0, 160.7, 141.2, 138.5, 137.7, 135.4, 134.9, 133.3, 132.0,
131.0, 130.7, 129.3, 128.3, 128.2, 128.0, 127.9 (two overlapping signals),
127.1, 126.2, 125.1, 124.6, 123.8, 122.7, 114.4, 66.3, 59.9, 36.4; IR 1733,
1652, 1622, 1476, 1157, 765, 698 cmꢀ1; HRMS (ESI) calcd for
[C31H23NO3 þ H]þ 458.1751; found 458.1763.
115.3, 58.9, 21.2; IR 1650, 1620, 1595, 1473, 1342, 1027, 766, 706 cmꢀ1
;
HRMS (ESI) calcd for [C24H16N2O þ H]þ 349.1335; found 349.1356.
1
Compound 3g. Yield 58% (conditions B); H NMR (400 MHz,
CDCl3) δ 8.53 (d, J = 7.6 Hz, 1H), 7.75 (d, J = 7.6 Hz, 1H), 7.54ꢀ7.62
(m, 4H), 7.44ꢀ7.51 (m, 2H), 7.27ꢀ7.36 (m, 2H), 7.21 (d, J = 8.0 Hz,
1H), 7.07 (t, J = 7.6 Hz, 1H), 6.38 (d, J = 8.0 Hz, 1H), 6.16 (dd, J = 9.2,
1.6 Hz, 1H), 4.11 (dd, J = 16.0, 4.0 Hz, 1H), 3.04 (s, CH3, 3H), 3.02 (s,
CH3, 3H), 2.51 (dd, J = 16.0, 8.0 Hz, 1H); 13C NMR (125 MHz,
CDCl3) δ 169.8, 160.9, 142.9, 138.8, 138.1, 135.3, 133.1, 132.1, 131.2,
131.0, 129.51, 129.46, 129.4, 128.4, 128.1, 127.3, 126.3, 125.2, 124.8,
124.3, 123.7, 114.4, 60.6. 37.2, 36.1, 35.5; IR 1648, 1620, 1601, 1476,
1151, 765, 702 cmꢀ1; HRMS (ESI) calcd for [C26H22N2O2 þ H]þ
395.1754; found 395.1741.
1
Compound 3h. Yield 51% (conditions A); H NMR (400 MHz,
CDCl3) δ 8.80 (s, 1H), 7.73 (dd, J = 8.4, 8.0 Hz, 1H), 7.60 (t, J = 3.2 Hz,
3H), 7.47 (d, J = 7.6 Hz, 1H), 7.18ꢀ7.35 (m, 9H), 7.11 (t, J = 7.6 Hz,
1H), 6.37 (d, J = 8.0 Hz, 1H), 6.02 (dd, J = 7.2, 4.0 Hz, 1H), 5.04ꢀ5.11
(m, 2H), 3.69 (dd, J = 16.0, 4.0 Hz, 1H), 3.29 (dd, J = 16.0, 7.2 Hz, 1H);
13C NMR (125 MHz, CDCl3) δ 169.9, 160.3, 141.6, 141.1, 140.2, 135.4,
134.4, 133.1, 131.1, 130.8, 130.1, 129.7, 128.6, 128.4, 128.2, 128.13
(q, JFꢀC = 3.2 Hz), 128.12 (q, JFꢀC = 32.9 Hz), 128.1, 126.0, 125.1
1
Compound 3b: Yield 82% (conditions A); H NMR (400 MHz,
CDCl3) δ 8.54 (d, J = 7.6 Hz, 1H), 7.59ꢀ7.61 (m, 4H), 7.50ꢀ7.45 (m,
3H), 7.31ꢀ7.36 (m, 2H), 7.2 (d, J = 8.0 Hz, 1H), 7.1 (t, J = 7.6 Hz, 1H),
6.38 (d, J = 8.0 Hz, 1H), 6.02 (dd, J = 8.0, 4.0 Hz, 1H), 3.79 (dd, J = 16.0,
3.6 Hz, 1H), 3.70 (s, 3H, CH3), 2.99 (dd, J = 16.0, 7.6 Hz, 1H); 13C
NMR (125 MHz, CDCl3) δ 170.9, 160.9, 141.7, 138.7, 137.9, 135.2,
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NOTE
(q, JFꢀC = 4.0 Hz), 124.44, 124.41, 124.0 (q, JFꢀC = 271 Hz), 122.9,
113.8, 66.6, 60.3, 36.4; IR 1728, 1659, 1622, 1330, 1312, 1164, 1141,
1112, 746, 696 cmꢀ1; HRMS (ESI) calcd for [C32H22F3NO3 þ H]þ
526.1625; found 526.1635.
7.22ꢀ7.33 (m, 8H), 7.06 (t, J = 8.4 Hz, 2H), 6.53 (d, J = 2.4 Hz, 1H),
6.32 (d, J = 7.6 Hz, 1H), 5.99 (dd, J = 7.6, 3.6 Hz, 1H), 5.07ꢀ5.13 (m,
2H), 3.71ꢀ3.80 (m, 4H), 3.15 (dd, J = 16.0, 8.0 Hz, 1H); 13C NMR (125
MHz, CDCl3) δ 170.2, 162.7, 160.6, 141.6, 140.8, 138.5, 135.5, 135.2,
133.5, 131.1, 130.8, 129.42, 129.37, 128.4 (two overlapping signals),
128.3, 128.1 (two overlapping signals), 124.0, 122.8, 118.9, 115.0, 114.2,
107.1, 66.4, 59.9, 55.2, 36.7; IR 1726, 1648, 1601, 1466, 1282, 768,
737 cmꢀ1; HRMS (ESI) calcd for [C32H25NO4 þ H]þ 488.1856; found
488.1864.
1
Compound 3i. Yield 88% (conditions A); H NMR (400 MHz,
CDCl3) δ 8.42 (d, J = 8.4 Hz, 1H), 7.57ꢀ7.58 (m, 3H), 7.43 (d, J = 7.6
Hz, 1H), 7.21ꢀ7.33 (m, 9H), 7.06 (t, J = 7.6 Hz, 1H), 6.94 (s, 1H), 6.30
(d, J = 8.0 Hz, 1H), 6.00 (dd, J = 7.6, 3.6 Hz, 1H), 5.07ꢀ5.13 (m, 2H),
3.79 (dd, J = 16.0, 3.6 Hz, 1H), 3.14 (dd, J = 16.0, 7.6 Hz, 1H), 2.37 (s,
CH3, 3H); 13C NMR (125 MHz, CDCl3) δ 170.2, 160.9, 142.7, 141.5,
138.9, 138.0, 135.6, 135.3, 133.6, 131.2, 131.0, 129.4, 129.3, 128.44,
128.37, 128.1, 128.0, 127.4, 124.9, 124.0, 122.9, 122.7, 114.4, 110.0, 66.5,
59.9, 36.8, 22.0; IR 1726, 1651, 1614, 1464, 1344, 1285, 1144, 970, 745,
697 cmꢀ1; HRMS (ESI) calcd for [C32H25NO3 þ H]þ 472.1907; found
472.1916.
1
Compound 3n. Yield 85% (conditions A); H NMR (500 MHz,
CDCl3) δ 8.48 (dd, J = 8.0, 1.0 Hz, 1H), 7.92 (d, J = 8.0 Hz, 1H), 7.77 (d,
J = 8.0 Hz, 1H), 7.66ꢀ7.70 (m,1H), 7.41ꢀ7.48 (m, 3H), 7.33ꢀ7.36 (m,
1H), 7.41ꢀ7.48 (m, 3H), 7.15 (d, J = 1.5 Hz, 1H), 7.14 (d, J = 2.5 Hz,
1H), 5.88 (dd, J = 7.5, 4.0 Hz, 1H), 5.00 (s, 2H, CH2), 3.64 (dd, J = 16.0,
4.0 Hz, 1H), 3.14 (dd, J = 16.5, 7.5 Hz, 1H), 2.60 (s, CH3,3H); 13C NMR
(125 MHz, CDCl3) δ 170.1, 160.6, 141.5, 138.5, 137.7, 135.5, 134.4,
132.1, 129.1, 128.7, 128.4, 128.2, 128.1, 127.7, 126.2, 125.1, 124.3, 123.2,
123.1, 108.2, 66.5, 59.8, 36.7, 12.4; IR 1729, 1648, 1616, 1383, 1159, 763,
694 cmꢀ1; HRMS (ESI) calcd for [C26H21NO3 þ H]þ 396.1594; found
396.1606.
1
Compound 3j. Yield 90% (conditions A); H NMR (400 MHz,
CDCl3) δ 8.33 (s, 1H), 7.54 (s, 3H), 7.21ꢀ7.43 (m, 11H), 7.03ꢀ7.10
(m, 2H), 6.34 (dd, J = 7.6 Hz, 1H), 5.99 (d, J = 3.6 Hz, 1H), 5.06ꢀ5.12
(m, 2H), 3.76 (dd, J = 15.6, 2.8 Hz, 1H), 3.16 (dd, J = 16.0, 7.6 Hz, 1H),
2.49 (s, 3H, CH3); 13C NMR (125 MHz, CDCl3) δ 170.1, 160.7, 141.2,
136.9, 136.4, 136.3, 135.5, 135.2, 133.55, 133.50, 131.0, 130.8, 129.3,
129.1, 128.31, 128.26, 128.25, 128.2, 128.0 (two overlapping signals),
126.9, 125.1, 124.7, 123.7, 122.7, 114.5, 66.4, 60.0, 36.6, 21.2; IR 1733,
1652, 1616, 1497, 1350, 1157, 670 cmꢀ1; HRMS (ESI) calcd for
[C32H25NO3 þ H]þ 472.1907; found 472.1916.
1
Compound 3o. Yield 88% (conditions A); H NMR (400 MHz,
CDCl3) δ 8.52 (d, J = 7.6 Hz, 1H), 7.50ꢀ7.61 (m, 5H), 7.24ꢀ7.28 (m,
7H), 7.13 (d, J = 8.0 Hz, 1H), 7.10 (d, J = 8.4 Hz, 1H), 6.33 (d, J = 8.4 Hz,
1H), 5.97 (dd, J = 7.2, 3.2 Hz, 1H), 5.07ꢀ5.13 (m, 1H), 3.75 (dd, J =
16.0, 4.0 Hz, 1H), 3.20 (dd, J = 16.0, 8.0 Hz, 1H); 13C NMR (125 MHz,
CDCl3) δ 169.9, 160.7, 143.2, 138.3, 137.2, 135.8, 135.4, 134.8, 133.3,
132.6, 132.4, 132,3, 131.9, 130.0, 129.9, 129.1, 128.5, 128.3, 128.1, 127.5,
126.8, 125.0, 124.9, 124.8, 123.5, 113.3, 66.7, 59.7, 36.2; IR 1726, 1653,
1
Compound 3k. Yield 41% (conditions A); H NMR (400 MHz,
CDCl3) δ 8.37 (d, J = 8.0 Hz, 1H), 7.48ꢀ7.52 (m, 3H), 7.41ꢀ7.46 (m,
2H), 7.34ꢀ7.36 (m, 2H), 7.20ꢀ7.29 (m, 8H), 7.04 (t, J = 7.6 Hz, 1H),
6.08 (d, J = 7.6 Hz, 1H), 5.98 (dd, J = 7.6, 3.6 Hz, 1H), 5.05ꢀ5.12 (m,
2H), 3.69 (dd, J = 16.0, 3.6 Hz, 1H), 3.19 (dd, J = 15.8, 7.2 Hz, 1H); 13C
NMR (125 MHz, CDCl3) δ 169.9, 159.7 (d, JCꢀF = 3.9 Hz), 159.0 (d,
JCꢀF = 253.8 Hz), 141.4, 139.1, 137.21 (d, JCꢀF = 2.1 Hz), 135.5, 133.4,
130.2 (d, JCꢀF = 2.8 Hz), 129.8 (d, JCꢀF = 4.2 Hz), 129.6, 128.8, 128.79,
128.5, 128.4, 128.13, 128.07, 128.0, 127.2 (d, JCꢀF = 9.5 Hz), 126.9 (d,
JCꢀF = 9.0 Hz), 126.8, 124.5, 123.5 (d, JCꢀF = 4.4 Hz), 122.7, 119.0 (d,
JCꢀF = 21.8 Hz), 111.0, 66.5, 60.1, 36. 5; IR 1731, 1653, 1613, 1472,
1233, 1165, 757, 706 cmꢀ1; HRMS (ESI) calcd for [C31H22FNO3 þ
H]þ 476.1656; found 476.1648.
1492, 1271, 1159, 731, 518 cmꢀ1
; HRMS (ESI) calcd for
[C31H21Cl2NO3 þ H]þ 526.0971; found 526.0977.
1
Compound 3p. Yield 87% (conditions A); H NMR (400 MHz,
CDCl3) δ 8.50 (d, J = 8.0 Hz, 1H), 7.55 (t, J = 7.6 Hz, 1H), 7.45 (t, J = 8.0
Hz, 1H), 7.19ꢀ7.28 (m, 8H), 7.07ꢀ7.10 (m, 2H), 6.98 (d, J = 1.6 Hz,
1H), 6.65 (dd, J = 8.8, 2.0 Hz, 1H), 6.36 (d, J = 8.8 Hz, 1H), 5.96 (dd,
J = 7.6, 3.6 Hz, 1H), 5.08ꢀ5.12 (m, 2H), 3.94 (s, 3H, CH3), 3.80 (dd,
J = 16.0, 3.6 Hz, 1H), 3.71 (s, CH3, 3H), 3.10 (dd, J = 16.0, 8.0 Hz, 1H);
13C NMR (125 MHz, CDCl3) δ 170.3, 160.9, 159.5, 143.5, 139.2, 138.2,
135.6, 132.3, 132.0, 131.9, 128.4, 128.1, 128.0, 127.3, 127.2, 126.2, 125.7,
125.1, 124.9, 124.3, 115.3, 114.8, 112.4, 107.6, 66.5, 59.8, 55.4, 56.3,
36.7; IR 1667, 1511, 1245, 1174, 1030, 766, 539 cmꢀ1; HRMS (ESI)
calcd for [C33H27NO5 þ H]þ 518.1962; found 518.1970.
1
Compound 3k0. Yield 45% (conditions A); H NMR (400 MHz,
CDCl3) δ 8.37 (d, J = 8.0 Hz, 1H), 7.48ꢀ7.52 (m, 3H), 7.41ꢀ7.46 (m,
2H), 7.34ꢀ7.36 (m, 2H), 7.20ꢀ7.29 (m, 8H), 7.04 (t, J = 7.6 Hz, 1H),
6.07 (d, J = 7.6 Hz, 1H), 5.98 (dd, J = 7.6, 3.6 Hz, 1H), 5.05ꢀ5.12 (m,
2H), 3.69 (dd, J = 16.0, 3.6 Hz, 1H), 3.19 (dd, J = 15.6, 7.2 Hz, 1H); 13C
NMR (125 MHz, CDCl3) δ 170.1, 161.3 (d, JCꢀF = 245.9 Hz), 160.1 (d,
1
Compound 3q. Yield 75% (conditions A); H NMR (400 MHz,
CDCl3) δ 8.51 (d, J = 8.0, 1H), 7.54 (t, J = 7.6 Hz, 1H), 7.45 (t, J = 7.2
Hz, 1H), 7.32 (d, J = 7.6 Hz, 1H), 7.19ꢀ7.26 (m, 2H), 7.08ꢀ7.13 (m,
3H), 6.67 (d, J = 8.8 Hz, 1H), 6.39 (d, J = 8.8 Hz, 1H), 5.91 (d, J = 5.2 Hz,
1H), 3.95 (s, 3H, CH3), 3.80 (s, 3H, CH3), 3.66 (dd, J = 16.0, 3.6 Hz,
1H), 3.02 (dd, J = 16.0, 8.0 Hz, 1H), 1.32 (s, 9H, 3CH3); 13C NMR (125
MHz, CDCl3) δ 169.6, 160.9, 159.5, 143.8, 139.3, 138.4, 132.25, 132.20,
131.9, 127.4, 127.3, 126.3, 125.7, 125.1, 124.8, 124.3, 115.4, 114.9, 114.8,
112.2, 107.7, 80.9, 60.1, 55.5, 55.3, 37.5, 27.9; IR 1724, 1648, 1609, 1478,
1154, 775, 539 cmꢀ1; HRMS (ESI) calcd for [C30H29NO5 þ H]þ
484.2118; found 484.2124.
JCꢀF = 4.6 Hz), 141.1, 137.4 (d, JCꢀF = 1.8 Hz), 135.5, 135.4 (d, JCꢀF
=
1.1 Hz), 134.9, 133.4, 131.1, 130.8, 129.52 (two overlapping signals),
129.47, 128.6, 128.5, 128.4, 128.2, 128.1, 127.7 (d, JCꢀF = 7.5 Hz), 126.4
(d, JCꢀF = 7.6 Hz), 123.9, 122.9, 120.8 (d, JCꢀF = 22.0 Hz), 114.0, 112.5
(d, JCꢀF = 22.8 Hz), 66.6, 60.1, 36.6; IR 1729, 1650, 1490, 1343, 1248,
1175, 735 cmꢀ1; HRMS (ESI) calcd for [C31H22FNO3 þ H]þ
476.1656; found 476.1648.
1
Compound 3l. Yield 91% (conditions A); H NMR (400 MHz,
CDCl3) δ 8.37 (d, J = 7.2 Hz, 1H), 7.57ꢀ7.59 (m, 4H), 7.44 (d, J = 7.6
Hz, 1H), 7.23ꢀ7.32 (m, 7H), 7.18ꢀ7.21 (m, 2H), 7.08 (t, J = 8 Hz, 1H),
6.81 (d, J = 8 Hz, 1H), 5.98 (dd, J = 6.8, 3.6 Hz, 1H), 5.05ꢀ5.11 (m, 2H),
3.72 (dd, J = 16.0, 3.6 Hz, 1H), 3.22 (dd, J = 16.0, 7.6 Hz, 1H); 13C NMR
(125 MHz, CDCl3) δ 170.1, 160.4, 141.6, 140.3, 139.3, 135.5, 134.4,
133.2, 131.1, 130.9, 129.8, 129.69, 129.66, 129.6, 129.2, 128.8, 128.5,
128.4, 128.2, 128.1, 127.7, 127.6, 124.2, 123.5, 122.9, 113.4, 66.6, 60.2,
Compound 3r. Yield 40%. 1H NMR (400 MHz, CDCl3) δ 8.43 (d,
J = 7.6 Hz, 1H), 7.47ꢀ7.61 (m, 6H), 7.36ꢀ7.43 (m, 2H), 7.22ꢀ7.27 (m,
2H), 7.17 (t, J = 7.6 Hz, 1H), 6.43 (d, J = 8.0 Hz, 1H), 4.00 (d, J = 18.0
Hz, 1H), 3.28 (s, 3H, CH3), 3.08 (d, J = 18.0 Hz, 1H); 13C NMR (125
MHz, CDCl3) δ 173.82, 173.76, 160.5, 140.6, 138.9, 137.2, 134.4, 133.6,
132.8, 131.0, 130.8, 130.3, 129.7, 129.6, 129.5, 128.7, 127.4, 127.0, 125.7,
124.7, 124.5, 120.6, 115.7, 70.9, 39.5, 25.8; IR 1742, 1645, 1619, 1477,
1366, 1177, 764, 704 cmꢀ1; HRMS (ESI) calcd for [C26H18N2O3 þ
H]þ 407.1390; found 407.1398.
36.5; IR 1728, 1653, 1591, 1459, 1340, 1188, 1149, 768, 714 cmꢀ1
;
HRMS (ESI) calcd for [C31H22BrNO3 þ H]þ 536.0865; found
536.0854.
Compound 3s. Yield 40% from diethyl maleate (conditions A) and
41% from diethyl fumarate (conditions A); 1H NMR (400 MHz,
CDCl3) δ 8.52 (d, J = 7.6 Hz, 1H), 7.57ꢀ7.59 (m, 4H), 7.45ꢀ7.52
1
Compound 3m. Yield 73% (conditions A); H NMR (400 MHz,
CDCl3) δ 8.45 (d, J = 9.2, 1H), 7.55ꢀ7.58 (m, 3H), 7.43 (d, J = 7.6, 1H),
2931
dx.doi.org/10.1021/jo2002209 |J. Org. Chem. 2011, 76, 2926–2932

The Journal of Organic Chemistry
NOTE
(m, 4H), 7.34 (t, J = 7.6 Hz, 1H), 7.23 (d, J = 8.0 Hz, 1H), 7.13 (t, J = 7.6
Hz, 1H), 6.39 (d, J = 7.6 Hz, 1H), 4.48 (d, J = 16.0 Hz, 1H), 4.16ꢀ4.27
(m, 2H), 3.72ꢀ3.74 (m, 2H), 3.65 (d, J = 15.6 Hz, 1H), 1.17 (t, J = 7.2
Hz, 3H), 0.80 (t, J = 6.8 Hz, 3H, CH3); 13C NMR (125 MHz, CDCl3) δ
168.4, 168.3, 160.6, 139.6, 138.8, 138.3, 134.9, 134.2, 132.2, 131.1, 131.0,
129.4 (two overlapping signals), 129.2, 128.5, 127.5, 126.4, 125.2, 125.1,
124.0, 121.6, 114.6, 72.1, 62.5, 60.1, 36.8, 13.9, 13.6; IR 1735, 1662,
1472, 1254, 1030, 765, 703 cmꢀ1; HRMS (ESI) calcd for [C29H25NO5
þ H]þ 468.1805; found 468.1812.
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Compound 5. Yield 81% (using DMF as a solvent) or 5% (using
MeCN as a solvent). 1H NMR (400 MHz, CDCl3) δ 9.33 (d, J = 16.0
Hz, 1H), 7.81 (d, J = 8.0 Hz, 1H), 7.53ꢀ7.55 (m, 2H), 7.34ꢀ7.47 (m,
7H), 7.27ꢀ7.31 (m, 1H), 6.95(d, J = 7.2 Hz, 1H), 6.34 (d, J = 15.6 Hz,
1H), 5.33 (s, 2H, CH2); 13C NMR (125 MHz, CDCl3) δ 168.7, 154.1,
151.1, 135.9, 135.8, 132.8, 130.4, 128.6, 128.3, 128.2, 126.4, 125.9, 125.5,
122.4, 120.5, 117.3, 111.1, 66.8; IR 1689, 1617, 1346, 1173, 819, 748,
695 cmꢀ1; HRMS (ESI) calcd for [C20H16O3 þ H]þ 305.1172; found
305.1165.
Compound 6. Yield 38% (using MeCN as a solvent). 1H NMR (400
MHz, CDCl3) δ 7.62 (d, J = 8.0 Hz, 1H), 7.30ꢀ7.45 (m, 7H), 7.24 (dd,
J = 8.4, 3.6 Hz, 1H), 7.11 (d, J = 6.8 Hz, 1H), 6.70 (dd, J = 7.6, 3.6 Hz,
1H), 6.35(t, J = 7.2 Hz, 1H), 5.23 (d, J = 12.4, 1H), 5.20 (d, J = 12.0 Hz,
1H), 2.92ꢀ3.08 (m, 2H); 13C NMR (125 MHz, CDCl3) δ 169.7, 160.3,
140.5, 135.5, 131.7, 129.6, 128.5 (two overlapping signals), 128.29,
128.26, 128.0, 123.6, 115.8, 115.6, 101.1, 84.4, 66.7, 40.9; IR 1730, 1596,
1489, 1376, 1169, 949, 756, 615, 492 cmꢀ1; HRMS (ESI) calcd for
[C20H16O3 þ H]þ 305.1172; found 305.1165.
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’ ASSOCIATED CONTENT
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Lett. 2010, 12, 5462.
S
Supporting Information. NMR spectra of all new com-
b
pounds. This material is available free of charge via the Internet at
http://pubs.acs.org.
’ AUTHOR INFORMATION
Corresponding Author
*E-mail: clinton_du@126.com; xwli@dicp.ac.cn.
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’ ACKNOWLEDGMENT
We thank the Dalian Institute of Chemical Physics, Chinese
Academy of Sciences for financial support. This work was also
supported by the NSFC (No. 21072188).
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