A facile and convenient sequential homobimetallic catalytic approach towards β-methylstyrenes. A one-pot Stille cross-coupling/isomerization strategy

Article abstract of DOI:10.1039/c4ob00604f

An efficient one-pot synthetic approach towards β-methylstyrenes is reported. The transformation, based on sequential homobimetallic catalysis, involves a Stille cross-coupling reaction between aryl halides and allyltributylstannane, followed by an in situ palladium-catalyzed conjugative isomerization. The reaction was optimized, and the best results were obtained with 10 mol% Pd(PPh₃)₂Cl₂, 8.0 equiv. LiCl, and 0.5 equiv. PPh₃ in diglyme at 130 °C for 12 h. It was demonstrated that the reaction tolerates a wide variety of functional groups. This journal is the Partner Organisations 2014.

Full text of DOI:10.1039/c4ob00604f

Organic &
Biomolecular Chemistry
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A facile and convenient sequential homobimetallic
catalytic approach towards β-methylstyrenes.
A one-pot Stille cross-coupling/isomerization
strategy†
Cite this: Org. Biomol. Chem., 2014,
12, 3735
Sebastián O. Simonetti, Enrique L. Larghi and Teodoro S. Kaufman*
An efficient one-pot synthetic approach towards β-methylstyrenes is reported. The transformation, based
on sequential homobimetallic catalysis, involves a Stille cross-coupling reaction between aryl halides and
allyltributylstannane, followed by an in situ palladium-catalyzed conjugative isomerization. The reaction
was optimized, and the best results were obtained with 10 mol% Pd(PPh3)2Cl2, 8.0 equiv. LiCl, and
0.5 equiv. PPh3 in diglyme at 130 °C for 12 h. It was demonstrated that the reaction tolerates a wide
variety of functional groups.
Received 20th March 2014,
Accepted 14th April 2014
DOI: 10.1039/c4ob00604f
www.rsc.org/obc
Introduction
Palladium-catalyzed cross-coupling reactions have become a
highly significant field in modern arene chemistry, now being
considered state of the art for C–C bond formation processes.1
The synthesis of β-methylstyrenes is of general interest
because this motif is present in many natural products, such
as the antibiotic agent fumimycin,2a,b the novel inhibitor of
the enzymes lipoxygenase and aldose reductase nigerloxin,2c,d
and the complex neolignan ratanhine, isolated from the med-
icinal plant Ratanhiae radix2e,f (Fig. 1).
The β-methylstyrene scaffold is also found in pharmaceuti-
cally and technologically relevant compounds3 such as
β-cathenin/tcf-4 inhibitors3a and the [l]benzothieno[3,2-b][l]-
benzothiophene derivative OSC5, useful for building photo-
electric converting elements.3c In addition, β-methylstyrenes
have been employed as precursors of more complex mole-
cules,4 as substrates for testing the scope and limitations of
new chemical reagents5 and as dehydrogenation agents.6
β-Methylstyrenes are commonly accessed by conjugative
migration of the double bond of allylbenzenes. This transform-
ation has been performed by treatment of the latter with bases
(KF/Al2O3 7a and K2CO3 7b) or transition metal complexes (from
Ti8a,b and Fe8c,d to softer Lewis acid derivatives of Rh,9a Ru,9b,c
Ir,10a Pd,10b,c Pt11a and Ni11b,c). It has also been shown that
Fig. 1 Selected natural and synthetic β-methylstyrene derivatives.
bulky palladium hydride complexes promote the selective con-
version of terminal alkenes into 2-alkenes.12
In spite of the widespread use of β-methylstyrenes, rather
few methods have been disclosed for their direct synthesis
from easily available starting materials, and for employing C–C
bond forming reactions to install the required three-carbon
Instituto de Química Rosario (IQUIR, CONICET-UNR) and Facultad de Ciencias
Bioquímicas y Farmacéuticas, Universidad Nacional de Rosario, Suipacha 531,
S2002LRK Rosario, Argentina. E-mail: kaufman@iquir-conicet.gov.ar;
Fax: +54-341-4370477
†Electronic supplementary information (ESI) available: Selected spectra of the
final products. See DOI: 10.1039/c4ob00604f
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atom moiety, and many of them require special equipment, transformation was optimized and its scope and limitations
have scarce applicability or exhibit serious drawbacks.
were studied.
These approaches include the cross-coupling reaction of
aryllithium, arylmagnesium and arylmanganese compounds
with vinyl halides,13 vinyl boronates,14 and allyl or vinyl sul-
fones;15 however, they should be performed under conditions
that are compatible with relatively few functional groups.
Results and discussion
The easy accessibility and comparative inexpensiveness of allyl-
Other alternatives are the arylation of propyne involving a tributyltin are advantageous for its use as a three carbon atom
vinylborane cross-coupling/oxidation protocol under strongly source. In contrast, (E/Z)-propenyl tributylstannanes are costly
basic conditions,16 the iron-promoted arylation of propene and not readily available,28 also being acid-sensitive and prone
with anilines17a and the electrochemically assisted nickel-cata- to proto-destannylation.29
lyzed reaction of aryl halides with propene.17b A Heck-type ary-
In order to find the appropriate reaction conditions, the Pd-
lation of allylsilanes, furnishing β-methylstyrenes as side/ catalyzed model reaction of 2-bromoanisole (1a) with allyltri-
unexpected products,18 and a nickel catalyzed cross-coupling butyltin, employing 8.0 equiv. LiCl and 0.5 equiv. PPh3, was
of modified alkyl and alkenyl Grignard reagents with aryl- and first used to evaluate the catalytic activity of several Pd sources.
heteroaryl nitriles have also been disclosed.19 However, this Compound 1a was selected for optimization of the transform-
group of transformations seems to have a rather narrow scope ation because it has an ortho electron donating group, which
and some of them give relatively low yields of products.
may hinder the reaction by exerting both steric and electronic
Propenylations with the use of 1-propenyltributyltin,20 allyl effects.
trifluoroborates,21 vinylboronic acids (Suzuki-Miyaura cross-
Among the catalysts tested, the results indicated that Pd-
coupling)22 and allyl/vinyl boronates have been reported as (PPh3)2Cl2 exhibited the best performance, furnishing 62%
alternatives,23 but these are comparatively expensive reagents.
overall yield of a 35/65 mixture of 2-allylanisole (2a) and (E/Z)-
The conversion of allyl benzenoids into their corresponding 1-methoxy-2-propenyl-benzene (3a, E/Z = 83/17) after 48 h at
1-propenyl derivatives has been occasionally observed as a sec- 130 °C in DMF (Table 1, entries 1–4). A good performance was
ondary process during Pd-catalyzed cross-couplings24 since the also observed with the use of Pd(PPh3)4 as the catalyst, in DMF
initial reports on Stille’s reaction.25 Significant amounts of the at 130 °C. This catalyst afforded the product in 60% yield; the
1-propenyl derivatives (produced at the expense of their corresponding allyl/propenyl derivative ratio was 2/98, with an
sought allyl congeners) were sometimes detected, especially E/Z relationship of 91/9 (entry 5).
when arenes carrying electron-withdrawing substituents were
Next, the effect of PPh3, PBu3 and Dppp and DavePhos as
employed as starting materials.26a However, this outcome was added phosphine ligands was examined, concluding that all of
qualified as a “very rare” and “unexpected” isomerization,26b them were acceptable (entries 4 and 6–8), and that PPh3 exhibi-
and its usefulness as a synthetic transformation has surpris- ted the best profile. Notably, DavePhos (0.5 equiv. regarding
ingly not been further explored.
the amount of the Pd catalyst) gave a 71% combined yield of
During our recent synthesis of the structure originally allyl/propenyl derivatives (ratio: 13/87) with an E/Z relationship
assigned to the marine alkaloid aspergillitine,27 we observed of 85/15 (entry 6).
the conjugative migration of the double bond of a 7-allyl chro-
However, after analysis of these results it was concluded
mone intermediate to the related 1-propenyl derivative. Since that the performances of Pd(PPh3)4 and DavePhos (entries 5
this sequence took place in a completely atom-economical and 6) do not show highly significant differences; therefore,
process and without addition of special reagents, and taking for price and convenience reasons their use was not further
into account that tandem protocols are considered to be tested.
superior to stepwise procedures because they shorten the syn-
thetic scheme, we considered optimizing the transformation N,N-dimethylacetamide (DMA) and N-methyl pyrrolidone
towards the preparation of β-methylstyrenes. (NMP) allowed carrying out the transformation at higher
During the stage of solvent selection (entries 4 and 9–11),
Therefore, here we report a facile and convenient one-pot temperatures; however, no meaningful improvements were
approach to the synthesis of β-methylstyrenes, as shown in observed.
Scheme 1, which involves a palladium-catalyzed Stille cross-
On the other hand, diglyme (entry 11) proved to be a
coupling reaction of aryl halides with allyltributylstannane, fol- superior solvent, furnishing a more efficient conversion of the
lowed by an in situ double bond conjugative migration. The allyl intermediate 2a into the corresponding β-methylstyrene
derivative 3a. This solvent had been demonstrated to possess
unique properties in previously reported Pd-catalyzed cross-
couplings.30
Diglyme allowed shortening of the reaction time up to 12 h
(entry 12), produced improvements in product yields, and
eased the reaction work up. Attempts to further reduce the
reaction time to 8 h or lower the temperature proved to be det-
Scheme 1 Proposed one-pot synthesis of β-methylstyrenes.
3736 | Org. Biomol. Chem., 2014, 12, 3735–3743
rimental to the process performance, specifically diminishing
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Table 1 Optimization of the reaction conditions
Entry No.
Catalysta
Ligand
Solvent
Temp. (°C)
Time (h)
Yieldb (%)
2a/3a (%)
E/Z (%)
1
2
3
4
5
6
7
8
Pd(MeCN)2Cl2
Pd(OAc)2
Pd2(dba)3
Pd(PPh3)2Cl2
Pd(PPh3)4
PPh3
PPh3
PPh3
PPh3
PPh3
DavePhos
Dppp
PBu3
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
130
130
130
130
130
130
130
130
140
160
130
130
130
110
90
48
48
48
48
48
48
48
48
48
24
48
12
8
60
93
30
62
60
71
68
55
56
43
36
59
65
65
76
80
49
49d
63/37
71/29
34/64
35/65
2/98
13/87
63/37
58/42
14/86
93/7
86/14
80/20
86/14
83/17
91/9
85/15
81/19
86/14
84/16
91/9
Pd(PPh3)2Cl2
Pd(PPh3)2Cl2
Pd(PPh3)2Cl2
Pd(PPh3)2Cl2
Pd(PPh3)2Cl2
Pd(PPh3)2Cl2
Pd(PPh3)2Cl2
Pd(PPh3)2Cl2
Pd(PPh3)2Cl2
Pd(PPh3)2Cl2
Pd(PPh3)2Cl2
Pd(PPh3)2Cl2 (5%)
Pd(PPh3)2Cl2
9
DMA
NMP
10
11
12
13
14
15
16
17
18c
Diglyme
Diglyme
Diglyme
Diglyme
Diglyme
Diglyme
Diglyme
Diglyme
0/100
4/96
92/8
100/0
90/10
90/10
90/10
—
87/13
45/55
63/37
17/83
51/49
100/0
63/37
83/17
12
12
4
12
12
90
130
130
a Catalyst loading 10%. b Yields after isolation and purification. Prior to purification, the crude mixture was analyzed by GC-MS and 1H NMR,
confirming that the yields of the isolated product are a true reflection of the reaction outcome. c Without addition of LiCl. d Based on 55% of the
recovered starting material.
the extent of the double bond conjugative migration stage
(entries 13–15). Only 2-allylanisole (2a) was detected after
heating for 4 h at 90 °C (entry 16).
Table 2 One pot synthesis of β-methylstyrenes 3a–m
It was also found that LiCl is critically important for obtain-
ing a successful transformation (entry 18). On the other hand,
the use of CsF in place of LiCl (DMF, 130 °C) slightly improved
the reaction performance (58% yield, 2a/3a: 6/94; E/Z: 91/9);
however, the system proved to be incompatible with certain
functional groups and study of its use was not further
pursued.
In order to demonstrate the efficiency and scope of the
present method, the optimized catalytic system was applied to
a representative set of aryl halides, containing various substitu-
ents and displaying different functionalization patterns. The
results (Table 2) revealed that, in general, the transformation
proceeded in good overall yield.
Taking into account that the process entails two consecutive
reactions, even the lowest performances represent the result of
individual transformations taking place in around 75% yield.
Furthermore, the optimized conditions were compatible with
several functional groups, including alkyl/aryl, ether, N,N-di-
methylamino, ketone, ester, nitro and cyano moieties.
In addition, it was observed that the presence of functional-
ities ortho to the halide did not hinder the transformation and
did not result in significantly lower yields of the corresponding
β-methylstyrene products (entries 1 vs. 2 and 3 and 6 vs. 7).
However, a closer inspection revealed that the best results
were obtained when the substrates carried electron withdraw-
ing groups placed para to the halide (entries 4 and 5) and that
compounds carrying electron withdrawing groups ortho to the
Entry R1
R2
R3
Yield (%) Prod.
2/3
E/Z
1
2
OMe
H
H
OMe
H
H
H
H
H
H
H
H
H
59
65
62
92
2a/3a
2b/3b
2c/3c
2d/3d
2e/3e
2f/3f
2 g/3g
2h/3h
2i/3i
2i/3i
2j/3j
2k/3k
2l/3l
4/96
4/96
3/97
0/100 95/5
0/100 94/6
0/100 100/0
0/100 94/6
0/100 90/10
0/100 100/0
0/100 93/7
100/0
92/8
95/5
3
4
H
H
OMe
CN
COMe 96
Me
H
OMe
H
H
H
NMe2
5
6
H
H
76
72
56
77a
72
76
59
76
7
8
9
10
11
12
13
14
Me
NO2
CO2Et
CO2Et
Ph
H
H
H
6/94
0/100 89/11
9/91 100/0
89/11
H
1-Bromonaphthalene
9-Bromophenanthrene 59
2m/3m 12/88 100/0
a The iodo derivative was employed.
halide exhibited better performances when compared with
substrates having an electron releasing group at the same posi-
tion (entries 1, 9 and 10).
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Although the exact details of the reaction mechanism of of 3c, when 2c was submitted to the optimized reaction
this transformation are still uncertain, a mechanistic picture conditions.
can be proposed based on several observations made during
Taking into account that the palladium source is added in
this study. Firstly, the formation of the isomerized product catalytic amounts and that complete conversion of the starting
should take place through the intermediacy of an allylbenze- material into the allyl derivative 2 has been clearly observed at
noid species, resulting from an initial Stille cross-coupling the earliest stages of the transformation, it should be con-
reaction. These compounds were chromatographically detected cluded that the allylarene derivative 2 could also be a source of
and spectroscopically identified. In addition, 1-propenyl stan- intermediate (iii), acting as a proxy towards 3.
nane should be ruled out as a reactant, since in the absence of
Observation of 2 as the first reaction product and its conver-
aryl halides, the starting allylstannane proved to be remarkably sion into 3 under higher temperature conditions can be
stable under the optimized reaction conditions, not isomeriz- regarded as a result of a process in which the allyl derivative 2
ing to the related 1-propenyl stannane.31
is the kinetically controlled product of a sequence, in which it
That the double bond migration requires the presence of a is driven towards the thermodynamic, most stable product 3
Pd catalyst and is not a merely thermal process was also when heated for a longer time.
assessed with a control experiment employing 4-allylanisole. It
Precipitation of the palladium metal has been associated
was observed that no conjugative isomerization took place with the isomerization of allyl moieties;34b in our case,
under the standard conditions in the absence of the catalyst.
however, it was observed that the addition of PPh3 avoids pre-
These observations enabled us to speculate that an initial cipitation of palladium black,34c while ensuring good overall
Stille cross-coupling reaction takes place between the aryl yields.
derivative (i) and the allylstannane (Scheme 2). It is known
On the other hand, LiCl may participate in the mechanism
that the Stille reaction is promoted by a Pd0 species, which can as a source of chloride ligand, stabilizing the Pd intermediates
be formed in situ by partial reduction of the PdII catalyst by and making the cross-coupling stage more efficient. It has
PPh3 or by the stannane itself.32
been demonstrated that LiCl is a powerful reaction rate accel-
After the well-established steps of oxidative addition of the erant, turning the Pd catalyst more active towards transmetala-
substrate to the Pd complex (ii) and transmetallation with tion and more prone to oxidative addition. Furthermore, LiCl
transfer of the allyl moiety to the Pd complex (iii), the latter enhances the polarity of the solvent, enhancing the leaving
may undergo reductive elimination to the allyl derivative (2), ability of anionic ligands. As an additive, it has been found
with either regeneration of the Pd0 catalyst, or formation of an necessary when the transformation is run in ethereal sol-
η3-allyl hydride (iv).
vents.35a,b
Interestingly, the presence of Bu3SnCl was detected during
The subsequent double-bond conjugative migration to yield
the isomerized alkene product 3 should involve a β-hydride GC-MS monitoring of the reactions (M+ = 326, with its charac-
elimination.33 Alternatively, the intermediate iv should give teristic isotopic cluster).
back the starting olefin (2) if the H returns to the same site it
The influence of diglyme as the reaction solvent may stem
from its ability to exchange with the Pd-ligands at various
left.34a
The intermediacy of the allyl derivatives 2 in this transform- stages of the cycle, also stabilizing the resulting intermediates.
ation was unequivocally demonstrated with control experi- It has been found that diglyme has an accelerating effect on
ments run with 2c. As expected, when 2c was exposed to Pd- some Pd-catalyzed C–C bond forming processes. The ether-O-
(PPh3)2Cl2 and LiCl in diglyme, in the presence of PPh3, the donor atoms may act initially by blocking the soft metal
reaction met with failure, due to the reduction of the Pd by the centers; in this way, at a later stage these are more rapidly sub-
phosphine.32b However, omission of PPh3 provided 78% yield stituted by the substrates, since PdII has a low affinity for
neutral O-ligands. Similarly, these solvent properties may offer
a more rapid product decomplexation step, favoring the whole
process.35c
Globally observed, the transformation may be regarded as a
novel case of sequential homobimetallic catalysis.36 This is a
recent concept designed to describe a condition where a tran-
sition metal catalyst, with the metal in a certain oxidation
state, catalyzes a given reaction to yield a product, which
in situ undergoes a subsequent transformation, catalyzed by
another complex of the same metal, but in a different oxi-
dation state.37
In the current case, the Pd0-catalyzed Stille cross-coupling
reaction is concatenated with a PdII-catalyzed conjugative
migration process, leading to the resulting β-methylstyrenes. It
is noteworthy that examples of this new but highly useful para-
Scheme 2 Proposed reaction mechanism.
3738 | Org. Biomol. Chem., 2014, 12, 3735–3743
digm of reactions in tandem are scarce.
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(3 min); then ΔT = 5 °C min−1 up to T1 = 180 °C; then ΔT =
20 °C min−1 up to TEnd = 310 °C.
Conclusions
In conclusion, we have developed a facile and convenient
Low resolution mass spectra were obtained under the fol-
alternative for the synthesis of β-methylstyrenes through an lowing conditions: TInterface = 300 °C; TIon
= 230 °C;
source
efficient sequential homobimetallic palladium catalyzed one- solvent cut time = 8 min; ionization voltage = 70 eV. The mass
pot process. spectra were compared against the NIST08 library. Diphenyl
The transformation entails two steps in tandem, namely a ether (Aldrich 99.5%) was employed as the internal standard
Stille cross-coupling reaction, followed by an in situ Pd-assisted for interpretation, comparison and quantitative purposes. The
double bond conjugative isomerization.
In light of its operational simplicity, tolerance to a wide NMR analysis of a small sample (1–2 mg) of the reaction.
range of functional groups, good overall yields and satisfactory The high resolution mass spectra were obtained on a
quality of the results was assessed against simultaneous 1H
regioselectivity, it is expected that this strategy will find wide Bruker MicroTOF-Q II instrument. Detection of the ions was
applications in organic synthesis of complex molecules, performed with electrospray ionization in positive ion mode.
including natural products.
General procedure for the preparation of β-methylstyrenes.
Allyltributyltin (1.2 equiv.) was added to a degassed solution of
the aryl halide (1 equiv.), anhydrous LiCl (8 equiv.), Ph3P
(0.5 equiv.) and Pd(Ph3P)2Cl2 (0.1 equiv.) in anhydrous
diglyme (final concentration ca. 0.15 M). The mixture was
heated at 130 °C for 14 h under an argon atmosphere until
complete consumption of the starting material as ascertained
by GC analysis. The reaction was left to reach room tempera-
ture, when it was diluted with Et2O (10 mL) and treated with a
saturated solution of KF (5 mL). The mixture was stirred for
30 min in order to quench the organotin-derivatives. The
organic phase was successively washed with brine (2 × 5 mL)
and H2O (2 × 5 mL). The organics were filtered through a short
pad of a 1 : 1 mixture of Florisil and Celite and dried over
Na2SO4 prior to concentration under reduced pressure.
Column chromatography of the residue gave the corres-
ponding propenyl derivatives.
For the more volatile compounds 3f and 3g, the work-up
was carried out as follows: the reaction was diluted with a
1 : 1 mixture of pentane and hexane (10 mL) and transferred to
a separation flask. The organics were sequentially treated with
a saturated solution of KF (5 mL) for 15 min, brine (5 mL) and
H2O (2 × 5 mL). The organic phase was then filtered through a
short pad of Celite and silica gel (1 : 1, w/w), and washed with
pentane (10 mL). The liquids were dried over Na2SO4 and con-
Experimental section
General information
The reactions were carried out under an anhydrous argon
atmosphere, employing oven-dried glassware. Dry DMF, NMP
and DMA were prepared by distillation from anhydrous BaO;
xylenes and diglyme were distilled from Na°/benzophenone
ketyl. Anhydrous solvents were stored in dry Young’s
ampoules. The other reagents were used as received.
In the conventional purification procedure, the crude
material was submitted to flash column chromatography with
silica gel 60 H (particle size 63–200 μm). Elution was carried
out with mixtures of hexane–Et2O, under positive pressure of
N2 and employing gradient of solvent polarity techniques.
All new compounds gave single spots when run on TLC
plates of Kieselgel 60 GF254, employing different hexane–Et2O
and hexane–EtOAc solvent systems. Chromatographic spots
were detected by exposure of the plates to UV light (254 nm),
followed by spraying with the ethanolic p-anisaldehyde/sulfuric
acid reagent and careful heating.
Apparatus
The IR spectra were recorded with a Shimadzu Prestige 21 centrated under a slow stream of nitrogen.
spectrophotometer of thin films held between NaCl cells.
(E)-1-Methoxy-2-(prop-1-enyl)benzene (3a).38a,b Yield = 59%;
1
The H and 13C NMR spectra were acquired at 300.13 and E/Z = 100 : 0; colourless oil. IR (Film, ν): 2924, 2852, 1463,
75.48 MHz, respectively, on a Bruker Avance 300 spectrometer. 1456, 1437, 1244, 1119, 750, 721 and 694 cm−1
.
1H NMR (δ):
1
The resonances of CHCl3 in CDCl3 (δ 7.26 and 77.0 for H and 1.90 (dd, J = 1.4 and 6.6, 3H), 3.84 (s, 3H), 6.22 (dq, J = 6.6 and
13C NMR, respectively) were used as internal standards. 16.0, 1H), 6.72 (dd, J = 1.4 and 16.0, 1H), 6.85 (d, J = 8.2, 1H),
Chemical shifts are reported in parts per million in the δ scale 6.90 (t, J = 7.6, 1H), 7.18 (dt, J = 1.5 and 7.6, 1H) and 7.39 (dd,
and the magnitudes of the coupling constants (J) are given in J = 1.5, 7.6, 1H). 13C NMR (δ): 18.9, 55.4, 110.7, 120.6, 125.6,
hertz. DEPT 135 and DEPT 90 experiments aided the interpret- 126.4, 126.6, 127.7, 133.2 and 156.2. EI-MS (m/z, %): 148 (M+,
ation of the fully decoupled 13C NMR spectra. In special cases, 100), 147 (10), 133 (22), 119 (55), 117 (33), 115 (46), 105 (69),
2D-NMR experiments (COSY, HSQC and HMBC) were also 103 (26), 91 (83), 79 (26) and 77 (34).
employed.
(E)-1-Methoxy-3-(prop-1-enyl)benzene (3b).38c,d Yield = 65%;
The GC-MS experiments were carried out with a Shimadzu E/Z = 92 : 8; colourless oil. IR (Film, ν): 2922, 2851, 1599, 1578,
QP2010 plus instrument equipped with an AOC-20i auto- 1489, 1464, 1454, 1435, 1288, 1263, 1252, 1155, 1047, 964, 768
1
sampler. The chromatographic runs were performed in the and 648 cm−1. H NMR (δ): 1.88 (dd, J = 1.2 and 6.4, 3H), 3.81
split injection mode (ratio: 50), on a SPB-1 column (28.5 m × (s, 3H), 6.23 (dq, J = 6.4 and 15.7, 1H), 6.38 (d, J = 15.7, 1H),
0.25 mm × 0.25 μm), with a helium flow of 1.05 mL min−1
.
6.75 (dd, J = 2.0 and 7.9, 1H), 6.87 (t, J = 2.1, 2H), 6.93 (dd, J =
The oven temperature program was as follows: TInit = 50 °C 1.9 and 7.7, 1H) and 7.20 (t, J = 7.8, 1H). 13C NMR (δ): 18.4,
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+
55.2, 111.2, 112.3, 118.5, 121.0, 126.1, 129.4, 139.4 and 159.8. HRMS (ESI-TOF, m/z) Found: 216.06311; C10H11NNaO3
EI-MS (m/z, %): 148 (M+, 36), 147 (16), 117 (64), 116 (25), 115 requires 216.0637.
(45), 105 (63), 103 (38), 92 (14), 91 (94), 89 (26), 79 (69), 78 (48)
and 77 (100).
(E)-Ethyl 2-(prop-1-enyl)benzoate (3i)
Procedure A. From the aryl iodide. Yield = 77%; E/Z = 100 : 0;
colourless oil. IR (Film, ν): 2980, 1714, 1479, 1444, 1279, 1246,
(E)-1-Methoxy-4-(prop-1-enyl)benzene (3c).39a,d Yield = 62%;
E/Z = 95 : 5; colourless oil. IR (Film, ν): 2924, 2851, 1732, 1607,
1132, 1099, 1072 and 964 cm−1 1H NMR (δ): 1.39 (t, J = 7.1,
.
1
1512, 1456, 1377, 1174 and 1034 cm−1. H NMR (δ): 1.85 (dd,
3H), 1.92 (dd, J = 1.7 and 6.6, 3H), 4.36 (q, J = 7.1, 2H), 6.14
(dq, J = 7.1 and 15.7, 1H), 7.14 (dd, J = 1.5 and 15.7, 1H), 7.25
(dt, J = 0.9 and 7.2, 1H), 7.42 (dt, J = 1.2 and 7.5, 1H), 7.51 (d,
J = 7.9, 1H), 7.83 (dd, J = 1.2 and 7.9, 1H). 13C NMR (δ): 14.3,
18.8, 60.9, 126.4, 127.1, 128.4, 129.5, 129.7, 130.1, 131.8, 139.5
and 167.7. EI-MS (m/z, %): 190 (M+, 49), 175 (46), 147 (86), 145
(47), 144 (24), 117 (67), 116 (45), 115 (100) and 91 (37). HRMS
J = 1.6 and 6.6, 3H), 3.80 (s, 3H), 6.09 (dq, J = 6.6, 15.8, 1H),
6.35 (dd, J = 1.5 and 15.8, 1H), 6.83 (d, J = 8.8, 2H) and 7.26 (d,
J = 8.8, 2H). 13C NMR (δ): 18.4, 55.3, 113.9, 123.5, 126.9, 130.3,
130.8 and 158.6. EI-MS (m/z, %): 148 (M+, 16), 119 (42), 115
(43), 105 (79), 103 (30), 91 (100), 79 (42), 78 (23) and 77 (56).
(E)-4-(Prop-1-enyl)benzonitrile (3d).39e,f Yield = 92%; E/Z =
95 : 5; colourless oil. IR (Film, ν): 3059, 2986, 2930, 2230, 1701,
1609, 1504, 1408, 1379, 1202, 1119, 1107, 1018, 843 and
(ESI-TOF, m/z) Found: 191.1067; C12H15O2 [M + H]+ requires
191.1072.
+
1
820 cm−1. H NMR (δ): 1.92 (d, J = 5.9, 3H), 6.31–6.44 (m, 2H),
Procedure B. From the aryl bromide. Yield = 72%; E/Z =
93 : 7; colourless oil. IR, NMR and EI-MS spectra fully agree
with those of 3i obtained according to Procedure A.
7.38 (d, J = 8.3, 2H) and 7.55 (d, J = 8.3, 2H). 13C NMR (δ): 18.6,
109.9, 119.9, 126.3 (2C), 129.8, 130.2, 132.3 (2C) and 142.4.
EI-MS (m/z, %): 143 (M+, 100), 142 (72), 140 (16), 117 (15), 116
(85), 115 (79), 89 (26) and 76 (13).
(E)-2-(Prop-1-enyl)-biphenyl (3j).41 Yield
= 76%; E/Z =
89 : 11; colourless oil. IR (Film, ν): 3061, 3040, 2928, 2914,
(E)-1-[4-(Prop-1-enyl)phenyl]ethanone (3e).40a,b Yield = 96%;
E/Z = 94 : 6; colourless oil. IR (Film, ν): 2914, 1674, 1603, 1409,
2851, 1584, 1487, 1236, 1163, 1072, 1022, 962, 866, 785, 748
1
and 691 cm−1. H NMR (δ): 2.01 (dd, J = 1.7 and 6.6, 3H), 6.26
1360, 1267, 1180, 958, 852, 789 and 590 cm−1 1H NMR (δ):
.
(dq, J = 6.6 and 15.4, 1H), 7.15 (dd, J = 1.8 and 15.4, 1H) and
7.16–8.16 (m, 9H). 13C NMR (δ): 19.0, 123.5, 124.0, 125.6,
125.7, 125.8, 127.2, 128.2, 128.3, 128.4, 128.6, 131.1, 133.6,
135.8 and 158.3. EI-MS (m/z, %): 194 (M+, 34), 179 (100), 178
(54), 165 (16), 152 (7) 115 (6), 89 (18), 83 (12) and 76 (9).
1.91 (d, J = 5.2, 3H), 2.57 (s, 3H), 6.32–6.47 (m, 2H), 7.39 (d, J =
8.4, 2H) and 7.88 (d, J = 8.4, 2H). 13C NMR (δ): 18.7, 26.5, 125.8
(2C), 128.7 (2C) 129.1, 130.3, 135.4, 142.6 and 197.6. EI-MS
(m/z, %): 160 (M+, 33), 146 (10), 145 (100), 117 (25), 116 (12),
115 (59) and 91 (30).
(E)-Dimethyl-(4-propenyl-phenyl)-amine (3k).23,40c,d Yield =
57%; E/Z = 89/11; yellow-pale oil. IR (Film, ν): 2924, 1732,
(E)-1-Methyl-4-(prop-1-enyl)benzene (3f).23,39f,40c,d Yield
76%; E/Z = 100 : 0; colourless oil. IR (Film, ν): 3023, 2921,
1638, 1551, 1432, 1110, 1015, 990, 962, 802 and 776 cm−1
=
1861, 1611, 1520, 1487, 1350, 1234 and 1165 cm−1 1H NMR
.
(δ): 1.85 (dd, J = 1.4 and 6.6, 3H), 2.94 (s, 6H), 6.03 (dq, J = 6.6
and 15.2, 1H), 6.32 (dd, J = 1.4 and 15.2, 1H), 6.68 (d, J = 8.8,
2H) and 7.23 (t, J = 8.8, 2H). 13C NMR (δ): 18.4, 40.7 (2C),
116.7, 121.4 (2C), 123.2 (2C), 126.8, 130.7 (2C) and 149.6.
EI-MS (m/z, %): 161 (M+, 100), 160 (76), 145 (15), 144 (10), 134
(19), 118 (12), 117 (33), 115 (32), 91 (29) and 77 (19).
.
1H NMR (δ): 1.89 (dd, J = 1.2 and 6.5, 3H), 2.34 (s, 3H),
6.20 (dq, J = 6.5 and 15.8, 1H), 6.39 (d, J = 15.8, 1H), 7.24 (d, J =
8.3, 2H) and 7.37 (d, J = 8.3, 2H). 13C NMR (δ): 18.5, 21.1,
124.6, 125.7 (2C), 129.2 (2C), 130.9, 135.2 and 136.4. EI-MS
(m/z, %): 132 (M+, 62), 117 (100), 115 (45), 105 (9), 91 (32)
and 77 (10).
(E)-1-(Prop-1-enyl)naphthalene (3l).42a,b Yield = 68%; E/Z =
81 : 19; colourless oil. IR (Film, ν): 3061, 3040, 2928, 2914,
2851, 1584, 1487, 1236, 1163, 1072, 1022, 962, 866, 785, 748
(E)-1-Methyl-2-(prop-1-enyl)benzene (3g).39d Yield = 72%;
E/Z = 94 : 6; colourless oil. IR (Film, ν): 3023, 2921, 1638, 1551,
1
and 691 cm−1. H NMR (δ): 1.83 (dd, J = 1.6 and 6.5, 3H), 6.20
1432, 1110, 1015, 990, 962, 802 and 776 cm−1 1H NMR (δ):
.
(dq, J = 6.5 and 15.7, 1H), 6.42 (d, J = 15.7, 1H), 7.24 (d, J = 8.3,
2H), 7.37 (d, J = 8.3, 2H), 7.48 (dt, J = 1.4 and 8.3, 1H), 7.60 (d,
J = 7.0, 1H) and 7.63 (dt, J = 1.5 and 8.1, 1H). 13C NMR (δ):
18.7, 125.8, 126.5, 126.7, 126.8, 127.2, 127.3, 127.4, 128.8,
130.2, 136.0, 140.2 and 141.3. EI-MS (m/z, %): 168 (M+, 50), 167
(27), 165 (27), 154 (13), 153 (100), 152 (36), 83 (17) and 82 (14).
(E)-9-(Prop-1-enyl)phenanthrene (3m).42c,d Yield = 69%; E/Z
= 88 : 12; colourless oil. IR (Film, ν): 3057, 3018, 2924, 2851,
1597, 1493, 1450, 1433, 1242, 962, 812, 744, 735, 723 and
1.89 (dd, J = 1.2 and 6.5, 3H), 2.34 (s, 3H), 6.20 (dq, J = 6.5 and
15.8, 1H), 6.39 (d, J = 15.8, 1H), 7.04 (d, J = 7.6, 1H), 7.12 (t, J =
7.6, 1H), 7.24 (d, J = 8.3, 1H) and 7.35 (t, J = 7.6, 1H). 13C NMR
(δ): 18.5, 21.1, 124.6, 125.7 (2C), 129.2 (2C), 130.9, 135.2 and
136.4. EI-MS (m/z, %): 132 (M+, 62), 131 (14), 117 (100), 116
(15),115 (51), 91 (34), 93 (28) and 91 (56).
(E)-4-Methoxy-2-nitro-1-(prop-1-enyl)benzene (3h). Yield
=
56%; E/Z = 90 : 10; yellowish oil. IR (Film, ν): 2914, 1674, 1651,
1
1602, 1409, 1360, 1267, 1180, 958, 852 and 789 cm−1. H NMR
1
618 cm−1. H NMR (δ): 2.04 (dd, J = 1.7 and 6.6, 3H), 6.33 (dq,
(δ): 1.91 (dd, J = 0.9 and 6.6, 3H), 3.85 (s, 3H), 6.13 (dq, J = 6.6
and 15.9, 1H), 6.78 (d, J = 15.9, 1H), 7.08 (dd, J = 2.6 and 8.7,
1H), 7.38 (d, J = 2.6, 1H) and 7.47 (d, J = 8.7 Hz, 1H). 13C NMR
(δ): 18.3, 55.5, 108.2, 108.7, 119.6, 125.6, 129.1, 129.2, 147.8
and 158.4. EI-MS (m/z, %): 193 (M+, 24), 176 (10), 151 (58), 150
(100), 133 (20), 122 (47), 121 (21), 115 (29), 107 (22), 106 (30),
105 (31), 104 (20), 103 (59), 94 (36), 93 (28), 91 (56) and 77 (92).
J = 6.6 and 16.1, 1H), 7.13 (d, J = 16.1, 1H), 7.37 (d, J = 8.3, 2H),
7.75 (s, 1H), 7.76 (d, J = 5.7, 1H), 7.85–7.92 (m, 2H), 8.18 (dd,
J = 0.9 and 8.3, 1H) and 8.64–8.74 (m, 4H). 13C NMR (δ): 18.9,
122.5, 122.7, 123.0, 124.3, 124.8, 126.9, 128.4, 128.6, 128.7,
129.3, 129.9, 130.3, 130.8, 132.0, 132.1 and 134.7. EI-MS (m/z,
%): 218 (M+, 58), 217 (24), 215 (19), 204 (17), 203 (100),
3740 | Org. Biomol. Chem., 2014, 12, 3735–3743
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Acknowledgements
The authors thank the Argentine National Research Council
(CONICET) and the National Agency for the Promotion of
Science and Technology (ANPCyT) for financial support (PIP
2011-0479 and PICT 2011-0399). S. Tindiglia, P. Duché and
G. Marcuzzi are acknowledged for running NMR and GC-MS
and Drs V. and I. Dragutan (Romanian Academy, Romania)
are thanked for helpful discussions regarding the
reaction mechanism. S. O. S. acknowledges CONICET for his
fellowship.
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