Regio- and stereoselective olefination of phenol carbamates through C-H bond functionalization

Article abstract of DOI:10.1002/ejoc.201201574

Two pathways that can be used to access ortho-olefinated phenol carbamate, including a ruthenium(II)-catalyzed oxidative olefination of phenol carbamate with acrylates and a rhodium(III)-catalyzed alkyne hydroarylation of phenol carbamate with internal alkynes through direct C-H activation, are reported. Both reactions afford substituted alkenes in a highly regio- and stereoselective manner. A highly regio- and stereoselective olefination of phenol carbamates through Ru^II-catalyzed oxidative olefination and Rh ^III-catalyzed alkyne hydroarylation are reported.

Full text of DOI:10.1002/ejoc.201201574

FULL PAPER
DOI: 10.1002/ejoc.201201574
Regio- and Stereoselective Olefination of Phenol Carbamates through C–H
Bond Functionalization
Bin Li,*[a] Jianfeng Ma,[a] Yujie Liang,[a] Nuancheng Wang,[a] Shansheng Xu,[a]
Haibin Song,[a] and Baiquan Wang*[a,b]
Keywords: Olefination / Protecting groups / C-H activation / Ruthenium / Rhodium
Two pathways that can be used to access ortho-olefinated
amate with internal alkynes through direct C–H activation,
phenol carbamate, including a ruthenium(II)-catalyzed oxi- are reported. Both reactions afford substituted alkenes in a
dative olefination of phenol carbamate with acrylates and a
rhodium(III)-catalyzed alkyne hydroarylation of phenol carb-
highly regio- and stereoselective manner.
tion. Later, rhodium-complex-catalyzed oxidative ole-
finations were independently developed by the research
groups of Satoh and Miura,[5] Glorius,[6] Ellmann,[7]
Chang,[8] Li,[9] Liu,[10] Loh,[11] and Zhu.[12] Although ruthe-
nium complexes have also been reported to catalyze this
type of reaction,[13] the successful applications of less-ex-
pensive ruthenium(II) catalysts for the oxidative olefination
of arenes were initiated just one year ago. The groups of
Satoh and Miura,[14] Ackermann,[15] Bruneau and
Dixneuf,[16] and Jeganmohan[17] have shown that use of the
[{RuL2(p-cymene)}2] (L = Cl or OAc) catalyst allows the
oxidative coupling of aromatic acids, aryl ketones, N-aryl-
pyrazoles, anilides, amides, aromatic aldehydes, and aro-
matic esters with olefins by using copper acetate as oxidant.
Moreover, we have reported the dehydrogenative alkenyl-
ation of N-methoxybenzamides with styrene and acrylates
in the presence of [{RuCl2(p-cymene)}2] as catalyst using
CONH(OMe) as an oxidizing directing group.[18] On the
other hand, hydroarylation reactions of internal alkynes is
a green pathway for redox-neutral olefination of aryl C–H
bonds. In this process, no oxidant is needed, and trisubsti-
tuted olefin products are formed. Although a variety of
transition-metal complexes, such as palladium,[19] rho-
dium,[20] iridium,[21] rhenium,[22] nickel,[23] cobalt,[24] and
ruthenium[25] have been used to catalyze this type of reac-
tion, several issues remain to be addressed such as the lim-
ited substrate scope and the regio- and stereoselectivity of
the reaction.
Introduction
The direct functionalization of C–H bonds catalyzed by
transition-metal complexes allows the use of less expensive
and more readily available starting materials for the con-
struction of complex products.[1] Among these reactions,
new carbon–carbon bonds can be formed through direct C–
H transformation.[2] Of these processes, catalytic oxidative
olefination and alkyne hydroarylation of aryl C–H bonds
are two important methods for the synthesis of substituted
alkenes in an atom- and step-economic fashion (Scheme 1).
Scheme 1. Catalytic oxidative olefination and alkyne hydroaryl-
ation of aryl C–H bonds to synthesize substituted alkenes.
As an attractive alternative to traditional Heck coupling
reactions, the catalytic oxidative alkenylation method
(known as the Fujiwara–Moritani reaction[3]) is a more ef-
ficient and greener process. Palladium[4] complexes were the
most frequently used catalysts for this useful transforma-
[a] State Key Laboratory of Element-Organic Chemistry, College
of Chemistry, Nankai University,
The orientation of the directing group was considered
useful for controlling the regioselectivity in C–H activation.
Aryl carbamate substrates have been widely used in cross-
coupling reactions because of their ease of preparation and
good stability.[26] However, these substrates have been less
well explored as directing groups in C–H bond activation
reactions.[27] In a continuation of our interest in transition-
metal-catalyzed C–H functionalization,[28] we here disclose
Tianjin 300071, P. R. of China
Fax: +86-22-2350-4781
E-mail: nklibin@nankai.edu.cn
bqwang@nankai.edu.cn
Homepage: http://www.nankai.edu.cn
[b] State Key Laboratory of Organometallic Chemistry, Chinese
Academy of Sciences,
Shanghai 200032, P. R. of China
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.201201574.
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Selective Olefination of Phenol Carbamates
our development of the ortho-olefination of carbamate-pro- outlines the scope of the reaction. Phenyl carbamates con-
tected phenols through (a) [{RuCl2(p-cymene)}2]/AgSbF6- taining either electron-donating or -withdrawing groups
catalyzed oxidative coupling of phenol carbamate with ac- participated well in this reaction and gave the correspond-
rylates,[29] and (b) [Cp*RhCl2]2/AgSbF6-catalyzed alkyne ing alkene derivatives (3a–l and 3p–w) in good to excellent
hydroarylation of phenol carbamate with internal alkynes. yields. Substrates bearing ortho-substituted groups did not
To our delight, both reactions afforded substituted alkenes affect the reactions and underwent the desired oxidative
in a highly regio- and stereoselective manner.
coupling with 2a to yield 3b–g. The reactions exhibited high
regioselectivity with C–H olefination at the sterically less
hindered position when meta-substituted substrates were
used (3h–l). It was interesting to find that in the case of
meta-OMe substituted substrate 1i, a minor amount of di-
olefinated product 3i-b was also obtained in 29% yield, sug-
gesting the strong electronic effect of the substrate 1i. Sim-
ilar results were also observed in Rh-catalyzed processes.[11]
When substrate 1p, containing both carbamate and carb-
oxylate groups, was employed in the reaction, a mixture of
mono- and diolefinated products was afforded, with
monoolefination occurring at the ortho position of the carb-
amate group. This result suggests that carbamate is a more
efficient C–H-activation-directing group in the current
RuII-catalyzed system. It is noteworthy that halide func-
tional groups were compatible in the present catalytic reac-
tion (o-Cl for 3e, m-Cl for 3j, m-Br for 3k, p-Cl for 3r, and
p-Br for 3s), which offers the opportunity for further cou-
pling to afford more complex molecules. However, although
o-Br-substituted carbamate produced the dehalogenated
complex in our Ru-catalyzed system,[31] it was tolerated in
the Rh-catalyzed reactions.[11] Under the standard reaction
conditions, the para-substituted substrates were inclined to
generate a mixture of mono- and diolefinated products (3q–
w). Interestingly, substrates containing an electron-donating
group at the para-position led to complete formation of the
diolefinated products by using twofold excess of catalyst
and acrylate (3u–w), whereas electron-neutral and -poor
substrates gave predominantly the diolefinated products
(3q–s) even when the amounts of catalyst and acrylate were
doubled. The p-NO2-substituted substrate, which exhibited
low reactivity in the Rh-catalyzed process,[10] afforded
monoolefinated compound 3t-a as the predominant prod-
uct in our reaction system. Moreover, various acrylates,
such as methyl acrylate, n-butyl acrylate, and benzyl acryl-
ate, were smoothly incorporated to produce the corre-
sponding products 3m–o in good to excellent yield. Other
alkenes bearing electron-withdrawing groups were also
tested: N,N-dimethylacrylamide and acrylonitrile showed
very low reactivity, whereas phenyl vinyl sulfone could be
used as substrate to yield the 3-sulfone in 43% yield
(Table 2). Disappointingly, styrene failed to react with
phenyl carbamates under these reaction conditions. It also
needs to be pointed out that the scope of the method in-
cludes alkenyl carbamates derived from α-tetralone, al-
though the desired olefinated products 3x–z were isolated
Results and Discussion
At the outset of our investigations, the reaction of naph-
thalen-1-yl dimethylcarbamate (1a) with ethyl acrylate (2a)
was examined as a model reaction (Table 1). After many
trials,[30] we found that treatment of 1a (1.0 equiv.) with 2a
(2.0 equiv.) in the presence of [{RuCl2(p-cymene)}2]
(5.0 mol-%), AgSbF6 (20 mol-%), and Cu(OAc)2
(2.0 equiv.) in tetrahydrofuran (THF) at 110 °C for 30 h
gave the desired Heck-type product 3a in 85% isolated yield
with excellent (E) stereoselectivity (Table 1, Entry 7). The
1
structure of 3a, which was confirmed by H and 13C NMR
spectroscopy and mass spectrometry, is consistent with
those reported previously.[11] Among the tested solvents,
THF was found to be optimal. Other solvents, such as 2-
methyl-2-butanol
(tert-AmOH),
1,2-dimethoxyethane
(DME), and dioxane gave lower yields, whereas CH3CN,
N,N-dimethylformamide (DMF), and CH3OH completely
inhibited the reaction (Table 1, Entries 1–6). Control experi-
ments showed that the absence of either catalyst or silver
salt resulted in complete inactivity of the catalytic reaction
(Table 1, Entries 8–10).
Table 1. Optimization of ruthenium-catalyzed oxidative C–H ole-
fination of 1a with acrylic esters.[a]
[a] Reaction conditions: carbamate (0.4 mmol), ethyl acrylate in moderate yields (Scheme 2).
(0.8 mmol),
[{RuCl2(p-cymene)}2]
(5.0 mol-%),
Cu(OAc)2
Experiments were conducted to examine the working
mode of the reactions. When the reaction of 1a was carried
out in CD3OD (2.0 mL) or a mixed solvent system of THF
(2.0 equiv.), solvent (2.0 mL), 110 °C, 30 h, under Ar. [b] Isolated
yield. [c] No [RuCl2(p-cymene)]2.
We then studied the reactions of various aryl carbamates (2.0 mL)/D2O (0.5 mL), 8 and 9% deuterium incorporation
1 with 2a under the optimized reaction conditions; Table 2 was detected at the ortho position of the recovered starting
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B. Li, J. Ma, Y. Liang, N. Wang, S. Xu, H. Song, B. Wang
FULL PAPER
Table 2. Results of ruthenium-catalyzed oxidative C–H olefination with acrylic esters.[a,b]
[a] Reaction conditions: carbamate (0.4 mmol), ethyl acrylate (0.8 mmol), [{RuCl2(p-cymene)}2] (5.0 mol-%), Cu(OAc)2 (2.0 equiv.), THF
(2.0 mL), 110 °C, 30 h, under Ar. [b] Isolated yield. [c] The diolefinated product 3i-b was also isolated in 29% yield. [d] 36 h. [e] 48 h.
[f] The data in parentheses refers to the yield of 3l performed on 3.0 mmol scale. [g] Reaction conditions: acrylate (5.0 equiv.), [RuCl2(p-
cymene)]2 (10.0 mol-%), AgSbF6 (40 mol-%), Cu(OAc)2 (4.0 equiv.), THF (0.2 m), 110 °C, 60 h. [h] The mono- and diolefinated com-
pounds were isolated separately. [i] The mono- and diolefinated compounds were isolated as an inseparable mixture, and the ratio of the
1
two species was determined by H NMR spectroscopy.
1.45 (at 30% conversion) was observed in the intermo-
lecular isotopic study [Equation (2)].[32]
Scheme 2. Results of ruthenium-catalyzed oxidative C–H ole-
fination of 3,4-dihydronaphthalen-1-yl dimethylcarbamate (1u)
with acrylate. Reagents and conditions: carbamate 1u (0.4 mmol),
ethyl acrylate (0.8 mmol), [{RuCl2(p-cymene)}2] (7.5 mol-%),
droarylation reaction of 1a with internal alkynes to synthe-
AgSbF6 (30 mol-%), AgOAc (3.0 equiv.), THP (2.0 mL), 110 °C,
Subsequently, we also explored the catalytic alkyne hy-
size more substituted alkenes. After many optimized experi-
ments,[30] we found that [{RuCl2(p-cymene)}2]/AgSbF6 ex-
hibited moderate catalytic activity in the model reaction of
40 h, under Ar.
material 1a, respectively [Equation (1)]. This fact suggests 1a with diphenylacetylene (4a) [50% isolated yield of 5a,
that, under the reaction conditions, C–H activation is a re- Equation (3)]. To our delight, almost quantitative isolated
versible but slow process. Moreover, a kinetic isotope effect yields were achieved when [Cp*RhCl2]2/AgSbF6 was chosen
(KIE) with values of kH/kD = 1.17 (at 15% conversion) and as catalyst [Equation (3)]. The reaction proceeded with high
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Selective Olefination of Phenol Carbamates
Table 3. Results of rhodium-catalyzed alkyne hydroarylation reac-
tion with internal alkynes.[a,b]
regio- and stereoselectivity, which was confirmed by single-
crystal X-ray diffraction analysis of compound 5a (Fig-
ure 1). Notably, control experiments showed that the use
of AgSbF6 and PivOH is essential for the success of the
reaction.
As shown in Table 3, hydroarylation of various aryl carb-
amates with diphenylacetylene was examined under similar
reaction conditions. It was clear that the electronic nature
of the substituents on the aryl carbamates had no signifi-
cant effect on the reactivity, and 5b–g were obtained in 62–
75% isolated yields with excellent (E) stereoselectivity. The
halide functional groups were again well tolerated (o-Cl for
5c, m-Cl for 5f, and m-Br for 5g) in this catalytic system.
In addition, the electron-deficient tolane derivatives, bis(4-
chlorophenyl)acetylene (4b) and bis(4-bromophenyl)acetyl-
ene (4c), were good candidates for this reaction, which cou-
pled with 1a to form the corresponding hydroarylation
[a] Reaction conditions: carbamate 1 (0.3 mmol), ethyl acrylate
(0·mmol), PivOH (2.4 mmol), [Cp*RhCl2]2 (5.0 mol-%), AgSbF6
(20.0 mol-%), PhCl (2.0 mL), 120 °C, 18–30 h, under Ar. [b] Iso-
lated yield. [c] The data in parentheses refers to the yield of 5a
conducted on 3.0 mmol scale.
Figure 1. ORTEP representation of compound 5a; thermal ellipsoids are set at 30% probability. Hydrogen atoms except H(18A) have
been omitted for clarity.
Eur. J. Org. Chem. 2013, 1950–1962
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B. Li, J. Ma, Y. Liang, N. Wang, S. Xu, H. Song, B. Wang
FULL PAPER
Figure 2. ORTEP representation of compound 5k; thermal ellipsoids are set at 30% probability. Hydrogen atoms except H(12A) have
been omitted for clarity.
products 5h and 5i in 86 and 96% yield, respectively. This methylcarbamate (1l) afforded 3l in 77% yield by using the
protocol could also be applied to carbamate-protected 4- ruthenium(II)-catalyzed oxidative olefination method
hydroxycoumarin, and the desired products 5j–l were iso- (Table 2), and naphthalen-1-yl dimethylcarbamate (1a)
lated in high yield. It is important to note that when unsym- yielded 5a in 89% yield by using the rhodium(III)-catalyzed
metrical (alkyl)(phenyl)acetylenes 1-phenylpropyne (4d) alkyne hydroarylation method (Table 3). Moreover, as a
and 1-phenylbutyne (4e) were applied, 5k and 5l were iso- protecting group for the phenol derivatives, the carbamate
lated as the only regio- and stereoisomers. The structure of directing group could be easily removed (Scheme 3), which
compound 5k was confirmed by single-crystal X-ray dif- highlights the potential of employing carbamate as a direct-
fraction analysis (Figure 2).
ing group.
In the rhodium-catalyzed alkyne hydroarylation reaction,
only very low deuterium incorporation (6%) in the product
and a decrease in deuterium incorporation (from 95 to
1
51%) in the starting material were detected by H NMR
spectroscopy when isotopically labeled substrate [D1]1a was
employed in the reaction for 1 h [Equation (4)]. The former
result excludes the possibility of an oxidative insertion reac-
tion pathway, which should retain deuterium incorporation
in the final product. The latter indicates an equilibrium be-
tween metalation and proto-demetalation before reaction
with the alkyne. These findings are consistent with those
found by Schipper et al.[20a] The addition of PivOH is essen-
tial for the final protonolysis, which yields the product and
regenerates the catalyst.[20a]
Scheme 3. Removal of the carbamate group.
Conclusions
We have developed two pathways that can be used to
access ortho-olefinated phenyl carbamates, including a ru-
thenium(II)-catalyzed oxidative olefination of phenyl carb-
amate with acrylates, and a rhodium(III)-catalyzed alkyne
hydroarylation of phenyl carbamate with internal alkynes
through direct C–H activation. Both reactions are highly
regio- and stereoselective. Considering that carbamates are
generally used as a protecting group for phenol derivatives,
these reactions are likely to be useful for the preparation of
Finally, both reactions were conducted on a large scale organic synthetic scaffolds such as substituted phenols or
with good performance: 3.0 mmol of naphthalen-2-yl di- substituted alkenes.
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Selective Olefination of Phenol Carbamates
H), 7.22 (d, J = 7.3 Hz, 1 H), 7.12 (t, J = 7.6 Hz, 1 H), 6.40 (d, J
= 16.1 Hz, 1 H), 4.23 (q, J = 7.1 Hz, 2 H), 3.18 (s, 3 H), 3.02 (s, 3
H), 2.19 (s, 3 H), 1.31 (t, J = 7.1 Hz, 3 H) ppm. 13C NMR (CDCl3,
100 MHz): δ = 166.7, 153.7, 148.7, 138.5, 132.6, 131.8, 127.8, 125.6,
124.8, 119.6, 60.2, 36.7, 36.3, 16.1, 14.1 ppm. MS (EI): calcd. for
C15H19NO4 [M+] 277.13; found 277.
Experimental Section
Analytical Methods: All the reactions were carried out under argon
by using standard Schlenk techniques. 1H (300 or 400 MHz) and
13C NMR (100 MHz) spectra were recorded with Bruker AV300 or
AV400 NMR spectrometers with CDCl3 or [D6]DMSO as solvent.
1
Chemical shifts of H and 13C NMR spectra are reported in parts
Ethyl
(E)-3-[2-(Dimethylcarbamoyloxy)biphenyl-3-yl]acrylate
per million (ppm). The residual solvent signals were used as refer-
ences and chemical shifts are given on the TMS scale (CDCl3: δH
= 7.26 ppm, δC = 77.00 ppm; [D6]DMSO: δH = 2.50 ppm, δC
(3c):[11] The title compound was isolated by column chromatog-
raphy (EtOAc/petroleum ether, 1:5) as an off-white solid (126.4 mg,
93%) from biphenyl-2-yl dimethylcarbamate (1c; 0.40 mmol,
96.5 mg, 1.0 equiv.) according to the General Procedure A. 1H
NMR (CDCl3, 400 MHz): δ = 7.81 (d, J = 16.1 Hz, 1 H), 7.60 (d,
J = 7.6 Hz, 1 H), 7.37–7.23 (m, 7 H), 6.45 (d, J = 16.1 Hz, 1 H),
4.22 (q, J = 7.1 Hz, 2 H), 2.89 (s, 3 H), 2.75 (s, 3 H), 1.30 (t, J =
7.1 Hz, 3 H) ppm. 13C NMR (CDCl3, 100 MHz): δ = 166.7, 153.7,
147.3, 138.5, 137.3, 136.5, 132.3, 128.8, 128.7, 128.0, 127.4, 126.3,
125.9, 120.1, 60.4, 36.6, 36.2, 14.2 ppm. MS (EI): calcd. for
C20H21NO4 [M+] 339.15; found 339.
=
39.52 ppm). All coupling constants (J values) are reported in Hertz
[Hz]. Multiplicities are reported as follows: singlet (s), doublet (d),
doublet of doublets (dd), doublet of doublet of doublets (ddd),
doublet of triplets (dt), triplet (t), triplet of doublets (td), quartet
(q), and multiplet (m). Column chromatography was performed on
silica gel 200–300 mesh. Analytical thin-layer chromatography
(TLC) was performed on precoated, glass-backed silica gel plates.
Visualization of the developed chromatogram was performed by
UV absorbance (254 nm). IR spectra were recorded as KBr disks
with a Nicolet 380 FTIR spectrometer. EI mass spectra and HRMS
data were recorded with Thermo Finnigan TRACE DSQ and Var-
ian 7.0 T FTICR mass spectrometers, respectively.
Ethyl (E)-3-[2-(Dimethylcarbamoyloxy)-3-methoxyphenyl]acrylate
(3d): The title compound was isolated by column chromatography
(EtOAc/petroleum ether, 1:5 to 1:2) as an off-white solid (92.8 mg,
79%) from 2-methoxyphenyl dimethylcarbamate (1d; 0.40 mmol,
78.1 mg, 1.0 equiv.) according to General Procedure A. M.p. 98–
Preparation of Chemicals: [{RuCl2(p-cymene)}2] was prepared from
RuCl3·xH2O according to a literature procedure.[33] All other rea-
gents were used as received from commercial sources. Unless other-
wise noted below, all other compounds have been reported in the
literature or are commercially available from Alfa Aesar China
(Tianjin) Chemical Co., Ltd. without any further purification. The
phenyl carbamate substrates were prepared according to a de-
scribed procedure.[34]
1
100 °C. H NMR (CDCl3, 300 MHz): δ = 7.82 (d, J = 16.1 Hz, 1
H), 7.22–7.14 (m, 2 H), 6.96 (dd, J = 7.4, 2.1 Hz, 1 H), 6.43 (d, J
= 16.1 Hz, 1 H), 4.25 (q, J = 7.1 Hz, 2 H), 3.84 (s, 3 H), 3.18 (s, 3
H), 3.03 (s, 3 H), 1.32 (t, J = 7.1 Hz, 3 H) ppm. 13C NMR (CDCl3,
100 MHz): δ = 166.6, 153.8, 152.1, 139.5, 138.1, 128.7, 125.9, 120.0,
118.4, 113.4, 60.3, 56.0, 36.7, 36.5, 14.1 ppm. HRMS (MALDI):
calcd. for C15H20NO5 [M + H]+ 294.1336; found 294.1331. IR: ν
˜
General Procedure for the RuII-Catalyzed Olefination of Phenyl
Carbamate Derivatives (General Procedure A): A mixture of 1
(0.40 mmol, 1.0 equiv.), [RuCl2(p-cymene)]2 (12.3 mg, 0.020 mmol,
5.0 mol-%), AgSbF6 (27.5 mg, 0.080 mmol, 20 mol-%), and
Cu(OAc)2 (145.3 mg, 0.80 mmol, 2.0 equiv.) was weighted in a
Schlenk tube equipped with a stir bar. Anhydrous THF (2.0 mL)
= 3088, 2984, 2940, 1721, 1635, 1582, 1482, 1280, 1185, 1158, 1028,
759, 751 cm–1.
Ethyl
(E)-3-[3-Chloro-2-(dimethylcarbamoyloxy)phenyl]acrylate
(3e):[11] The title compound was isolated by column chromatog-
raphy (EtOAc/petroleum ether, 1:5) as a colorless oil (95 mg, 80%)
from 2-chlorophenyl dimethylcarbamate (1e; 0.40 mmol, 79.8 mg,
1.0 equiv.) according to General Procedure A. 1H NMR (CDCl3,
400 MHz): δ = 7.74 (d, J = 16.1 Hz, 1 H), 7.50 (d, J = 7.8 Hz, 1
H), 7.42 (d, J = 8.0 Hz, 1 H), 7.16 (t, J = 7.9 Hz, 1 H), 6.43 (d, J
= 16.1 Hz, 1 H), 4.24 (q, J = 7.1 Hz, 2 H), 3.19 (s, 3 H), 3.03 (s, 3
H), 1.31 (t, J = 7.1 Hz, 3 H) ppm. 13C NMR (CDCl3, 100 MHz):
δ = 166.4, 153.0, 146.4, 137.6, 131.3, 130.2, 128.7, 126.4, 125.6,
121.1, 60.5, 36.9, 36.5, 14.2 ppm. MS (EI): calcd. for C14H16ClNO4
[M+] 297.08; found 297.
was added followed immediately by alkene
2 (0.80 mmol,
2.0 equiv.) and the mixture was stirred at 110 °C under Ar for 30 h.
The reaction mixture was cooled to room temp. and diluted with
CH2Cl2 and transferred to a round-bottomed flask. Silica was
added to the flask, and volatiles were evaporated under reduced
pressure. Purification was performed by flash column chromatog-
raphy on silica gel.
Ethyl
(E)-3-[1-(Dimethylcarbamoyloxy)naphthalen-2-yl]acrylate
(3a):[11] The title compound was isolated by column chromatog-
raphy (EtOAc/petroleum ether, 1:10 to 1:5) as an off-white solid
(106.6 mg, 85%) from naphthalen-1-yl dimethylcarbamate (1a;
0.40 mmol, 86.1 mg, 1.0 equiv.) according to General Procedure A.
1H NMR (CDCl3, 400 MHz): δ = 7.98 (d, J = 16.0 Hz, 1 H), 7.88–
7.82 (m, 2 H), 7.73–7.68 (m, 2 H), 7.55–7.50 (m, 2 H), 6.54 (d, J
= 16.0 Hz, 1 H), 4.28 (q, J = 7.1 Hz, 3 H), 3.36 (s, 3 H), 3.10 (s, 3
H), 1.35 (t, J = 7.1 Hz, 3 H) ppm. 13C NMR (CDCl3, 100 MHz):
δ = 166.8, 154.2, 146.6, 138.0, 135.2, 127.8, 127.3, 127.0, 126.1,
123.9, 122.7, 122.1, 119.8, 60.4, 36.9, 36.6, 14.2 (one signal missing
due to overlap) ppm. MS (EI): calcd. for C18H19NO4 [M+] 313.13;
found 313.
Ethyl (E)-3-[2-(Dimethylcarbamoyloxy)-3,5-dimethylphenyl]acrylate
(3f): The title compound was isolated by column chromatography
(EtOAc/petroleum ether, 1:5) as a colorless oil (96.8 mg, 83%) from
2,4-dimethylphenyl dimethylcarbamate (1f; 0.40 mmol, 77.3 mg,
1.0 equiv.) according to General Procedure A. 1H NMR (CDCl3,
400 MHz): δ = 7.73 (d, J = 16.1 Hz, 1 H), 7.25 (br. s, 1 H), 7.03
(br. s, 1 H), 6.39 (d, J = 16.0 Hz, 1 H), 4.22 (q, J = 7.1 Hz, 2 H),
3.17 (s, 3 H), 3.01 (s, 3 H), 2.28 (s, 3 H), 2.14 (s, 3 H), 1.30 (t, J =
7.1 Hz, 3 H) ppm. 13C NMR (CDCl3, 100 MHz): δ = 166.8, 153.9,
146.6, 138.7, 135.0, 133.5, 131.3, 127.3, 125.1, 119.3, 60.2, 36.7,
36.3, 20.6, 15.9, 14.1 ppm. HRMS (MALDI): calcd. for
C16H22NO4 [M + H]+ 292.1543; found 292.1538. IR: ν = 2929,
˜
1716, 1636, 1473, 1387, 1275, 1203, 1158, 1037, 983, 863, 755 cm–1.
Ethyl
(E)-3-[2-(Dimethylcarbamoyloxy)-3-methylphenyl]acrylate
(3b):[11] The title compound was isolated by column chromatog-
raphy (EtOAc/petroleum ether, 1:5) as an off-white solid (97.8 mg,
88%) from o-tolyl dimethylcarbamate (1b; 0.40 mmol, 71.7 mg,
1.0 equiv.) according to General Procedure A. 1H NMR (CDCl3,
400 MHz): δ = 7.77 (d, J = 16.1 Hz, 1 H), 7.45 (d, J = 7.6 Hz, 1
Ethyl
(E)-3-[3,5-Di-tert-butyl-2-(dimethylcarbamoyloxy)phenyl]-
acrylate (3g): The title compound was isolated by column
chromatography (EtOAc/petroleum ether, 1:15 to 1:5) as a colorless
oil (90.3 mg, 60%) from 2,4-di-tert-butylphenyl dimethylcarbamate
(1g; 0.40 mmol, 111.0 mg, 1.0 equiv.) according to General Pro-
Eur. J. Org. Chem. 2013, 1950–1962
© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
1955

B. Li, J. Ma, Y. Liang, N. Wang, S. Xu, H. Song, B. Wang
FULL PAPER
cedure A. H NMR (CDCl3, 400 MHz): δ = 7.64 (d, J = 15.9 Hz,
1
3085, 2988, 2941, 1724, 1708, 1631, 1596, 1382, 1308, 1207, 1161,
1082, 916, 836, 751, 459 cm–1.
1 H), 7.47 (d, J = 2.3 Hz, 1 H), 7.44 (d, J = 2.3 Hz, 1 H), 6.38 (d,
J = 15.9 Hz, 1 H), 4.23 (q, J = 7.1 Hz, 2 H), 3.22 (s, 3 H), 3.03 (s,
3 H), 1.35 (s, 9 H), 1.31 (s, 9 H), 1.31 (t, J = 7.1 Hz) ppm. 13C
NMR (CDCl3, 100 MHz): δ = 166.8, 154.5, 147.6, 146.6, 141.6,
139.8, 128.3, 126.4, 122.1, 119.2, 60.2, 36.9, 36.4, 34.9, 34.6, 31.3,
30.5, 14.2 ppm. HRMS (MALDI): calcd. for C22H33NO4Na [M +
Ethyl
(E)-3-[4-Bromo-2-(dimethylcarbamoyloxy)phenyl]acrylate
(3k): The title compound was isolated by column chromatography
(EtOAc/petroleum ether, 1:5) as an off-white solid (94.5 mg, 69%)
from 3-bromophenyl dimethylcarbamate (1k; 0.40 mmol, 97.6 mg,
1.0 equiv.) according to General Procedure A for 48 h. M.p. 63–
65 °C. 1H NMR (CDCl3, 400 MHz): δ = 7.72 (d, J = 16.1 Hz, 1
H), 7.44 (d, J = 8.4 Hz, 1 H), 7.35 (d, J = 1.8 Hz, 1 H), 7.32 (dd,
J = 8.4, 1.7 Hz, 1 H), 6.40 (d, J = 16.1 Hz, 1 H), 4.22 (q, J =
7.1 Hz, 2 H), 3.13 (s, 3 H), 3.00 (s, 3 H), 1.29 (t, J = 7.1 Hz, 3 H)
ppm. 13C NMR (CDCl3, 100 MHz): δ = 166.5, 153.6, 150.2, 137.1,
128.8, 128.0, 126.6, 126.3, 123.9, 120.1, 60.5, 36.8, 36.4, 14.1 ppm.
HRMS (MALDI): calcd. for C14H17BrNO4 [M + H]+ 342.0336;
Na]+ 398.2302; found 398.2305. IR: ν = 2957, 1728, 1707, 1441,
˜
1386, 1364, 1275, 1158, 1041, 981, 870, 751, 614 cm–1.
Ethyl
(E)-3-[2-(Dimethylcarbamoyloxy)-4-methylphenyl]acrylate
(3h):[11] The title compound was isolated by column chromatog-
raphy (EtOAc/petroleum ether, 1:5) as a colorless oil (98.9 mg,
89%) from m-tolyl dimethylcarbamate (1h; 0.40 mmol, 71.7 mg,
1.0 equiv.) according to General Procedure A. 1H NMR (CDCl3,
300 MHz): δ = 7.80 (d, J = 16.1 Hz, 1 H), 7.51 (d, J = 8.0 Hz, 1
H), 7.03 (d, J = 8.0 Hz, 1 H), 6.98 (s, 1 H), 6.39 (d, J = 16.1 Hz, 1
H), 4.24 (q, J = 7.1 Hz, 2 H), 3.17 (s, 3 H), 3.03 (s, 3 H), 2.36 (s,
3 H), 1.32 (t, J = 7.1 Hz, 3 H) ppm. 13C NMR (CDCl3, 100 MHz):
δ = 166.9, 154.2, 149.9, 141.7, 138.2, 126.9, 126.6, 124.3, 123.7,
118.5, 60.3, 36.7, 36.4, 21.2, 14.2 ppm. MS (EI): calcd. for
C15H19NO4 [M+] 277.13; found 277.
found 342.0334. IR: ν = 2986, 1734, 1716, 1637, 1591, 1482, 1386,
˜
1319, 1217, 1185, 984, 890, 818, 748 cm–1.
Ethyl
(E)-3-[3-(Dimethylcarbamoyloxy)naphthalen-2-yl]acrylate
(3l): The title compound was isolated by column chromatography
(EtOAc/petroleum ether, 1:5) as an off-white solid (111.5 mg, 89%)
from naphthalen-2-yl dimethylcarbamate (1l; 0.40 mmol, 86.1 mg,
1.0 equiv.) according to General Procedure A. M.p. 73–75 °C. 1H
NMR (CDCl3, 400 MHz): δ = 8.09 (s, 1 H), 7.94 (d, J = 16.1 Hz,
1 H), 7.81 (d, J = 7.8 Hz, 1 H), 7.75 (d, J = 7.8 Hz, 1 H), 7.62 (s,
1 H), 7.49–7.42 (m, 2 H), 6.59 (d, J = 16.0 Hz, 1 H), 4.28 (q, J =
7.1 Hz, 2 H), 3.21 (s, 3 H), 3.05 (s, 3 H), 1.35 (t, J = 7.1 Hz, 3 H)
ppm. 13C NMR (CDCl3, 100 MHz): δ = 166.7, 154.4, 147.2, 138.8,
134.3, 130.9, 128.1, 127.9, 127.3, 127.2, 126.9, 126.0, 120.18,
120.16, 60.4, 36.8, 36.4, 14.2 ppm. HRMS (MALDI): calcd. for
Ethyl (E)-3-[2-(Dimethylcarbamoyloxy)-4-methoxyphenyl]acrylate
(3i-a): The title compound was isolated by column chromatography
(EtOAc/petroleum ether, 1:10 to 1:5) as a white solid (71.7 mg,
61%) from 3-methoxyphenyl dimethylcarbamate (1i; 0.40 mmol,
78.1 mg, 1.0 equiv.) according to General Procedure A. M.p. 70–
71 °C. 1H NMR (CDCl3, 400 MHz): δ = 7.75 (d, J = 16.0 Hz, 1
H), 7.53 (d, J = 8.8 Hz, 1 H), 6.76 (dd, J = 8.8, 2.4 Hz, 1 H), 6.70
(d, J = 2.5 Hz, 1 H), 6.30 (d, J = 16.0 Hz, 1 H), 4.22 (q, J = 7.1 Hz,
2 H), 3.79 (s, 3 H), 3.16 (s, 3 H), 3.01 (s, 3 H), 1.30 (t, J = 7.1 Hz,
3 H) ppm. 13C NMR (CDCl3, 100 MHz): δ = 167.1, 161.8, 154.0,
151.3, 138.0, 128.1, 119.8, 117.0, 112.5, 108.3, 60.2, 55.5, 36.8, 36.4,
14.2 ppm. HRMS (MALDI): calcd. for C15H19NO5Na [M + Na]+
C18H19NO4Na [M + Na]+ 336.1206; found 336.1209. IR: ν = 3056,
˜
2988, 2944, 1740, 1715, 1639, 1624, 1387, 1314, 1241, 1173, 981,
881, 741, 667, 468 cm–1.
Methyl (E)-3-[1-(Dimethylcarbamoyloxy)naphthalen-2-yl]acrylate
(3m): The title compound was isolated by column chromatography
(EtOAc/petroleum ether, 1:5) as an off-white solid (100.6 mg, 84%)
from naphthalen-1-yl dimethylcarbamate (1a; 0.40 mmol, 86.1 mg,
1.0 equiv.) according to General Procedure A for 36 h. M.p. 99–
316.1155; found 316.1151. IR: ν = 2978, 2937, 2898, 1731, 1633,
˜
1612, 1508, 1389, 1303, 1170, 980, 827, 804, 753 cm–1.
1
101 °C. H NMR (CDCl3, 300 MHz): δ = 7.99 (d, J = 16.1 Hz, 1
Diethyl (2E,2ЈE)-3,3Ј-[2-(Dimethylcarbamoyloxy)-4-methoxy-1,3-
phenylene]diacrylate (3i-b):[11] The title compound was isolated by
column chromatography (EtOAc/petroleum ether, 1:10 to 1:5) as a
yellow solid (45.5 mg, 29%) from 1i (0.40 mmol, 78.1 mg,
1.0 equiv.) according to General Procedure A. 1H NMR (CDCl3,
400 MHz): δ = 7.71 (d, J = 16.0 Hz, 1 H), 7.67 (d, J = 15.5 Hz, 1
H), 7.59 (d, J = 8.9 Hz, 1 H), 6.83 (d, J = 8.9 Hz, 1 H), 6.72 (d, J
= 16.3 Hz, 1 H), 6.31 (d, J = 16.0 Hz, 1 H), 4.23 (q, J = 7.1 Hz, 2
H), 4.22 (q, J = 7.1 Hz, 2 H), 3.91 (s, 3 H), 3.23 (s, 3 H), 3.01 (s,
3 H), 1.31 (t, J = 7.1 Hz, 3 H), 1.30 (t, J = 7.1 Hz, 3 H) ppm. 13C
NMR (CDCl3, 100 MHz): δ = 167.4, 166.8, 160.9, 153.5, 150.0,
137.8, 134.3, 128.8, 123.1, 121.4, 118.1, 117.9, 108.9, 60.3, 55.9,
36.9, 36.5, 14.2 ppm. MS (EI): calcd. for C20H25NO7 [M+] 391.16;
found 391.
H), 7.88–7.81 (m, 2 H), 7.73–7.66 (m, 2 H), 7.55–7.49 (m, 2 H),
6.55 (d, J = 16.0 Hz, 1 H), 3.82 (s, 3 H), 3.35 (s, 3 H), 3.09 (s, 3 H)
ppm. 13C NMR (CDCl3, 100 MHz): δ = 167.4, 154.3, 146.8, 138.4,
135.4, 128.03, 127.99, 127.5, 127.2, 126.2, 124.0, 122.9, 122.3,
119.5, 51.8, 37.1, 36.8 ppm. HRMS (MALDI): calcd. for
C17H17NO4Na [M + Na]+ 322.1050; found 322.1048. IR: ν = 3053,
˜
2947, 1223, 1710, 1632, 1427, 1364, 1313, 1190, 1172, 1155, 985,
819, 760 cm–1.
Butyl
(E)-3-[1-(Dimethylcarbamoyloxy)naphthalen-2-yl]acrylate
(3n): The title compound was isolated by column chromatography
(EtOAc/petroleum ether, 1:10 to 1:4) as an off-white solid
(114.8 mg, 84%) from 1a (0.40 mmol, 86.1 mg, 1.0 equiv.) accord-
ing to General Procedure A for 48 h. M.p. 61–62 °C. 1H NMR
(CDCl3, 400 MHz): δ = 7.99 (d, J = 16.0 Hz, 1 H), 7.88–7.86 (m,
1 H), 7.82–7.80 (m, 1 H), 7.71–7.66 (m, 2 H), 7.54–7.49 (m, 2 H),
6.55 (d, J = 16.0 Hz, 1 H), 4.23 (t, J = 6.6 Hz, 2 H), 3.33 (s, 3 H),
3.08 (s, 3 H), 1.74–1.67 (m, 2 H), 1.51–1.42 (m, 2 H), 0.99 (t, J =
7.4 Hz, 3 H) ppm. 13C NMR (CDCl3, 100 MHz): δ = 166.8, 154.1,
146.6, 137.9, 135.1, 127.8, 127.3, 126.9, 126.0, 123.8, 122.6, 122.1,
119.7, 64.2, 36.8, 36.5, 30.6, 19.1, 13.6 (one signal missing due to
overlap) ppm. HRMS (MALDI): calcd. for C20H23NO4Na [M +
Ethyl (E)-3-[4-Chloro-2-(dimethylcarbamoyloxy)phenyl]acrylate (3j):
The title compound was isolated by column chromatography
(EtOAc/petroleum ether, 1:5) as an off-white solid (90.6 mg, 76%)
from 3-chlorophenyl dimethylcarbamate (1j; 0.40 mmol, 79.8 mg,
1.0 equiv.) according to General Procedure A for 36 h. M.p. 69–
70 °C. 1H NMR (CDCl3, 300 MHz): δ = 7.76 (d, J = 16.1 Hz, 1
H), 7.54 (d, J = 8.3 Hz, 1 H), 7.22–7.18 (m, 2 H), 6.41 (d, J =
16.1 Hz, 1 H), 4.25 (q, J = 7.1 Hz, 3 H), 3.16 (s, 3 H), 3.03 (s, 3
H), 1.33 (t, J = 7.1 Hz, 3 H) ppm. 13C NMR (CDCl3, 100 MHz):
δ = 166.5, 153.6, 150.3, 137.1, 136.1, 127.9, 126.0, 125.9, 123.8,
120.1, 60.5, 36.8, 36.5, 14.2 ppm. HRMS (MALDI): calcd. for
Na]+ 364.1519; found 364.1514. IR: ν = 3060, 2963, 2868, 1727,
˜
1630, 1362, 1297, 1249, 1174, 979, 806, 750, 663, 547 cm–1.
Benzyl
(E)-3-[1-(Dimethylcarbamoyloxy)naphthalen-2-yl]acrylate
(3o): The title compound was isolated by column chromatography
C14H16ClNO4Na [M + Na]+ 320.0660; found 320.0655. IR: ν =
˜
1956
www.eurjoc.org
© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2013, 1950–1962

Selective Olefination of Phenol Carbamates
(EtOAc/petroleum ether, 1:10 to 1:5) as an off-white solid
(136.7 mg, 91%) from 1a (0.40 mmol, 86.1 mg, 1.0 equiv.) accord-
ing to General Procedure A. M.p. 87–89 °C. 1H NMR (CDCl3,
300 MHz): δ = 8.04 (d, J = 16.0 Hz, 1 H), 7.90–7.80 (m, 2 H), 7.73–
7.67 (m, 2 H), 7.56–7.50 (m, 2 H), 7.46–7.36 (m, 5 H), 6.60 (d, J
= 16.0 Hz, 1 H), 5.28 (s, 2 H), 3.32 (s, 3 H), 3.07 (s, 3 H) ppm. 13C
NMR (CDCl3, 100 MHz): δ = 166.5, 154.2, 146.8, 138.6, 136.0,
135.3, 128.5, 128.1, 127.9, 127.4, 127.0, 126.1, 123.8, 122.7, 122.2,
119.3, 66.3, 36.9, 36.6 (two signals missing due to overlap) ppm.
HRMS (MALDI): calcd. for C23H21NO4Na [M + Na]+ 398.1363;
138.2, 130.9, 127.2, 127.1, 125.6, 123.3, 119.6, 60.4, 36.7, 36.4,
14.2 ppm. MS (EI): calcd. for C14H17NO4 [M+] 263.12; found 263.
Diethyl (2E,2ЈE)-3,3Ј-[2-(Dimethylcarbamoyloxy)-1,3-phenylene]di-
acrylate (3q-b):[11] 1H NMR (CDCl3, 400 MHz): δ = 7.76 (d, J =
16.1 Hz, 2 H), 7.66 (d, J = 7.8 Hz, 2 H), 7.30–7.28 (m, 1 H), 6.45
(d, J = 16.0 Hz, 2 H), 4.26 (q, J = 7.1 Hz, 4 H), 3.27 (s, 3 H), 3.05
(s, 3 H), 1.34 (t, J = 7.1 Hz, 6 H) ppm. 13C NMR (CDCl3,
100 MHz): δ = 166.4, 153.6, 148.6, 137.6, 129.1, 128.7, 126.1, 120.7,
60.5, 36.9, 36.5, 14.2 ppm. MS (EI): calcd. for C19H23NO6 [M+]
361.15; found 361.
found 398.1358. IR: ν = 3028, 2827, 1717, 1703, 1376, 1256, 1239,
˜
1163, 1148, 1013, 820, 756, 701, 553 cm–1.
Compounds 3r: According to General Procedure A, 3r-a (72.7 mg,
61%; off-white solid) and 3r-b (44.3 mg, 28%; off-white solid) were
isolated by column chromatography (EtOAc/petroleum ether, 1:10
to 1:5) from 4-chlorophenyl dimethylcarbamate (1o; 0.40 mmol,
79.8 mg, 1.0 equiv.). By using [RuCl2(p-cymene)]2 (10.0 mol-%),
AgSbF6 (40 mol-%), Cu(OAc)2 (4.0 equiv.), and acrylates
(5.0 equiv.), according to General Procedure A for 60 h, 3r-a
(46.5 mg, 39%; off-white solid) and 3r-b (95.1 mg, 60%; off-white
solid) were isolated.
Compounds 3p: According to the General Procedure A, 3p-a
(59.1 mg, 46% yield, off-white solid) and 3p-b (53.8 mg, 32% yield,
yellow solid) were isolated by column chromatography (EtOAc/pe-
troleum ether, 1:10 to 1:5) from methyl 2-(dimethylcarbamoyl-
oxy)benzoate (1m; 0.40 mmol, 89.3 mg, 1.0 equiv.). By using
[RuCl2(p-cymene)]2 (10.0 mol-%), AgSbF6 (40 mol-%), Cu(OAc)2
(4.0 equiv.), and acrylates (5.0 equiv.), according to the General
Procedure A for 60 h, 3p-a (41.1 mg, 32% yield, off-white solid)
and 3p-b (94.1 mg, 56% yield, yellow solid) were isolated.
Ethyl (E)-3-[5-Chloro-2-(dimethylcarbamoyloxy)phenyl]acrylate (3r-
1
a): M.p. 118–119 °C. H NMR (CDCl3, 400 MHz): δ = 7.74 (d, J
Methyl
(E)-2-(Dimethylcarbamoyloxy)-3-(3-ethoxy-3-oxoprop-1-
= 16.1 Hz, 1 H), 7.58 (d, J = 2.4 Hz, 1 H), 7.33 (dd, J = 8.7, 2.5 Hz,
1 H), 7.12 (d, J = 8.7 Hz, 1 H), 6.42 (d, J = 16.1 Hz, 1 H), 4.26 (q,
J = 7.1 Hz, 2 H), 3.16 (s, 3 H), 3.03 (s, 3 H), 1.33 (t, J = 7.1 Hz, 3
H) ppm. 13C NMR (CDCl3, 100 MHz): δ = 166.3, 153.8, 148.4,
136.9, 131.0, 130.6, 128.8, 126.8, 124.7, 120.9, 60.6, 36.8, 36.4,
14.2 ppm. HRMS (MALDI): calcd. for C14H16ClNO4Na
enyl)benzoate (3p-a): M.p. 69–70 °C. 1H NMR (CDCl3, 400 MHz):
δ = 8.00 (dd, J = 7.8, 1.5 Hz, 1 H), 7.87 (d, J = 16.1 Hz, 1 H), 7.80
(dd, J = 7.9, 1.3 Hz, 1 H), 7.30 (t, J = 7.9 Hz, 1 H), 6.45 (d, J =
16.1 Hz, 1 H), 4.26 (q, J = 7.1 Hz, 2 H), 3.87 (s, 3 H), 3.20 (s, 3
H), 2.04 (s, 3 H), 1.33 (t, J = 7.1 Hz, 3 H) ppm. 13C NMR (CDCl3,
100 MHz): δ = 166.5, 164.8, 154.0, 149.7, 137.6, 133.1, 131.2, 129.5,
125.4, 124.7, 120.9, 60.6, 52.2, 36.8, 36.6, 14.2 ppm. HRMS
(MALDI): calcd. for C16H20NO6 [M + H]+ 322.1285; found
[M + Na]+ 320.0660; found 320.0658. IR: ν = 3088, 3065, 2984,
˜
2934, 2906, 1732, 1704, 1481, 1388, 1285, 1221, 1181, 1166, 976,
871, 801, 754, 675, 459 cm–1.
322.1287. IR: ν = 2935, 1724, 1634,1437, 1385, 1322, 1301, 1264,
˜
1160, 1136, 1090, 994, 848, 758 cm–1. The structure of compound
3p-a was further confirmed by HMBC and NOE experiments, see
the Supporting Information (S6–S8) for details.
Diethyl
(2E,2ЈE)-3,3Ј-[5-Chloro-2-(dimethylcarbamoyloxy)-1,3-
phenylene]diacrylate (3r-b): M.p. 125–127 °C. 1H NMR (CDCl3,
400 MHz): δ = 7.66 (d, J = 16.0 Hz, 2 H), 7.59 (s, 2 H), 6.43 (d, J
= 16.0 Hz, 2 H), 4.25 (q, J = 7.1 Hz, 4 H), 3.24 (s, 3 H), 3.03 (s, 3
H), 1.33 (t, J = 7.1 Hz, 6 H) ppm. 13C NMR (CDCl3, 100 MHz):
δ = 166.1, 153.4, 147.1, 136.5, 131.9, 130.8, 128.2, 122.0, 60.8, 37.1,
36.6, 14.2 ppm. HRMS (MALDI): calcd. for C19H22ClNO6Na [M
Diethyl (2E,2ЈE)-3,3Ј-[2-(Dimethylcarbamoyloxy)-3-(methoxycarb-
onyl)-1,4-phenylene]diacrylate (3p-b): M.p. 94–96 °C. 1H NMR
(CDCl3, 400 MHz): δ = 7.77–7.68 (m, 3 H), 7.49 (d, J = 8.4 Hz, 1
H), 6.45 (d, J = 16.1 Hz, 1 H), 6.38 (d, J = 15.8 Hz, 1 H), 4.23 (q,
J = 7.1 Hz, 4 H), 3.90 (s, 3 H), 3.11 (s, 3 H), 3.00 (s, 3 H), 1.30 (t,
J = 7.1 Hz, 6 H) ppm. 13C NMR (CDCl3, 100 MHz): δ = 166.3,
166.0, 165.6, 153.4, 147.9, 140.4, 136.8, 135.9, 130.2, 128.7, 128.1,
124.1, 122.2, 121.4, 60.7, 60.6, 52.6, 36.9, 36.5, 14.2 (one signal
missing due to overlap) ppm. HRMS (MALDI): calcd. for
+ Na]+ 418.1028; found 418.1026. IR: ν = 3082, 2990, 2904, 1717,
˜
1637, 1388, 1318, 1259, 1184, 1154, 1035, 973, 751, 565 cm–1.
Compounds 3s: According to General Procedure A, 3s-a (82.1 mg,
60%; off-white solid) and 3s-b (66.9 mg, 38%; off-white solid) were
isolated by column chromatography (EtOAc/petroleum ether, 1:10
to 1:5) from 4-bromophenyl dimethylcarbamate (1p; 0.40 mmol,
97.6 mg, 1.0 equiv.). By using [RuCl2(p-cymene)]2 (10.0 mol-%),
AgSbF6 (40 mol-%), Cu(OAc)2 (4.0 equiv.), and acrylates
(5.0 equiv.), according to General Procedure A for 60 h, 3s-a
(43.8 mg, 32%; off-white solid) and 3s-b (103.9 mg, 59%; off-white
solid) were isolated.
C21H26NO8 [M + H]+ 420.1653; found 420.1654. IR: ν = 2982,
˜
1736, 1714, 1635, 1473, 1392, 1321, 1282, 1175, 1042, 980, 822,
750 cm–1.
Compounds 3q: According to General Procedure A, 3q-a (53.7 mg,
51%; off-white solid) and 3q-b (63.7 mg, 44%; off-white solid) were
isolated by column chromatography (EtOAc/petroleum ether, 1:10
to 1:5) from phenyl dimethylcarbamate (1n; 0.40 mmol, 66.1 mg,
1.0 equiv.). By using [RuCl2(p-cymene)]2 (10.0 mol-%), AgSbF6
(40 mol-%), Cu(OAc)2 (4.0 equiv.), and acrylates (5.0 equiv.), ac-
cording to General Procedure A for 60 h, 3q-a (29.6 mg, 28%; off-
white solid) and 3q-b (99.8 mg, 69%; off-white solid) were isolated
by column chromatography (EtOAc/petroleum ether, 1:10 to 1:5)
from 1n (0.40 mmol, 66.1 mg, 1.0 equiv.).
Ethyl (E)-3-[2-(Dimethylcarbamoyloxy)phenyl]acrylate (3q-a):[11] 1H
NMR (CDCl3, 400 MHz): δ = 7.83 (d, J = 16.1 Hz, 1 H), 7.60 (dd,
J = 7.8, 1.4 Hz, 1 H), 7.39–7.34 (m, 1 H), 7.20 (t, J = 7.5 Hz, 1 H),
7.15 (dd, J = 8.2, 0.8 Hz, 1 H), 6.43 (d, J = 16.1 Hz, 1 H), 4.24 (q,
J = 7.1 Hz, 2 H), 3.16 (s, 3 H), 3.01 (s, 3 H), 1.31 (t, J = 7.1 Hz, 3
H) ppm. 13C NMR (CDCl3, 100 MHz): δ = 166.7, 154.1, 150.0,
Ethyl (E)-3-[5-Bromo-2-(dimethylcarbamoyloxy)phenyl]acrylate (3s-
1
a): M.p. 102–104 °C. H NMR (CDCl3, 400 MHz): δ = 7.76–7.71
(m, 2 H), 7.47 (dd, J = 8.6, 2.2 Hz, 1 H), 7.07 (d, J = 8.7 Hz, 1 H),
6.42 (d, J = 16.1 Hz, 1 H), 4.26 (q, J = 7.1 Hz, 2 H), 3.16 (s, 3 H),
3.02 (s, 3 H), 1.33 (t, J = 7.1 Hz, 3 H) ppm. 13C NMR (CDCl3,
100 MHz): δ = 166.3, 153.7, 148.9, 136.7, 133.4, 129.8, 129.2, 125.0,
120.9, 118.6, 60.5, 36.8, 36.4, 14.1 ppm. HRMS (MALDI): calcd.
for C14H17BrNO4 [M + H]+ 342.0336; found 342.0338. IR: ν =
˜
3086, 2983, 2932, 1704, 1477, 1388, 1285, 1219, 1165, 1105, 975,
870, 753, 660, 455 cm–1.
Diethyl
(2E,2ЈE)-3,3Ј-[5-Bromo-2-(dimethylcarbamoyloxy)-1,3-
phenylene]diacrylate (3s-b): M.p. 151–158 °C. 1H NMR (CDCl3,
300 MHz): δ = 7.74 (s, 2 H), 7.65 (d, J = 16.0 Hz, 2 H), 6.42 (d, J
Eur. J. Org. Chem. 2013, 1950–1962
© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
1957

B. Li, J. Ma, Y. Liang, N. Wang, S. Xu, H. Song, B. Wang
FULL PAPER
= 16.0 Hz, 2 H), 4.25 (q, J = 7.1 Hz, 4 H), 3.24 (s, 3 H), 3.03 (s, 3 Compounds 3v: According to General Procedure A, 3v-a (57.5 mg,
H), 1.33 (t, J = 7.1 Hz, 6 H) ppm. 13C NMR (CDCl3, 100 MHz):
δ = 166.1, 153.3, 147.6, 136.4, 131.21, 131.15, 122.0, 119.5, 60.8,
37.1, 36.6, 14.2 ppm. HRMS (MALDI): calcd. for C19H23BrNO6
49%; off-white solid) and 3v-b (70.6 mg, 45%; off-white solid) were
isolated by column chromatography (EtOAc/petroleum ether, 1:10
to 1:5) from 4-methoxyphenyl dimethylcarbamate (1s; 0.40 mmol,
78.1 mg, 1.0 equiv.). By using [RuCl2(p-cymene)]2 (10.0 mol-%),
[M + H]+ 440.0703; found 440.0706. IR: ν = 3078, 2988, 2902,
˜
1720, 1638, 1317, 1258, 1183, 1152, 1036, 1003, 972, 860, 750 cm–1. AgSbF6 (40 mol-%), Cu(OAc)2 (4.0 equiv.), and acrylates
(5.0 equiv.), according to General Procedure A for 60 h, only 3v-b
(131.6 mg, 84%; off-white solid) was isolated.
Compounds 3t: According to General Procedure A, 3t-a (58%
yield) and 3t-b (7% yield) were isolated by column chromatography
Ethyl (E)-3-[2-(Dimethylcarbamoyloxy)-5-methoxyphenyl]acrylate
(EtOAc/petroleum ether, 1:10 to 1:5) as an inseparable mixture
(83.2 mg, off-white solid) from 4-nitrophenyl dimethylcarbamate
(1q; 0.40 mmol, 84.1 mg, 1.0 equiv.). By using [RuCl2(p-cymene)]2
(10.0 mol-%), AgSbF6 (40 mol-%), Cu(OAc)2 (4.0 equiv.), and ac-
rylates (5.0 equiv.), according to General Procedure A for 60 h, 3t-
a (59% yield) and 3t-b (16% yield) were isolated as an inseparable
mixture (98.8 mg, off-white solid).
1
(3v-a): M.p. 96–98 °C. H NMR (CDCl3, 300 MHz): δ = 7.78 (d,
J = 16.1 Hz, 1 H), 7.09–7.06 (m, 2 H), 6.93 (dd, J = 9.0, 3.0 Hz, 1
H), 6.41 (d, J = 16.1 Hz, 1 H), 4.26 (q, J = 7.1 Hz, 2 H), 3.82 (s, 3
H), 3.16 (s, 3 H), 3.02 (s, 3 H), 1.33 (t, J = 7.1 Hz, 3 H) ppm. 13C
NMR (CDCl3, 100 MHz): δ = 166.6, 156.8, 154.6, 143.8, 138.2,
127.8, 124.2, 119.8, 117.0, 111.0, 60.4, 55.5, 36.7, 36.4, 14.2 ppm.
HRMS (MALDI): calcd. for C15H19NO5Na [M + Na]+ 316.1155;
Ethyl (E)-3-[2-(Dimethylcarbamoyloxy)-5-nitrophenyl]acrylate (3t-a)
and Diethyl (2E,2ЈE)-3,3Ј-[2-(Dimethylcarbamoyloxy)-5-nitro-1,3-
found 316.1149. IR: ν = 2930, 1718, 1637, 1490, 1387, 1275, 1242,
˜
1203, 1158, 1037, 983, 863, 755 cm–1.
1
phenylene]diacrylate (3t-b): H NMR (CDCl3, 400 MHz) (mixture
Diethyl (2E,2ЈE)-3,3Ј-[2-(Dimethylcarbamoyloxy)-5-methoxy-1,3-
phenylene]diacrylate (3v-b): M.p. 126–128 °C. 1H NMR (CDCl3,
300 MHz): δ = 7.70 (d, J = 16.0 Hz, 2 H), 7.15 (s, 2 H), 6.41 (d, J
= 16.0 Hz, 2 H), 4.25 (q, J = 7.1 Hz, 4 H), 3.84 (s, 3 H), 3.24 (s, 3
H), 3.03 (s, 3 H), 1.33 (t, J = 7.1 Hz, 6 H) ppm. 13C NMR (CDCl3,
100 MHz): δ = 166.4, 156.9, 154.1, 142.7, 137.7, 129.7, 120.8, 113.8,
60.6, 55.6, 36.9, 36.5, 14.2 ppm. HRMS (MALDI): calcd. for
of 3t-a and 3t-b): δ = 8.50 (d, J = 2.6 Hz, 1 H, 3t-a), 8.49 (br. s, 2
H, 3t-b), 8.23 (dd, J = 9.0, 2.7 Hz, 1 H, 3t-a), 7.82 (d, J = 16.1 Hz,
1 H, 3t-a), 7.71 (d, J = 16.0 Hz, 2 H, 3t-b), 7.41 (d, J = 9.0 Hz, 1
H, 3t-a), 6.57 [d, J = 16.1 Hz, 1 H (3t-a) + 2 H (3t-b)], 4.28 [q, J
= 7.1 Hz, 2 H (3t-a) + 4H (3t-b)], 3.27 (s, 3 H, 3t-b), 3.19 (s, 3 H,
3t-a), 3.05 [br. s, 3 H (3t-a) + 3 H (3t-b)], 1.35 [t, J = 7.1 Hz, 3 H
(3t-a) + 3 H (3t-b)] ppm. 13C NMR (CDCl3, 100 MHz) (mixture
of 3t-a and 3t-b): δ = 166.0, 154.3, 152.9, 152.6, 144.9, 136.0, 135.6,
130.9, 128.3, 125.4, 124.1, 123.5, 123.0, 122.6, 122.5, 61.0, 60.9,
37.1, 37.0, 36.7, 36.6, 14.2 ppm. HRMS (MALDI): calcd. for
C14H16N2O6Na (3t-a) [M + Na]+ 331.0901; found 331.0905; calcd.
for C19H22N2O8Na (3t-b) [M + Na]+ 429.1268; found 429.1271. IR:
C20H25NO7Na [M + Na]+ 414.1523; found 414.1516. IR: ν = 2984,
˜
2930, 1735, 1709, 1638, 1462, 1391, 1341, 1265, 1182, 1158, 984,
856, 756, 577 cm–1.
Compounds 3w: According to General Procedure A, 3w-a (62.7 mg,
49%; off-white solid) and 3w-b (71.7 mg, 43%; off-white solid) were
isolated by column chromatography (EtOAc/petroleum ether, 1:10
to 1:5) from 4-tert-butylphenyl dimethylcarbamate (1t; 0.40 mmol,
88.5 mg, 1.0 equiv.). By using [RuCl2(p-cymene)]2 (10.0 mol-%),
AgSbF6 (40 mol-%), Cu(OAc)2 (4.0 equiv.), and acrylates
(5.0 equiv.), according to General Procedure A for 60 h, only 3w-b
(143.8 mg, 86%; off-white solid) was isolated.
ν = 2925, 2360, 1733, 1716, 1687, 1519, 1508, 1387, 1346, 1283,
˜
1256, 1159, 1045, 979, 877, 744, 667 cm–1.
Compounds 3u: According to General Procedure A, 3u-a (51.1 mg,
46%; off-white solid) and 3u-b (78.1 mg, 52%; off-white solid) were
isolated by column chromatography (EtOAc/petroleum ether, 1:10
to 1:5) from p-tolyl dimethylcarbamate (1r; 0.40 mmol, 71.7 mg,
1.0 equiv.). By using [RuCl2(p-cymene)]2 (10.0 mol-%), AgSbF6
(40 mol-%), Cu(OAc)2 (4.0 equiv.), and acrylates (5.0 equiv.), ac-
cording to General Procedure A for 60 h, only 3u-b (139.7 mg,
93%; off-white solid) was isolated.
Ethyl (E)-3-[5-tert-Butyl-2-(dimethylcarbamoyloxy)phenyl]acrylate
(3w-a): M.p. 138–140 °C. 1H NMR (CDCl3, 300 MHz): δ = 7.83
(d, J = 16.1 Hz, 1 H), 7.59 (s, 1 H), 7.40 (d, J = 8.5 Hz, 1 H), 7.08
(d, J = 8.6 Hz, 1 H), 6.44 (d, J = 16.1 Hz, 1 H), 4.25 (q, J = 7.1 Hz,
2 H), 3.15 (s, 3 H), 3.01 (s, 3 H), 1.32 (t, J = 7.3 Hz, 3 H), 1.31 (s,
9 H) ppm. 13C NMR (CDCl3, 100 MHz): δ = 166.8, 154.3, 148.3,
147.8, 138.9, 128.3, 126.3, 123.9, 122.7, 119.2, 60.3, 36.7, 36.3, 34.4,
31.2, 14.2 ppm. HRMS (MALDI): calcd. for C18H26NO4 [M +
Ethyl
(E)-3-[2-(Dimethylcarbamoyloxy)-5-methylphenyl]acrylate
1
(3u-a): M.p. 88–89 °C. H NMR (CDCl3, 300 MHz): δ = 7.80 (d,
J = 16.0 Hz, 1 H), 7.41 (s, 1 H), 7.18 (d, J = 8.3 Hz, 1 H), 7.04 (d,
J = 8.3 Hz, 1 H), 6.42 (d, J = 16.0 Hz, 1 H), 4.25 (q, J = 7.1 Hz,
2 H), 3.16 (s, 3 H), 3.02 (s, 3 H), 2.34 (s, 3 H), 1.33 (t, J = 7.1 Hz,
3 H) ppm. 13C NMR (CDCl3, 100 MHz): δ = 166.6, 154.2, 147.8,
138.2, 135.0, 131.6, 127.3, 126.7, 122.9, 119.3, 60.2, 36.6, 36.2, 20.6,
14.1 ppm. HRMS (MALDI): calcd. for C15H20NO4 [M + H]+
H]+ 320.1856; found 320.1856. IR: ν = 3080, 2985, 2958, 2901,
˜
2868, 1727, 1707, 1637, 1493, 1390, 1364, 1325, 1222, 1162, 1035,
990, 858, 751 cm–1.
Diethyl (2E,2ЈE)-3,3Ј-[5-tert-Butyl-2-(dimethylcarbamoyloxy)-1,3-
phenylene]diacrylate (3w-b): M.p. 115–117 °C. 1H NMR (CDCl3,
400 MHz): δ = 7.72 (d, J = 16.1 Hz, 2 H), 7.63 (s, 2 H), 6.42 (d, J
= 16.0 Hz, 2 H), 4.23 (q, J = 7.1 Hz, 4 H), 3.22 (s, 3 H), 3.01 (s, 3
H), 1.32 (s, 9 H), 1.31 (t, J = 7.3 Hz, 6 H) ppm. 13C NMR (CDCl3,
100 MHz): δ = 166.5, 153.8., 148.7, 146.5, 138.3, 128.2, 126.1,
120.3, 60.4, 36.9, 36.4, 34.5, 31.1, 14.2 ppm. HRMS (MALDI):
calcd. for C23H31NO6Na [M + Na]+ 440.2044; found 440.2047. IR:
278.1387; found 278.1392. IR: ν = 3075, 3055, 2990, 2926, 1719,
˜
1495, 1394, 1280, 1228, 1208, 1162, 1042, 997, 857, 811, 750,
559 cm–1.
Diethyl
(2E,2ЈE)-3,3Ј-[2-(Dimethylcarbamoyloxy)-5-methyl-1,3-
phenylene]diacrylate (3u-b): M.p. 121–122 °C. 1H NMR (CDCl3,
400 MHz): δ = 7.70 (d, J = 16.0 Hz, 2 H), 7.44 (s, 2 H), 6.41 (d, J
= 16.0 Hz, 2 H), 4.24 (q, J = 7.1 Hz, 4 H), 3.24 (s, 3 H), 3.02 (s, 3
H), 2.36 (s, 3 H), 1.31 (t, J = 7.1 Hz, 6 H) ppm. 13C NMR (CDCl3,
100 MHz): δ = 166.5, 153.9, 146.6, 137.8, 135.7, 129.4, 128.6, 120.4,
60.4, 36.9, 36.5, 20.8, 14.2 ppm. HRMS (MALDI): calcd. for
ν = 3066, 2959, 1731, 1714, 1699, 1639, 1387, 1368, 1278, 1243,
˜
1181, 1161, 1041, 991, 880, 753, 702, 581 cm–1.
2-[(E)-2-(Phenylsulfonyl)vinyl]naphthalen-1-yl Dimethylcarbamate
(3-Sulfone): The title compound was isolated by column
chromatography (EtOAc/petroleum ether, 1:1, then MeOH/
CH2Cl2, 1:1) as a brown solid (65.1 mg, 43%) from 1a (0.40 mmol,
C20H25NO6Na [M + Na]+ 398.1574; found 398.1570. IR: ν = 2989,
˜
2934, 1716, 1637, 1457, 1389, 1321, 1266, 1182, 1043, 975, 857,
753, 568 cm–1.
1958
www.eurjoc.org
© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2013, 1950–1962

Selective Olefination of Phenol Carbamates
86 mg, 1.0 equiv.) according to General Procedure A for 24 h. M.p.
0.3 mmol), PivOH (245 mg, 2.4 mmol), and alkyne (0.6 mmol) was
combined in a Schlenk tube with a stir bar, then PhCl (2.0 mL) was
205–206 °C. 1H NMR (CDCl3, 400 MHz): δ = 7.98–7.95 (m, 3 H),
7.89–7.86 (m, 1 H), 7.83–7.81 (m, 1 H), 7.69 (d, J = 8.7 Hz, 1 H), added under Ar. The reaction mixture was heated to the desired
7.63–7.61 (m, 1 H), 7.58–7.54 (m, 4 H), 7.53 (d, J = 5.7 Hz, 1 H), temperature with stirring for the desired reaction time, then the vial
6.93 (d, J = 15.5 Hz, 1 H), 3.36 (s, 3 H), 3.10 (s, 3 H) ppm. 13C was cooled to room temp., and the crude product was purified by
NMR (CDCl3, 100 MHz): δ = 154.0, 147.5, 140.5, 136.4, 135.6,
133.4, 129.7, 129.3, 128.6, 128.0, 127.9, 127.8, 127.3, 126.4, 122.8,
122.4, 122.1, 37.1, 36.8 ppm. HRMS (MALDI): calcd. for
flash chromatography on silica gel.
(E)-2-(1,2-Diphenylvinyl)naphthalen-1-yl Dimethylcarbamate (5a):
The title compound was isolated by column chromatography
(EtOAc/petroleum ether, 1:20) as a yellow solid (116.9 mg, 99%)
from 1a (0.30 mmol, 64.6 mg, 1.0 equiv.) according to General Pro-
cedure B for 18 h. M.p. 101–102 °C. 1H NMR (CDCl3, 300 MHz):
δ = 7.94–7.91 (m, 1 H), 7.85 (dd, J = 6.3, 2.9 Hz, 1 H), 7.69 (d, J
= 8.5 Hz, 1 H), 7.55–7.47 (m, 2 H), 7.35 (d, J = 8.5 Hz, 1 H), 7.28–
7.24 (m, 5 H), 7.20–7.12 (m, 5 H), 6.92 (s, 1 H), 2.86 (s, 3 H), 2.84
(s, 3 H) ppm. 13C NMR (CDCl3, 100 MHz): δ = 154.1, 144.5,
140.1, 138.9, 137.3, 133.9, 133.2, 131.5, 130.2, 129.4, 128.20,
128.17, 128.1, 127.9, 127.7, 127.2, 126.8, 126.5, 126.2, 125.2, 121.9,
36.6, 36.2 ppm. HRMS (MALDI): calcd. for C27H23NO2Na [M +
C21H19NNaO4S [M + Na]+ 404.0927; found 404.0926. IR: ν =
˜
3054, 2962, 2926, 1722, 1616, 1450, 1364, 1304, 1262, 1146, 1086,
846, 740, 610, 559 cm–1.
Ethyl (E)-3-[1-(Dimethylcarbamoyloxy)-3,4-dihydronaphthalen-2-yl-
]acrylate (3x): The title compound was isolated by column
chromatography (EtOAc/petroleum ether, 1:10 to 1:5) as a yellow
solid (42.5 mg, 45%) from 3,4-dihydronaphthalen-1-yl dimethyl-
carbamate (1u; 0.30 mmol, 65.1 mg, 1.0 equiv.) according to Gene-
ral Procedure A for 40 h, but [RuCl2(p-cymene)]2 (7.5 mol-%),
AgSbF6 (30 mol-%), and AgOAc (3.0 equiv.) were used. M.p. 102–
1
Na]+ 416.1621; found 416.1623. IR: ν = 3055, 3019, 2925, 1719,
103 °C. H NMR (CDCl3, 400 MHz): δ = 7.77 (d, J = 15.8 Hz, 1
˜
1599, 1490, 1445, 1343, 1146, 1083, 820, 751, 670 cm–1.
H), 7.22–7.15 (m, 4 H), 6.01 (d, J = 15.8 Hz, 1 H), 4.23 (q, J =
7.1 Hz, 2 H), 3.23 (s, 3 H), 3.02 (s, 3 H), 2.94 (t, J = 7.9 Hz, 2 H),
2.60 (t, J = 7.9 Hz, 2 H), 1.31 (t, J = 7.1 Hz, 3 H) ppm. 13C NMR
(CDCl3, 100 MHz): δ = 167.3, 153.9, 147.9, 138.5, 137.4, 130.9,
128.9, 127.5, 126.7, 122.4, 122.3, 118.0, 60.3, 36.9, 36.6, 27.2, 22.8,
14.3 ppm. HRMS (MALDI): calcd. for C18H21NO4Na [M + Na]+
(E)-2-(1,2-Diphenylvinyl)-6-methoxyphenyl Dimethylcarbamate (5b):
The title compound was isolated by column chromatography
(EtOAc/petroleum ether, 1:20 to 1:10) as a colorless oil (69.5 mg,
62%) from 2-methoxyphenyl dimethylcarbamate (1d; 0.30 mmol,
58.6 mg, 1.0 equiv.) according to General Procedure B for 30 h.
338.1363; found 338.1366. IR: ν = 3066, 2976, 2951, 2891, 1732,
˜
1
1614, 1392, 1314, 1171, 1230, 1029, 973, 858, 771 cm–1.
M.p. 145–147 °C. H NMR (CDCl3, 300 MHz): δ = 7.30 (br. s, 5
H), 7.23–7.16 (m, 6 H), 7.03–6.99 (m, 2 H), 6.87 (s, 1 H), 3.92 (s,
3 H), 2.86 (s, 3 H), 2.77 (s, 3 H) ppm. 13C NMR (CDCl3,
100 MHz): δ = 153.6, 152.3, 139.9, 138.8, 138.5, 138.2, 137.2, 130.9,
129.8, 129.4, 128.0, 127.8, 126.9, 126.7, 125.5, 122.6, 111.5, 56.1,
36.5, 36.1 ppm. HRMS (MALDI): calcd. for C24H24NO3 [M +
Butyl (E)-3-[1-(Dimethylcarbamoyloxy)-3,4-dihydronaphthalen-2-yl-
]acrylate (3y): The title compound was isolated by column
chromatography (EtOAc/petroleum ether, 1:10 to 1:5) as a yellow
oil (40.2 mg, 39%) from 1u (0.30 mmol, 65.1 mg, 1.0 equiv.) ac-
cording to General Procedure A for 40 h, but [RuCl2(p-cymene)]2
(7.5 mol-%), AgSbF6 (30 mol-%), and AgOAc (3.0 equiv.) were
used. 1H NMR (CDCl3, 300 MHz): δ = 7.76 (d, J = 15.8 Hz, 1 H),
7.22–7.16 (m, 4 H), 6.01 (d, J = 15.8 Hz, 1 H), 4.17 (t, J = 6.6 Hz,
2 H), 3.23 (s, 3 H), 3.02 (s, 3 H), 2.93 (t, J = 8.0 Hz, 2 H), 2.60 (t,
J = 8.0 Hz, 2 H), 1.71–1.62 (m, 3 H), 1.49–1.36 (m, 3 H), 0.96 (t,
J = 7.3 Hz, 3 H) ppm. 13C NMR (CDCl3, 100 MHz): δ = 167.3,
153.8, 147.9, 138.4, 137.3, 130.8, 128.9, 127.4, 126.6, 122.34,
122.25, 118.0, 64.2, 36.8, 36.5, 30.7, 27.1, 22.7, 19.1, 13.7 ppm.
HRMS (MALDI): calcd. for C20H25NO4Na [M + Na]+ 366.1676;
H]+ 374.1751; found 374.1745. IR: ν = 3021, 2936, 1725, 1576,
˜
1468, 1441, 1387, 1271, 1204, 1164, 1080, 779, 754, 697 cm–1.
(E)-2-[2-Chloro-6-(1,2-diphenylvinyl)phenyl]-N,N-dimethylacetamide
(5c): The title compound was isolated by column chromatography
(EtOAc/petroleum ether, 1:20) as an off-white solid (72.6 mg, 64%)
from 2-chlorophenyl dimethylcarbamate (1e; 0.30 mmol, 59.9 mg,
1.0 equiv.) according to General Procedure B for 30 h. M.p. 177–
179 °C. 1H NMR (CDCl3, 300 MHz): δ = 7.38 (dd, J = 7.9, 1.6 Hz,
1 H), 7.24–7.17 (m, 6 H), 7.16–7.12 (m, 4 H), 7.08–7.06 (m, 2 H),
6.78 (s, 1 H), 2.79 (s, 3 H), 2.69 (s, 3 H) ppm. 13C NMR (CDCl3,
100 MHz): δ = 152.7, 145.4, 139.61, 139.59, 138.3, 136.9, 131.5,
129.9, 129.4, 129.2, 128.5, 128.1, 127.9, 127.2, 127.0, 126.0, 36.6,
36.1 (one signal missing due to overlap) ppm. HRMS (MALDI):
calcd. for C23H20ClNO2Na [M + Na]+ 400.1075; found 400.1073.
found 366.1672. IR: ν = 2957, 1732, 1615, 1507, 1457, 1394, 1313,
˜
1245, 1168, 1078, 764 cm–1.
Butyl (E)-3-[1-(Dimethylcarbamoyloxy)-3,4-dihydronaphthalen-2-yl-
]acrylate (3z): The title compound was isolated by column
chromatography (EtOAc/petroleum ether, 1:10 to 1:5) as a yellow
oil (66.9 mg, 59%) from 1u (0.30 mmol, 65.1 mg, 1.0 equiv.) ac-
cording to General Procedure A for 40 h, but [RuCl2(p-cymene)]2
(7.5 mol-%), AgSbF6 (30 mol-%), and AgOAc (3.0 equiv.) were
used. 1H NMR (CDCl3, 300 MHz): δ = 7.88 (d, J = 15.8 Hz, 1 H),
7.45–7.38 (m, 6 H), 7.31–7.22 (m, 3 H), 6.13 (d, J = 15.8 Hz, 1 H),
5.28 (s, 2 H), 3.26 (s, 3 H), 3.06 (s, 3 H), 2.99 (t, J = 8.0 Hz, 2 H),
2.65 (t, J = 7.9 Hz, 2 H) ppm. 13C NMR (CDCl3, 100 MHz): δ =
167.0, 153.8, 148.1, 139.1, 137.4, 136.1, 130.8, 129.0, 128.5, 128.1,
127.4, 126.6, 122.30, 122.28, 117.5, 66.1, 36.8, 36.5, 27.1, 22.6 ppm.
HRMS (MALDI): calcd. for C23H23NO4Na [M + Na]+ 400.1519;
IR: ν = 3020, 2924, 1736, 1638, 1617, 1438, 1379, 1222, 1157, 780,
˜
705, 691, 601 cm–1.
(E)-2-(1,2-Diphenylvinyl)-4,6-dimethylphenyl
Dimethylcarbamate
(5d): The title compound was isolated by column chromatography
(EtOAc/petroleum ether, 1:20) as an off-white solid (75.8 mg, 68%)
from 2,4-dimethylphenyl dimethylcarbamate (1f; 0.30 mmol,
58.0 mg, 1.0 equiv.) according to General Procedure B for 24 h.
1
M.p. 142–144 °C. H NMR (CDCl3, 300 MHz): δ = 7.22 (br. s, 5
H), 7.16–7.12 (m, 3 H), 7.10–7.08 (m, 2 H), 7.01 (s, 1 H), 6.96 (s,
1 H), 6.76 (s, 1 H), 2.77 (s, 3 H), 2.67 (s, 3 H), 2.30 (s, 3 H), 2.17
(s, 3 H) ppm. 13C NMR (CDCl3, 100 MHz): δ = 153.7, 145.3,
140.1, 139.4, 137.4, 137.1, 134.6, 131.2, 131.0, 130.5, 129.9, 129.4,
129.3, 127.9, 127.8, 126.9, 126.6, 36.4, 36.0, 20.7, 16.3 ppm. HRMS
(MALDI): calcd. for C25H25NO2Na [M + Na]+ 394.1778; found
found 400.1525. IR: ν = 3031, 2940, 1727, 1613, 1454, 1393, 1310,
˜
1246, 1160, 1077, 981, 757, 698 cm–1.
General Procedure for the RhIII-Catalyzed Alkyne Hydroarylation
of Phenol Carbamate Derivatives (General Procedure B): A mixture
of [Cp*RhCl2]2 (9.18 mg, 0.015 mmol, 5.0 mol-%), AgSbF6
(20.7 mg, 0.06 mmol, 20.0 mol-%), phenyl carbamate (1;
394.1776. IR: ν = 3044, 2954, 2925, 1724, 1712, 1493, 1444, 1383,
˜
1205, 1169, 1141, 860, 698 cm–1.
Eur. J. Org. Chem. 2013, 1950–1962
© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
1959

B. Li, J. Ma, Y. Liang, N. Wang, S. Xu, H. Song, B. Wang
FULL PAPER
(E)-2,4-Di-tert-Butyl-6-(1,2-diphenylvinyl)phenyl
Dimethylcarb-
ral Procedure B for 24 h. M.p. 168–169 °C. 1H NMR (CDCl3,
300 MHz): δ = 7.91–7.88 (m, 1 H), 7.85–7.82 (m, 1 H), 7.67 (d, J
= 8.5 Hz, 1 H), 7.54–7.49 (m, 2 H), 7.37 (d, J = 8.5 Hz, 2 H), 7.32
(d, J = 8.5 Hz, 2 H), 7.28–7.25 (m, 1 H), 7.12 (d, J = 8.4 Hz, 2 H),
6.97 (d, J = 8.4 Hz, 2 H), 6.82 (s, 1 H), 2.84 (s, 6 H) ppm. 13C
NMR (CDCl3, 100 MHz): δ = 153.9, 144.6, 138.63, 138.60, 135.9,
amate (5e): The title compound was isolated by column chromatog-
raphy (EtOAc/petroleum ether, 1:20) as an off-white solid
(101.1 mg, 74%) from 2,4-di-tert-butylphenyl dimethylcarbamate
(1g; 0.30 mmol, 78.7 mg, 1.0 equiv.) according to General Pro-
cedure B for 18 h. M.p. 122–124 °C. 1H NMR (CDCl3, 300 MHz):
δ = 7.35 (d, J = 2.4 Hz, 1 H), 7.25–7.21 (m, 2 H), 7.20–7.15 (m, 4 134.1, 132.3, 132.0, 131.5, 131.3, 130.9, 130.6, 128.1, 127.8, 127.7,
H), 7.12–7.10 (m, 4 H), 7.05 (d, J = 2.4 Hz, 1 H), 6.78 (s, 1 H), 126.7, 126.5, 125.4, 121.9, 121.6, 121.0, 36.7, 36.2 ppm. HRMS
2.80 (s, 3 H), 2.58 (s, 3 H), 1.36 (s, 9 H), 1.26 (s, 9 H) ppm. 13C (MALDI): calcd. for C27H21Br2NO2Na [M + Na]+ 571.9831; found
NMR (CDCl3, 100 MHz): δ = 154.1, 146.8, 145.5, 141.1, 140.3,
571.9830. IR: ν = 3054, 2925, 1723, 1486, 1354, 1150, 1161, 1070,
˜
139.9, 137.82, 137.79, 130.4, 130.3, 129.3, 127.84, 127.79, 127.0, 1009, 813, 748, 493 cm–1.
126.6, 126.4, 123.4, 36.6, 35.8, 34.9, 34.5, 31.4, 30.6 ppm. HRMS
(E)-3-(1,2-Diphenylvinyl)-2-oxo-2H-chromen-4-yl
Dimethylcarb-
amate (5j): The title compound was isolated by column chromatog-
raphy (EtOAc/petroleum ether, 1:20 to 1:3) as a yellow solid
(113.5 mg, 92%) from 2-oxo-2H-chromen-4-yl dimethylcarbamate
(1v; 0.30 mmol, 69.9 mg, 1.0 equiv.) according to General Pro-
cedure B for 24 h. M.p. 223–225 °C. 1H NMR (CDCl3, 300 MHz):
δ = 7.70–7.62 (m, 2 H), 7.48–7.41 (m, 4 H), 7.38–7.33 (m, 4 H),
7.28–7.26 (m, 2 H), 7.23–7.20 (m, 2 H), 6.97 (s, 1 H), 2.99 (s, 3 H),
2.96 (s, 3 H) ppm. 13C NMR (CDCl3, 100 MHz): δ = 161.0, 156.1,
(MALDI): calcd. for C31H37NO2Na [M + Na]+ 478.2717; found
478.2714. IR: ν = 3045, 3019, 2863, 1723, 1437, 1386, 1360, 1221,
˜
1205, 1167, 1146, 779, 750, 694 cm–1.
(E)-5-Chloro-2-(1,2-diphenylvinyl)phenyl Dimethylcarbamate (5f):
The title compound was isolated by column chromatography
(EtOAc/petroleum ether, 1:20) as a yellow solid (85.1 mg, 75%)
from 3-chlorophenyl dimethylcarbamate (1j; 0.30 mmol, 59.9 mg,
1.0 equiv.) according to General Procedure B for 24 h. M.p. 79–
1
80 °C. H NMR (CDCl3, 300 MHz): δ = 7.34–7.28 (m, 5 H), 7.27– 152.4, 152.0, 137.9, 136.0, 133.6, 132.0, 131.7, 129.4, 129.3, 128.1,
7.25 (m, 1 H), 7.24 (d, J = 1.9 Hz, 1 H), 7.23–7.21 (m, 3 H), 7.19 127.9, 127.4, 127.3, 124.2, 123.5, 121.8, 117.1, 116.4, 36.7,
(d, J = 2.0 Hz, 1 H), 7.16–7.14 (m, 2 H), 6.83 (s, 1 H), 2.82 (s, 3
H), 2.66 (s, 3 H) ppm. 13C NMR (CDCl3, 100 MHz): δ = 153.6,
149.4, 139.5, 138.1, 137.0, 135.8, 133.5, 131.9, 131.1, 129.9, 129.4,
128.1, 128.0, 127.3, 127.0, 125.7, 123.9, 36.5, 36.0 ppm. HRMS
(MALDI): calcd. for C23H20ClNO2Na [M + Na]+ 400.1075; found
36.4 ppm. HRMS (MALDI): calcd. for C26H21NO4Na [M + Na]+
434.1363; found 434.1361. IR: ν = 3022, 2930, 1725, 1605, 1489,
˜
1443, 1339, 1144, 1047, 963, 764, 708, 693, 524 cm–1.
(E)-2-Oxo-3-(1-phenylprop-1-en-2-yl)-2H-chromen-4-yl Dimethyl-
carbamate (5k): The title compound was isolated by column
chromatography (EtOAc/petroleum ether, 1:20 to 1:3) as an off-
white solid (93.3 mg, 89%) from 1v (0.30 mmol, 69.9 mg, 1.0 equiv.)
according to General Procedure B for 24 h. M.p. 127–129 °C. 1H
NMR (CDCl3, 300 MHz): δ = 7.64 (d, J = 7.8 Hz, 1 H), 7.54 (t, J
= 7.7 Hz, 1 H), 7.39–7.28 (m, 7 H), 6.55 (s, 1 H), 3.04 (s, 3 H), 2.95
(s, 3 H), 2.20 (s, 3 H) ppm. 13C NMR (CDCl3, 100 MHz): δ =
161.2, 154.8, 152.3, 152.0, 136.7, 131.9, 131.8, 129.6, 128.8, 128.1,
400.1070. IR: ν = 2925, 1733, 1684, 1653, 1473, 1490, 1386, 1206,
˜
1155, 775, 703, 693, 487 cm–1.
(E)-5-Bromo-2-(1,2-diphenylvinyl)phenyl Dimethylcarbamate (5g):
The title compound was isolated by column chromatography
(EtOAc/petroleum ether, 1:20) as an off-white solid (79.8 mg, 63%)
from 3-bromophenyl dimethylcarbamate (1k; 0.30 mmol, 73.2 mg,
1.0 equiv.) according to General Procedure B for 24 h. M.p. 109–
111 °C. 1H NMR (CDCl3, 300 MHz): δ = 7.34 (dd, J = 8.2, 1.8 Hz, 127.0, 124.2, 123.3, 122.4, 117.0, 116.5, 36.9, 36.6, 16.7 ppm.
1 H), 7.28 (d, J = 1.7 Hz, 1 H), 7.24–7.14 (m, 9 H), 7.10–7.08 (m, HRMS (MALDI): calcd. for C21H19NO4Na [M + Na]+ 372.1206;
2 H), 6.77 (s, 1 H), 2.76 (s, 3 H), 2.60 (s, 3 H) ppm. 13C NMR found 372.1209. IR: ν = 2924, 1747, 1734, 1716, 1541, 1489, 1457,
˜
(CDCl3, 100 MHz): δ = 153.6, 149.5, 139.4, 138.1, 136.9, 136.2, 1339, 1141, 1110, 1018, 766, 696, 668 cm–1.
132.1, 131.1, 129.8, 129.4, 128.5, 128.1, 127.9, 127.3, 127.0, 126.7,
(E)-2-Oxo-3-(1-phenylbut-1-en-2-yl)-2H-chromen-4-yl
Dimethyl-
121.2, 36.4, 36.0 ppm. HRMS (MALDI): calcd. for
carbamate (5l): The title compound was isolated by column
chromatography (EtOAc/petroleum ether, 1:20 to 1:3) as a yellow
oil (99.2 mg, 91%) from 1v (0.30 mmol, 69.9 mg, 1.0 equiv.) accord-
ing to General Procedure B for 24 h. 1H NMR (CDCl3, 300 MHz):
δ = 7.45–7.42 (m, 2 H), 7.28 (br. s, 1 H), 7.24 (br. s, 1 H), 7.22–
7.14 (m, 5 H), 6.48 (s, 1 H), 2.99 (s, 3 H), 2.87 (s, 3 H), 2.58 (q, J
= 7.4 Hz, 3 H), 0.94 (t, J = 7.6 Hz, 4 H) ppm. 13C NMR (CDCl3,
100 MHz): δ = 161.3, 156.0, 152.7, 152.4, 136.7, 134.9, 131.8, 131.6,
128.6, 128.2, 127.9, 127.0, 124.2, 123.5, 122.0, 117.1, 116.5, 36.8,
C23H20BrNO2Na [M + Na]+ 444.0570; found 444.0573. IR: ν =
˜
3059, 2926, 1727, 1652, 1489, 1388, 1203, 1156, 775, 744, 702,
692 cm–1.
(E)-2-[1,2-Bis(4-chlorophenyl)vinyl]naphthalen-1-yl Dimethylcarb-
amate (5h): The title compound was isolated by column chromatog-
raphy (EtOAc/petroleum ether, 1:20) as a yellow solid (59.6 mg,
86%) from naphthalen-1-yl dimethylcarbamate (1a; 0.15 mmol,
32.3 mg, 1.0 equiv.) according to General Procedure B for 30 h.
1
M.p. 199–201 °C. H NMR (CDCl3, 300 MHz): δ = 7.90–7.87 (m, 36.6, 23.4, 12.9 ppm. HRMS (MALDI): calcd. for C22H21NO4Na
1 H), 7.83–7.80 (m, 1 H), 7.65 (d, J = 8.5 Hz, 1 H), 7.52–7.46 (m, [M + Na]+ 386.1363; found 386.1362. IR: ν = 3055, 3023, 2967,
˜
2 H), 7.23–7.13 (m, 7 H), 7.01 (d, J = 8.5 Hz, 2 H), 6.82 (s, 1 H),
2934, 2876, 1733, 1608, 1489, 1456, 1338, 1267, 1148, 1093, 1048,
2.82 (s, 6 H) ppm. 13C NMR (CDCl3, 100 MHz): δ = 153.9, 144.6, 752, 702, 592 cm–1.
138.5, 138.1, 135.5, 134.0, 133.3, 132.7, 132.3, 131.6, 130.6, 128.5,
Deprotection of Carbamate 3a; (E)-3-(1-Hydroxynaphthalen-2-yl)-
128.3, 128.1, 127.8, 127.7, 126.7, 126.5, 125.4, 121.9, 36.6, 36.2 (one
signal missing due to overlap) ppm. HRMS (MALDI): calcd. for
acrylic Acid (6):[35] NaOH (200 mg, 5 mmol) was added to a solu-
tion of carbamate 3a (156.5 mg, 0.5 mmol) in EtOH (5 mL), and
the reaction mixture was stirred at 80 °C for 16 h. EtOH was evapo-
rated, the residue was diluted with Et2O (20 mL), and the excess of
NaOH was neutralized at 0 °C by using a solution of 3 m HCl. The
aqueous solution was extracted with Et2O (3ϫ 20 mL), and the
combined organic layers were washed with brine, dried with
Na2SO4, and concentrated under reduced pressure. The crude
product was washed with CH2Cl2 to afford 6 (92 mg, 86%) as a
C27H21Cl2NO2Na [M + Na]+ 484.0841; found 484.0844. IR: ν =
˜
3057, 2925, 1723, 1489, 1356, 1151, 1092, 1081, 1012, 814,
750 cm–1.
(E)-2-[1,2-Bis(4-bromophenyl)vinyl]naphthalen-1-yl Dimethylcarb-
amate (5i): The title compound was isolated by column chromatog-
raphy (EtOAc/petroleum ether, 1:20) as a yellow solid (79.4 mg,
96%) from 1a (0.15 mmol, 32.3 mg, 1.0 equiv.) according to Gene-
1960
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© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2013, 1950–1962

Selective Olefination of Phenol Carbamates
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yellow solid. H NMR ([D6]DMSO, 400 MHz): δ = 12.27 (s, 1 H),
10.21 (s, 1 H), 8.30 (d, J = 9.0 Hz, 1 H), 8.22 (d, J = 16.0 Hz, 1
H), 7.86–7.84 (m, 1 H), 7.74 (d, J = 8.7 Hz, 1 H), 7.56–7.50 (m, 2
H), 7.42 (d, J = 8.7 Hz, 1 H), 6.51 (d, J = 15.9 Hz, 1 H) ppm. 13C
NMR ([D6]DMSO, 100 MHz): δ = 168.2, 152.5, 139.2, 135.2,
127.8, 127.5, 125.7, 125.6, 124.0, 123.0, 120.2, 117.5, 116.4 ppm.
MS (EI): calcd. for C13H10O3 [M+] 214.06; found 214.
Deprotection of Carbamate 5a; 2-[(E)-1,2-Diphenylvinyl]naphthalen-
1-ol (7): NaOH (400mg, 10.0 mmol) was added to a solution of
carbamate 5a (196.6 mg, 0.5 mmol) in EtOH (5 mL), and the reac-
tion mixture was stirred at 80 °C for 25 h. EtOH was evaporated,
the residue was diluted with Et2O (20 mL), and the excess of NaOH
was neutralized at 0 °C by using a solution of 3 m HCl. The aque-
ous solution was extracted with Et2O (3ϫ 20 mL), and the com-
bined organic layers were washed with brine, dried with Na2SO4,
and concentrated under reduced pressure. The crude product was
washed with EtOAc/petroleum ether (1:20) to afford 7 (145 mg,
90%) as a yellow liquid. 1H NMR (CDCl3, 400 MHz): δ = 8.31 (d,
J = 8.1 Hz, 1 H), 7.94 (d, J = 7.7 Hz, 1 H), 7.66–7.56 (m, 4 H),
7.51–7.46 (m, 3 H), 7.45–7.43 (m, 2 H), 7.38 (d, J = 9.8 Hz, 2 H),
7.29 (d, J = 8.4 Hz, 1 H), 7.24–7.25 (m, 3 H), 5.77 (s, 1 H) ppm.
13C NMR (CDCl3, 100 MHz): δ = 148.3, 141.7, 136.7, 136.2, 134.5,
130.9, 129.0, 128.6, 128.5, 128.3, 128.2, 128.0, 127.5, 127.3, 126.6,
125.3, 124.4, 122.8, 120.7, 119.0 ppm. HRMS (MALDI): calcd. for
[2]
C24H19O [M + H]+ 323.1430; found 323.1430. IR: ν = 3517, 3055,
3022, 1598, 1571, 1492, 1447, 1389, 1263, 1080, 878, 764, 694,
˜
567 cm–1.
X-ray Crystallography: Data collection was performed with a Ri-
gaku Saturn 70 diffractometer equipped with a rotating anode sys-
tem by using graphite-monochromated Mo-Kα radiation (ω-2θ
scans). Semiempirical absorption corrections were applied for all
complexes.[36] The structures were solved by direct methods and
refined by full-matrix least squares. All calculations were carried
out by using the SHELXL-97 program system.[37] All non-hydro-
gen atoms were refined anisotropically. Hydrogen atoms were as-
signed idealized positions and were included in structure-factor cal-
culations. The crystal data and summary of the X-ray data collec-
tion are presented in Table S3. CCDC-911370 (5a) and 911369 (5k)
contain the supplementary crystallographic data. These data can
be obtained free of charge from The Cambridge Crystallographic
Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
[3]
[4]
Supporting Information (see footnote on the first page of this arti-
cle): Detailed procedures of remaining experiments, crystal data of
compounds 5a and 5k, and full spectroscopic data for all new com-
pounds.
Acknowledgments
We thank the National Natural Science Foundation of China
(21072097, 21072101) for funding of this work. We are grateful to
two referees for their valuable comments and suggestions.
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Eur. J. Org. Chem. 2013, 1950–1962
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www.eurjoc.org
1961

B. Li, J. Ma, Y. Liang, N. Wang, S. Xu, H. Song, B. Wang
FULL PAPER
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Received: November 22, 2012
Published Online: February 12, 2013
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