Synthesis of allyl acetates via palladium-catalysed functionalisation of allenes and 1,3-dienes

Article abstract of DOI:10.1055/s-0031-1289658

-Allylpalladium intermediates are known to participate efficiently in transformations involving nucleophilic species. Exploring these processes, we have developed a method for the preparation of allyl acetates via palladium-catalysed functionalisation of

Full text of DOI:10.1055/s-0031-1289658

PAPER
399
Synthesis of Allyl Acetates via Palladium-Catalysed Functionalisation of
Allenes and 1,3-Dienes
Synthesis of
A
u
llyl
A
cetatesren Husinec,a Milos Petkovic,b Vladimir Savic,*b Milena Simicb
a
Institute for Chemistry, Technology and Metallurgy (ICTM), Centre for Chemistry, P.O. Box 815, Njegoseva 12, 11000 Belgrade, Serbia
University of Belgrade, Faculty of Pharmacy, Department of Organic Chemistry, Vojvode Stepe 450, 11221 Belgrade, Serbia
Fax +381(11)3972 840; E-mail: vladimir.savic@pharmacy.bg.ac.rs
b
Received 18 October 2011; revised 1 December 2011
by the acetate substituent. 1,3-Dienes have also shown to
be suitable starting materials for the preparation of allyl
acetate derivatives via halo-acetoxylation catalysed by
palladium.7
Abstract: p-Allylpalladium intermediates are known to participate
efficiently in transformations involving nucleophilic species. Ex-
ploring these processes, we have developed a method for the prep-
aration of allyl acetates via palladium-catalysed functionalisation of
allenes and 1,3-dienes. Reactions of aryl iodides with either of these
two classes of compounds and excess sodium acetate in the pres-
ence of Pd(OAc)2 and Ph3P as the catalytic system afforded the re-
spective allyl acetates in moderate to good yields. The scope of this
process has been investigated. The described method is an addition
to the synthetic repertoire for the preparation of allyl acetates, and
may be useful, in particular, for the synthesis of structurally com-
plex compounds of this type.
Our interest in the palladium-promoted chemistry of al-
lenes prompted an investigation of their reactivity in the
presence of an acetate as nucleophilic species
(Scheme 1).8 The initial idea is based on the well-docu-
mented reactivity of p-allylpalladium intermediates in the
presence of heteroatom nucleophiles (Scheme 1).9 Inter-
molecular reactions with carboxylic nucleophiles have
not been widely explored, while an intramolecular variant
has been used for the preparation of lactones.10 Although
the product of the proposed allene–acetate reaction, an
allyl acetate, is a substrate for palladium-catalysed trans-
formations and equilibrium (Scheme 1) that may lead to
unwanted processes, our approach was shown to provide
a direct access to structurally complex allyl acetates. In
this paper we give a full account of our previously com-
municated work on the synthesis of allyl acetates employ-
ing palladium-catalysed processes.8
Key words: allyl acetates, palladium catalysis, allenes, dienes, syn-
thesis
Allyl acetates represent a useful class of organic com-
pounds extensively used in the allylation processes catal-
ysed by a range of transition metals.1 An additional
synthetic methodology employing allyl acetates or related
esters is the Claisen–Ireland 3,3-sigmatropic rearrange-
ment, which produces g-unsaturated carboxylic acids or
their derivatives.2 If directly prepared, they can also be a
source of synthetically very useful allyl alcohols via hy-
drolytic processes.
Ar
R1
R1
R2
X
R2
A frequently used procedure for the preparation of allyl
acetates is based on the acetylation of allyl alcohols,3a
which are usually accessible via the vinylation of alde-
hydes or ketones.3b–e Although useful, this method often
requires the application of sensitive magnesium- or
lithium-based organometallic reagents. Direct synthesis
of allyl acetates can be achieved by allylic acetoxylation
and this methodology has been investigated for a long
time leading to the development of a number of oxidative
X
Ar
R1
X = heteroatom
ArX
R1
R1
•
R1
Pd(0)
Pd
Ar
R1
R1
_
+
AcONa
OAc
Scheme 1 Reactivity of the p-allylpalladium species
reagents.4 In recent decades, related palladium-catalysed The optimal reaction conditions for the acetoxylation of
activation of the allylic C–H bond emerged as an efficient allenes, as previously shown, include an excess of sodium
method for the preparation of this class of compounds.5 acetate, palladium(II) acetate and triphenylphosphine as
An alternative approach is based on the highly regioselec- the catalytic system, and dimethyl sulfoxide as a solvent.8
tive palladium-catalysed functionalisation of allyl ace- The reaction reversibility (Scheme 1) prompted the use of
tates employing boronic acids.6 These reactions were a longer reaction time (12 h) and an elevated temperature
carried out without a ligand and in the presence of the ox- (85–90 °C) in order to obtain the thermodynamically
idative reagent. A high degree of regioselectivity was at- favoured product.8 Using these conditions, exploration of
tributed to the chelatation of the palladium-intermediate the reaction scope commenced with allene 1 (Table 1). In
reaction with various iodides 2, allene 1 afforded the re-
gioisomeric products 3 and 4 in moderate to good yields.
The major product in all cases was compound 3, obtained
via nucleophilic substitution on the less sterically hin-
SYNTHESIS 2012, 44, 399–408
Advanced online publication: 29.12.2011
DOI: 10.1055/s-0031-1289658; Art ID: T98111SS
x
x
.x
x
.2
0
1
1
© Georg Thieme Verlag Stuttgart · New York

400
S. Husinec et al.
PAPER
dered side.11a The results suggested that the product com-
position was also controlled by the stereochemical
properties of the aryl iodide. Thus, larger iodides, such as
1-naphthyl iodide (entry 5), or iodides possessing an ortho
substituent, such as 1-iodo-2-nitrobenzene (entry 6),
showed a higher level of regioselectivity than other sub-
strates. In addition, the electronic properties of these reac-
tants were also influential and the results suggested better
efficiency of the electron-rich than electron-poor aryl ha-
lides (entries 3, 4 vs. 6, 7), which afforded the products in
slightly lower yields. The major product, compound 3,
was in all cases obtained as inseparable mixture of Z- and
E-isomers. Although the E-alkene was the main compo-
nent in many reactions, a significant level of selectivity
was not observed.
Table 2 Synthesis of Allyl Acetates from Allene 5a
Ph
Pd(OAc)2
Ph3P
R
N
OAc
Ph
•
N
Ts
NaOAc
DMSO
85–90 °C
5
6
Ts
+
RI
Entry
R
Product
6a
Ratiob Z/E
1:1
Yieldc (%)
1
2
3
4-MeC6H4
4-MeOC6H4
Ph
64
68
63
6b
1.1:1
1:1
6c
a Reaction conditions: allene 5 (0.1 mmol), RI (0.15 mmol), NaOAc
(0.5 mmol), Pd(OAc)2 (0.01 mmol), Ph3P (0.02 mmol), DMSO (2
mL), 12 h, 85–90 °C.
Table 1 Synthesis of Allyl Acetates from Allene 1a
b Established by analysis of 1H NMR spectra of the isolated products.
c Yields after column chromatography.
R
BnO
OAc
BnO
Pd(OAc)2
Ph3P
•
3
1
+
isomers (Scheme 2). The product was a suitable substrate
for further elaboration via the Diels–Alder reaction af-
fording highly substituted cyclic allyl acetate 9.
+
R
RI
2
NaOAc
DMSO
85–90 °C
BnO
OAc
4
OMe
Ph
Pd(OAc)2
N
Ph3P
Entry
R
Product
Ratio
Ratiob
E/Z in 3 (%)
Yieldc
•
Ts
OAc
3/4
NaOAc
DMSO
85–90 °C
Ph
N
5
+
I
Ts
1
2
3
4
5
6
7
4-MeC6H4
Ph
3a/4a
3b/4b
3c/4c
3d/4d
3e/4e
3f/4f
2.6:1
3:1
1.4:1
1.2:1
1.8:1
1.8:1
0.8:1
0.8:1
0.9:1
64
64
63
66
60
50
31
73%
OMe
8
7
3-MeOC6H4
3,4-Me2C6H3
1-naphthyl
2-O2NC6H4
4-AcC6H4
1.4:1
1.7:1
6.5:1
5.2:1
2.7:1
DMAD
CO2Me
toluene
48%
MeO
CO2Me
Ts
OAc
N
Bn
9
3g/4g
Scheme 2 Vinyl iodide 7 in the synthesis of allyl acetates
a Reaction conditions: allene 1 (0.1 mmol), RI 2 (0.15 mmol), NaOAc
(0.5 mmol), Pd(OAc)2 (0.01 mmol), Ph3P (0.02 mmol), DMSO (2
mL), 12 h, 85–90 °C.
We next explored the effect of a heteroatom directly
bound to the allenic moiety at the reactive site (Table 3).
This structural feature added electronic factors, in addi-
tion to steric ones, as important controlling components of
the reaction pathway. As a result, in the reactions of this
type, the major product is usually obtained via nucleo-
philic attack on the more (heteroatom) substituted end.11a
Literature results suggest that in some cases the regiose-
lectivity in reactions involving amine nucleophiles and
heteroatom-substituted p-allylpalladium species may be
controlled by the selection of the base.11b Thus, while po-
tassium carbonate favoured nucleophilic attack on the
less-substituted terminus, silver carbonate, in contrast,
provided access to the product from the reaction at the
more-substituted carbon atom. This was attributed to the
formation of the cationic palladium-intermediate in the
presence of silver–base promoting the nucleophilic attack
at the most electron-deficient allylic centre adjacent to the
b Determined by 1H NMR.
c Combined yields after column chromatography.
To follow this initial work, we further explored the related
aminoallenes. Since the above results clearly showed the
influence of the sterics on the reaction pathway, it was in-
teresting to screen the related aminoallene 5, which was
expected to potentiate the steric effects due to the different
substitution pattern of nitrogen compared to oxygen. In-
deed, allene 5 in reactions with several aryl iodides afford-
ed exclusively product 6, obtained via nucleophilic attack
at the less-substituted terminus (Table 2). As in previous
cases, in all reactions the products were isolated as mix-
tures of almost equal amount of Z- and E-isomers.
These results were further expanded in an additional ex-
ample using vinyl iodide 7 in place of the aryl iodide,
yielding the diene product 8 as 2.5:1 mixture of E- and Z-
Synthesis 2012, 44, 399–408
© Thieme Stuttgart · New York

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Synthesis of Allyl Acetates
401
heteroatom. Substrates possessing the allene functionality Cyclisation processes were also incorporated into the re-
substituted with an N-Ts group did not show the above re- action sequence affording the cyclic allyl- or benzyl-type
activity pattern most likely due to significant dominance products in moderate yields (Table 4). Both rings, five-
of the sterics imposed by the bulky substituent. In light of and six-membered, were generated with equal efficiency.
these literature results, we were not surprised with the out- Additionally, no significant differences between process-
come of experiments outlined in Table 3.
es leading to indole or benzofuran ring formation were ob-
served.
Allenes 10a and 10b in reactions with 4-methoxyphenyl
iodide under the described conditions afforded both regio-
isomeric acetates, 11 and 12. As the major component,
compound 12 was obtained via nucleophilic attack on the
heteroatom-substituted, more-electron-deficient carbon
atom. It is interesting to compare the results obtained with
allene 5 and related allene 10a. While the former allene
yielded product 6b exclusively (Table 2, entry 2), the lat-
ter afforded a mixture of both regioisomers 11a and 12a
(Table 3, entry 1). Obviously, the results showed that
these processes were influenced by a fine balance between
steric and electronic properties of the allene moiety.
Table 4 The Cyclisation/Nucleophilic Substitution Processesa
OAc
Pd(OAc)2
I
.
•
Ph3P
NaOAc
DMSO
85–90 °C
X
X
14
15
Entry Allene 14
Product 15
Yieldb (%)
OAc
I
•
1
52
N
Table 3 Reactivity of the Heteroatom-Substituted Allenes 10a
N
Ts
Ts
R1R2N
14a
14b
15a
15b
OMe
OMe
•
Pd(OAc)2
Ph3P
OAc
10
+
•
I
+
2
3
47
48
NaOAc
DMSO
85–90 °C
I
N
R1R2N
Ts
R1R2N
OAc
O
MeO
11
OAc
12
OAc
•
I
Entry R1
R2 Ratio 11/12
Ts 11a/12a 1:1.6
Ms 11b/12b 1:2
Ratiob E/Z for 11 Yieldc (%)
N
1
2
Bn
Ph
2:1
48
61
Ts
N
Ts
1.3:1
14c
15c
a Reaction conditions: allene 10 (0.1 mmol), 4-MeOC6H4I (0.15
mmol), NaOAc (0.5 mmol), Pd(OAc)2 (0.01 mmol), Ph3P (0.02
mmol), DMSO (2 mL), 12 h, 85–90 °C.
OAc
N
I
•
b Established by analysis of 1H NMR spectra of the isolated products.
c Combined yields after column chromatography.
4
46
N
Me
Me
O
O
14d
15d
The possibility to use functionalised carboxylic nucleo-
philes would be particularly interesting from a synthetic
point of view. Therefore we briefly explored this idea us-
ing the sodium salt of pentenoic acid (Scheme 3). Under
standard conditions, employing allene 5, this salt was less
efficient than the acetate affording 13 as the sole product
in 33% yield as 1.7:1 mixture of E- and Z-isomers.
a Reaction conditions: allene 14 (0.1 mmol), NaOAc (0.5 mmol),
Pd(OAc)2 (0.01 mmol), Ph3P (0.02 mmol) and DMSO (2 mL), 12 h,
85–90 °C.
b Combined yields after column chromatography.
Interesting results were obtained in the reaction per-
formed with 14b at room temperature. The expected prod-
uct was isolated as a separable 1:1 mixture of two
regioisomeric products 15b and 16 (Scheme 4).
OMe
Ph
N
•
Ts
Pd(OAc)2
Ph3P
OAc
5
O
Pd(OAc)2
Ph3P
+
Ph
+
N
I
DMSO
85–90 °C
I
•
Ts
O
OAc
+
NaOAc
DMSO
r.t.
13
O
_
ONa
O
O
MeO
14b
15b
1:1
16
61%
O
33%
Scheme 4 The cyclisation/nucleophilic substitution processes at
room temperature
Scheme 3 The sodium salt of pentenoic acid as a nucleophile
© Thieme Stuttgart · New York
Synthesis 2012, 44, 399–408

402
S. Husinec et al.
PAPER
This suggested, as expected, that the kinetic product, com- NMR spectra were recorded on a Bruker Avance III (500 MHz) or
Varian Gemini 2000 (200 MHz) spectrometer with TMS as the in-
prised of both regioisomers, at higher temperature equili-
ternal standard and CDCl3 as solvent, unless otherwise stated. Mass
brated to the more stable product. At least in some cases
spectral data were recorded using Agilent MSD TOF spectrometer
coupled with Agilent 1200 HPLC or Agilent Technologies 5975C
MS coupled with Agilent Technologies 6890N GC. IR spectra were
(Table 4, entries 1 and 2), the aromaticity of the final com-
pounds contributed to the preferential formation of the ob-
served product. While in the reactions where the p-
allylpalladium intermediate was generated in an intramo-
lecular fashion the process afforded the single product at
higher temperature (Table 4), this effect was not observed
in the intermolecular reactions under the same conditions
(Table 1) unless steric factors were dominant (Table 2).
recorded on an IR Termo Scientific NICOLET iS10 (4950) spectro-
photometer. Melting points were determined on Gallenkamp Melt-
ing Point Apparatus and are uncorrected. Flash chromatography
employed silica gel 60 (230–400 mesh) while TLC was carried out
using alumina plates with 0.25 mm silica layer (Kieselgel 60 F254
,
Merck); PE = petroleum ether. The solvents were purified by distil-
lation before use.
Apart from studying the reactivity of allenes, we briefly
explored the reactivity of 1,3-dienes in the same transfor-
mations (Table 5), which are also known to generate p-al-
lylpalladium species. Reactions with 1,3-diene 17 were
performed under the same experimental conditions to af-
ford acetates 18a–c in moderate to good yields. Although
the expected products were formed, generally, 1,3-dienes
proved to be less efficient than allenes in these transfor-
mations.
Allenes 1,12a 10a,12b 14a,12c 14b,12d and 14d12e and diene 1713 were
synthesised according to the literature procedures.12f
N-Benzyl-N-tosylbuta-2,3-dien-1-amine (5); Typical Procedure
A mixture of N-benzyl-N-tosylprop-2-yn-1-amine (299 mg, 1
mmol), paraformaldehyde (75.0 mg, 2.5 mmol, 2.5 equiv), i-Pr2NH
(282 mg, 2 mmol, 2 equiv), and CuBr (71.5 mg, 0.5 mmol, 0.5
equiv) in dioxane (10 mL) was heated at 110 °C (oil bath tempera-
ture) under an N2 atmosphere for 12 h. The mixture was allowed to
cool to r.t., filtered through a Celite plug, and the solvent was evap-
orated. Flash chromatography (silica gel, PE–Et2O, 1:1) afforded
the product (203.4 mg, 65%) as a brown, amorphous solid; mp 67–
70 °C; Rf = 0.63 (silica gel, PE–Et2O, 1:1).
Table 5 Synthesis of Allyl Acetates from 1,3-Diene 17a
Pd(OAc)2
Ph3P
IR: 1950, 2338, 1158, 1091, 734, 655 cm–1.
EtO2C
EtO2C
OAc
RI
+
1H NMR (500 MHz, CDCl3): d = 7.74 (d, J = 8.0 Hz, 2 H), 7.32–
7.26 (m, 7 H), 4.77 (t, J = 6.5 Hz, 1 H), 4.62–4.60 (m, 2 H), 4.38 (s,
2 H), 3.80–3.77 (m, 2 H), 2.44 (s, 3 H).
13C NMR (125 MHz, CDCl3): d = 209.6, 143.3, 137.6, 135.8, 129.7,
128.6, 128.5, 127.7, 127.2, 85.1, 76.0, 50.1, 45.5, 21.5.
MS (EI): m/z = 313 (M+), 274, 155, 139, 91, 65.
HRMS (ESI): m/z [M + Na]+ calcd for C18H19NNaO2S: 336.10287;
NaOAc
DMSO
85–90 °C
EtO2C
EtO2C
17
18
R
Entry
R
Product
Yieldb (%)
1
2
3
4-MeOC6H4
Ph
18a
18b
18c
51
22
40
found: 336.10272.
3,4-Me2C6H3
a Reaction conditions: diene 17 (0.1 mmol), RI (0.15 mmol), NaOAc
(0.5 mmol), Pd(OAc)2 (0.01 mmol), Ph3P (0.02 mmol) and DMSO (2
mL), 12 h, 85–90 °C.
N-(Buta-2,3-dienyl)-2-iodo-N-tosylbenzenamine (14c)
The title compound was prepared according to the procedure for
compound 5. Flash chromatography (silica gel, PE–Et2O, 3:1) af-
forded the product (263.5 mg, 62%) as a pale yellow, amorphous
solid; mp 76–79 °C; Rf = 0.40 (silica gel, PE–Et2O, 3:1).
b Isolated yields after column chromatography.
IR: 1951, 1446, 1341, 1152, 824, 716 cm–1.
In conclusion, our results have demonstrated the utility of
allenes and dienes in the synthesis of complex allyl ace-
tates via palladium-catalysed transformations. Although
the product itself is a substrate for palladium-catalysed re-
actions, we developed conditions allowing the synthesis
of this class of compounds in acceptable yields. Nonsym-
metrical allenes, generally, afforded a separable mixture
of regioisomeric acetates. Although, at least in some
cases, where steric factors prevailed, a single regioisomer
was obtained via the nucleophilic attack on the p-allylpal-
ladium intermediate from the less sterically hindered side.
The regioselectivity issue was also resolved in the reac-
tions in which p-allylpalladium species was generated in
the intramolecular reaction prior to the reaction with ace-
tate. It was shown that conditions usually employed were
in favour of the thermodynamically more stable product
with the endocyclic double bond. 1,3-Dienes were also
shown to be suitable substrates for these transformations
although slightly less efficient than allenes.
1H NMR (200 MHz, CDCl3): d = 7.89 (d, J = 8.0 Hz, 1 H), 7.66 (d,
J = 8.5 Hz, 2 H), 7.31–7.24 (m, 3 H), 7.06–6.96 (m, 2 H), 5.17 (t,
J = 6.0 Hz, 1 H), 4.58–4.52 (m, 2 H), 4.21–4.15 (m, 2 H), 2.43 (s, 3
H).
13C NMR (50 MHz, CDCl3): d = 209.9, 143.7, 141.0, 140.3, 136.6,
133.8, 132.5, 131.1, 129.9, 129.5, 128.6, 128.1, 127.8, 127.7, 103.1,
85.6, 75.9, 50.7, 21.5.
MS (EI): m/z = 425 (M+), 386, 356, 230, 203, 155, 91.
HRMS (ESI): m/z [M + K]+ calcd for C17H16IKNO2S: 463.95780;
found: 463.95759.
N-Mesyl-N-(propa-1,2-dienyl)benzenamine (10b)
A mixture of N-mesyl-N-prop-2-ynylbenzenamine (211.0 mg, 1
mmol) and t-BuOK (140.0 mg, 1.25 mmol, 1.25 equiv) in t-BuOH–
THF (9 mL:3 mL) was stirred under an N2 atmosphere for 12 h. The
solvent was evaporated and flash chromatography (silica gel, PE–
Et2O, 1:1) afforded the product (142.1 mg, 68%) as a pale yellow,
amorphous solid; mp 47–50 °C; Rf = 0.34 (silica gel, PE–Et2O, 1:1).
IR: 3048, 1961, 1331, 1154, 764, 695 cm–1.
Synthesis 2012, 44, 399–408
© Thieme Stuttgart · New York

PAPER
Synthesis of Allyl Acetates
403
1H NMR (200 MHz, CDCl3): d = 7.42–7.32 (m, 5 H), 6.95 (t, J = 7.0
Hz, 1 H), 5.16 (s, 1 H), 5.13 (s, 1 H), 3.05 (s, 3 H).
3b
Yellow oil; yield: 14.2 mg (48%); E/Z 1.2:1 mixture; Rf = 0.47 (sil-
ica gel, PE–Et2O, 3:1).
IR: 1737, 1367, 1223, 1095, 1026, 735 cm–1.
13C NMR (50 MHz, CDCl3): d = 220.9, 137.3, 129.3, 129.2, 128.7,
128.0, 125.4, 101.8, 87.6, 38.1.
MS (EI): m/z = 210 (M+ + 1), 130, 128, 117, 104, 103, 95, 77, 51.
HRMS (ESI): m/z [M + NH4]+ calcd for C10H15N2O2S: 227.08487;
1H NMR (500 MHz, CDCl3): d = 7.41–7.17 (m, 20 H, E and Z), 6.17
(t, J = 6.5 Hz, 1 H, Z), 5.98 (t, J = 6.5 Hz, 1 H, E), 4.99 (s, 2 H, Z),
4.81 (s, 2 H, E), 4.57 (s, 2 H, Z), 4.42 (s, 2 H, E), 4.31 (d, J = 6.5 Hz,
2 H, Z), 4.00 (d, J = 6.5 Hz, 2 H, E), 2.03 (s, 3 H, E), 1.98 (s, 3 H, Z).
found: 227.08493.
Allyl Acetates from Allenes and Dienes; General Procedure
A mixture of allene or diene (0.1 mmol), aryl or vinyl iodide, (0.15
mmol, 1.5 equiv), Pd(OAc)2 (10 mol%), Ph3P (20 mol%), and
NaOAc (0.5 mmol, 5 equiv) in DMSO (2 mL) was heated at 85–90
°C (oil bath temperature) under N2 atmosphere for 12 h. The mix-
ture was then allowed to cool to r.t., Et2O (20 mL) was added and
the mixture washed with H2O (3 × 5 mL). The organic layer was
dried (Na2SO4), filtered, and the filtrate evaporated under reduced
pressure. The crude residue was purified by column chromatogra-
phy (silica gel, PE–Et2O or PE–EtOAc) to afford the product.
13C NMR (125 MHz, CDCl3): d = 170.8, 170.6, 139.7, 139.0, 138.1,
138.0, 136.9, 130.6, 128.5, 128.4, 128.3, 128.2, 127.9, 127.8, 127.7,
127.6, 126.8, 126.3, 72.6, 72.5, 67.7, 67.0, 66.5, 65.8, 61.1, 20.9,
15.3.
MS (EI): m/z = 236 (M+ – AcOH), 145, 130, 117, 91, 72, 43.
HRMS (ESI): m/z [M + NH4]+ calcd for C19H24NO3: 314.17507;
found: 314.17539.
4b
Yellow oil; yield: 4.7 mg (16%); Rf = 0.52 (silica gel, PE–Et2O,
3:1).
(E/Z)-4-(Benzyloxy)-2-p-tolylbut-2-enyl Acetate (3a) and
1-(Benzyloxy)-3-p-tolylbut-3-en-2-yl Acetate (4a)
Flash chromatography (silica gel, PE–Et2O, 4:1) afforded 3a and 4a
in 64% combined yield.
IR: 1739, 1368, 1229, 1026, 697 cm–1.
1H NMR (500 MHz, CDCl3): d = 7.43–7.24 (m, 10 H), 5.99–5.95
(m, 1 H), 5.36 (s, 1 H), 5.34 (s, 1 H), 4.54–4.45 (m, 2 H), 3.61–3.53
(m, 2 H), 2.14 (s, 3 H).
13C NMR (125 MHz, CDCl3): d = 170.2, 145.5, 139.1, 137.9, 128.5,
128.3, 128.0, 127.5, 126.8, 114.6, 74.2, 73.0, 71.1, 21.2.
3a
Yellow oil; yield: 14.3 mg (46%); E/Z 1.4:1 mixture; Rf = 0.37 (sil-
ica gel, PE–Et2O, 4:1).
MS (EI): m/z = 236 (M+ – AcOH), 145, 133, 117, 91, 43.
IR: 2860, 1738, 1244, 1091, 1026, 735 cm–1.
HRMS (ESI): m/z [M + H]+ calcd for C19H21O3: 297.14852; found:
297.14867.
1H NMR (500 MHz, CDCl3): d = 7.36–7.07 (m, 18 H, E and Z), 6.16
(t, J = 6.5 Hz, 1 H, Z), 5.95 (t, J = 6.5 Hz, 1 H, E), 4.98 (s, 2 H, Z),
4.80 (s, 2 H, E), 4.57 (s, 2 H, Z), 4.42 (s, 2 H, E), 4.30 (d, J = 6.5 Hz,
2 H, Z), 4.02 (d, J = 6.5 Hz, 2 H, E), 2.36 (s, 3 H, E), 2.34 (s, 3 H,
Z), 2.03 (s, 3 H, E), 1.98 (s, 3 H, Z).
13C NMR (125 MHz, CDCl3): d = 170.9, 170.6, 138.9, 138.1, 138.0,
137.6, 137.5, 136.9, 136.7, 133.9, 129.7, 129.1, 128.9, 128.4, 128.3,
128.2 (2 C), 127.8, 127.7, 127.6, 126.5, 126.1, 72.6, 72.4, 67.7,
67.1, 66.5, 61.1, 21.2, 21.1, 20.9, 20.8.
(E/Z)-4-(Benzyloxy)-2-(3-methoxyphenyl)but-2-enyl Acetate
(3c) and 1-(Benzyloxy)-3-(3-methoxyphenyl)but-3-en-2-yl Ace-
tate (4c)
Flash chromatography (silica gel, PE–Et2O, 3:1) afforded 3c and 4c
in 63% combined yield.
3c
MS (EI): m/z = 250 (M+ – AcOH), 159, 131, 91, 43.
HRMS (ESI): m/z [M + NH4]+ calcd for C20H26NO3: 328.19072;
Yellow oil; yield: 12.1 mg (37%); E/Z 1.8:1 mixture; Rf = 0.39 (sil-
ica gel, PE–Et2O, 3:1).
IR: 1732, 1576, 1225, 1027, 698 cm–1.
found: 328.19003.
1H NMR (500 MHz, CDCl3): d = 7.35–6.82 (m, 18 H, E and Z), 6.19
(t, J = 6.5 Hz, 1 H, Z), 5.97 (t, J = 6.5 Hz, 1 H, E), 4.98 (s, 2 H, Z),
4.79 (s, 2 H, E), 4.56 (s, 2 H, Z), 4.43 (s, 2 H, E), 4.32 (d, J = 6.5 Hz,
2 H, Z), 4.02 (d, J = 6.5 Hz, 2 H, E), 3.81 (s, 3 H, Z), 3.79 (s, 3 H,
E), 2.03 (s, 3 H, E), 1.98 (s, 3 H, Z).
13C NMR (125 MHz, CDCl3): d = 170.6, 159.4, 138.8, 138.3, 138.0,
129.3, 128.3, 127.8, 127.7, 126.9, 120.7, 114.0, 113.2, 72.5, 67.6,
67.0, 55.2, 20.9.
4a
Yellow oil; yield: 5.6 mg (18%); Rf = 0.42 (silica gel, PE–Et2O,
4:1).
IR: 1735, 1369, 1229, 1019, 823, 732 cm–1.
1H NMR (500 MHz, CDCl3): d = 7.32–7.12 (m, 9 H), 5.94–5.92 (m,
1 H), 5.33 (s, 1 H), 5.29 (s, 1 H), 4.47 (m, 2 H), 3.58–3.54 (m, 2 H),
2.34 (s, 3 H), 2.14 (s, 3 H).
13C NMR (125 MHz, CDCl3): d = 170.2, 145.3, 138.0, 137.8, 137.4,
136.1, 133.6, 128.8, 128.4, 127.6, 113.9, 74.2, 73.0, 71.3, 21.2,
21.1.
MS (EI): m/z = 266 (M+ – AcOH), 175, 160, 147, 129, 91, 43.
HRMS (ESI): m/z [M + Na]+ calcd for C20H22NaO4: 349.14103;
found: 349.14013.
MS (EI): m/z = 250 (M+ – AcOH), 235, 159, 144, 131, 91, 43.
HRMS (ESI): m/z [M + H]+ calcd for C20H23O3: 311.16417; found:
311.16459.
4c
Yellow oil; yield: 8.5 mg (26%); Rf = 0.43 (silica gel, PE–Et2O,
3:1).
IR: 1739, 1576, 1229, 1042, 735 cm–1.
(E/Z)-4-(Benzyloxy)-2-phenylbut-2-enyl Acetate (3b) and
1-(Benzyloxy)-3-phenylbut-3-en-2-yl Acetate (4b)
Flash chromatography (silica gel, PE–Et2O, 3:1) afforded 3b and 4b
in 64% combined yield.
1H NMR (500 MHz, CDCl3): d = 7.30–7.22 (m, 7 H), 7.08 (d,
J = 6.5 Hz, 1 H), 6.97 (s, 1 H), 6.85 (d, J = 8.5 Hz, 1 H), 5.37 (s, 1
H), 5.33 (s, 1 H), 4.54–4.52 (m, 2 H), 3.80 (s, 3 H), 3.61–3.54 (m, 2
H), 2.14 (s, 3 H).
© Thieme Stuttgart · New York
Synthesis 2012, 44, 399–408

404
S. Husinec et al.
PAPER
13C NMR (125 MHz, CDCl3): d = 170.2, 159.6, 145.4, 140.5, 137.8,
129.4, 128.3, 127.6, 127.5, 119.3, 114.8, 112.5, 74.2, 73.0, 71.0,
55.2, 21.2.
MS (EI): m/z = 326 (M+), 266, 175, 160, 134, 91, 43.
HRMS (ESI): m/z [M + Na]+ calcd for C20H22NaO4: 349.14103;
125.9, 125.7, 125.3, 125.2, 125.1, 125.0, 72.6, 72.4, 67.7, 67.3,
66.3, 63.2, 20.8, 20.2.
MS (EI): m/z = 346 (M+), 286, 195, 165, 91, 43.
HRMS (ESI): m/z [M + Na]+ calcd for C23H22NaO3: 369.14612;
found: 369.14573.
found: 349.13993.
4e
(E/Z)-4-(Benzyloxy)-2-(3,4-dimethylphenyl)but-2-enyl Acetate
(3d) and 1-(Benzyloxy)-3-(3,4-dimethylphenyl)but-3-en-2-yl
Acetate (4d)
Flash chromatography (silica gel, PE–Et2O, 4:1) afforded 3d and 4d
in 66% combined yield.
Yellow oil; yield: 2.8 mg (8%); Rf = 0.22 (silica gel, PE–Et2O, 3:1).
IR: 1738, 1364, 1024, 736, 697 cm–1.
1H NMR (500 MHz, CDCl3): d = 7.87–7.84 (m, 1 H), 7.80 (d,
J = 8.0 Hz, 1 H), 7.49–7.37 (m, 4 H), 7.28–7.19 (m, 6 H), 5.90–5.88
(m, 1 H), 5.68 (s, 1 H), 5.29 (s, 1 H), 4.47–4.37 (m, 2 H), 3.56–3.51
(m, 2 H), 2.18 (s, 3 H).
3d
13C NMR (125 MHz, CDCl3): d = 170.3, 143.8, 137.8, 137.3, 133.7,
131.7, 128.3, 128.2, 127.6, 127.5, 126.2, 126.1, 125.9, 125.7, 125.1,
117.3, 75.6, 73.0, 70.3, 21.2.
MS (EI): m/z = 346 (M+), 286, 195, 165, 91, 43.
HRMS (ESI): m/z [M + H]+ calcd for C23H23O3: 347.16417; found:
Yellow oil; yield: 13.6 mg (42%); E/Z 1.8:1 mixture; Rf = 0.47 (sil-
ica gel, PE–Et2O, 4:1).
IR: 1738, 1453, 1371, 1244, 909, 730 cm–1.
1H NMR (500 MHz, CDCl3): d = 7.35–6.91 (m, 16 H, E and Z), 6.15
(t, J = 6.5 Hz, 1 H, Z), 5.93 (t, J = 6.5 Hz, 1 H, E), 4.97 (s, 2 H, Z),
4.79 (s, 2 H, E), 4.57 (s, 2 H, Z), 4.42 (s, 2 H, E), 4.31 (d, J = 6.5 Hz,
2 H, Z), 4.03 (d, J = 6.5 Hz, 2 H, E), 2.26–2.25 (m, 12 H, E and Z),
2.04 (s, 3 H, E), 1.99 (s, 3 H, Z).
13C NMR (125 MHz, CDCl3): d = 170.9, 170.7, 138.9, 138.2, 138.1,
137.2, 136.9, 136.5, 136.4, 136.2, 134.4, 129.7, 129.6, 129.5, 129.4,
128.4, 128.3, 127.9, 127.8, 127.7, 127.6, 127.5, 126.2, 125.8, 123.6,
72.5, 72.4, 67.8, 67.2, 66.6, 61.1, 21.0, 20.9, 19.9, 19.8, 19.5, 19.1.
347.16417.
(E/Z)-4-(Benzyloxy)-2-(2-nitrophenyl)but-2-enyl Acetate (3f)
and 1-(Benzyloxy)-3-(2-nitrophenyl)but-3-en-2-yl Acetate (4f)
Flash chromatography (silica gel, PE–Et2O, 7:3) afforded 3f and 4f
in 50% combined yield.
3f
MS (EI): m/z = 325 (M+ + 1), 265, 249, 173, 145, 128, 91, 43.
HRMS (ESI): m/z [M + Na]+ calcd for C21H24NaO3: 347.16177;
Yellow oil; yield: 14.4 mg (42%); E/Z 0.8:1 mixture; Rf = 0.30 (sil-
ica gel, PE–Et2O, 7:3).
found: 347.16136.
IR: 1739, 1524, 1302, 1223, 1026, 743, 697 cm–1.
1H NMR (500 MHz, CDCl3): d = 7.99 (d, J = 8.0 Hz, 2 H, Z), 7.60–
7.56 (m, 2 H, E and Z), 7.47 (d, J = 8.0 Hz, 2 H, E), 7.38–7.21 (m,
12 H, E and Z), 6.08 (t, J = 6.5 Hz, 1 H, Z), 5.88 (t, J = 6.5 Hz, 1 H,
E), 4.99 (s, 2 H, Z), 4.81 (s, 2 H, E), 4.58 (s, 2 H, Z), 4.36 (s, 2 H,
E), 4.29 (d, J = 6.5 Hz, 2 H, Z), 3.77 (d, J = 6.5 Hz, 2 H, E), 2.00 (s,
3 H, E), 1.90 (s, 3 H, Z).
13C NMR (125 MHz, CDCl3): d = 170.3, 148.6, 148.1, 137.9, 137.8,
136.3, 135.9, 135.8, 133.1, 133.0, 132.3, 132.1, 131.7, 131.0, 128.9,
128.7, 128.6, 128.4, 128.3, 127.9, 127.7, 127.6, 127.5, 124.4, 124.2,
72.5, 72.4, 67.3, 66.7, 65.8, 62.0, 20.7, 20.5.
4d
Yellow oil; yield: 7.8 mg (24%); Rf = 0.52 (silica gel, PE–Et2O,
4:1).
IR: 1740, 1370, 1230, 1091, 733 cm–1.
1H NMR (500 MHz, CDCl3): d = 7.32–7.05 (m, 8 H), 5.95–5.92 (m,
1 H), 5.32 (s, 1 H), 5.27 (s, 1 H), 4.54–4.44 (m, 2 H), 3.60–3.53 (m,
2 H), 2.27 (s, 3 H), 2.25 (s, 3 H), 2.14 (s, 3 H).
13C NMR (125 MHz, CDCl3): d = 170.2, 145.3, 137.9, 137.3, 136.6,
136.4, 136.2, 135.6, 129.7, 128.3, 127.9, 127.5, 124.1, 113.5, 74.2,
72.9, 71.2, 21.2, 19.8, 19.4.
MS (EI): m/z = 264 (M+ – AcOH), 249, 173, 158, 145, 128, 91, 43.
HRMS (ESI): m/z [M + Na]+ calcd for C21H24NaO3: 347.16177;
MS (EI): m/z = 282 (M+ – AcOH), 250, 222, 160, 134, 91, 43.
HRMS (ESI): m/z [M + K]+ calcd for C19H19KNO5: 380.08948;
found: 380.08929.
found: 347.16093.
4f
(E/Z)-4-(Benzyloxy)-2-(naphthalen-1-yl)but-2-enyl Acetate (3e)
and 1-(Benzyloxy)-3-(naphthalen-1-yl)but-3-en-2-yl Acetate
(4e)
Flash chromatography (silica gel, PE–Et2O, 3:1) afforded 3e and 4e
in 60% combined yield.
Yellow oil; yield: 2.7 mg (8%); Rf = 0.33 (silica gel, PE–Et2O, 7:3).
IR: 1740, 1524, 1223, 1071, 787, 697 cm–1.
1H NMR (500 MHz, CDCl3): d = 7.85 (d, J = 8.0 Hz, 1 H), 7.54 (d,
J = 7.5 Hz, 1 H), 7.48–7.42 (m, 2 H), 7.33–7.27 (m, 5 H), 5.81–5.78
(m, 1 H), 5.50 (s, 1 H), 5.19 (s, 1 H), 4.59–4.48 (m, 2 H), 3.71–3.62
(m, 2 H), 2.09 (s, 3 H).
13C NMR (125 MHz, CDCl3): d = 170.0, 142.0, 137.8, 134.3, 132.4,
131.5, 128.6, 128.3, 127.7, 124.0, 117.8, 74.2, 73.1, 70.6, 21.0.
MS (EI): m/z = 282 (M+ – AcOH), 220, 178, 160, 91, 43.
3e
Yellow oil; yield: 18.0 mg (52%); E/Z 0.8:1 mixture; Rf = 0.18 (sil-
ica gel, PE–Et2O, 3:1).
IR: 1738, 1364, 1099, 778, 697 cm–1.
1H NMR (500 MHz, CDCl3): d = 7.92–7.77 (m, 6 H, E and Z), 7.49–
7.15 (m, 18 H, E and Z), 6.22 (t, J = 6.5 Hz, 1 H, Z), 5.98 (t, J = 6.5
Hz, 1 H, E), 4.99 (s, 2 H, E), 4.84 (d, J = 7.5 Hz, 2 H, Z), 4.63 (s, 2
H, Z), 4.42 (d, J = 6.0 Hz, 2 H, E), 4.29 (s, 2 H, Z), 3.76 (d, J = 6.0
Hz, 2 H, Z), 2.03 (s, 3 H, E), 1.86 (s, 3 H, Z).
13C NMR (125 MHz, CDCl3): d = 170.6, 170.5, 138.8, 138.0, 137.1,
136.8, 134.6, 133.6, 133.5, 133.0, 131.5, 131.2, 128.5, 128.4, 128.3,
128.1, 128.0, 127.8, 127.7, 127.6, 127.5, 126.4, 126.2, 126.1, 126.0,
HRMS (ESI): m/z [M + Na]+ calcd for C19H19NNaO5: 364.11554;
found: 364.11516.
(E/Z)-2-(4-Acetylphenyl)-4-(benzyloxy)but-2-enyl Acetate (3g)
and 3-(4-Acetylphenyl)-1-(benzyloxy)but-3-en-2-yl Acetate (4g)
Flash chromatography (silica gel, PE–Et2O, 7:3) afforded 3g and 4g
in 31% combined yield.
Synthesis 2012, 44, 399–408
© Thieme Stuttgart · New York

PAPER
Synthesis of Allyl Acetates
IR: 1736, 1574, 1224, 1156, 768 cm–1.
405
3g
Light-yellow amorphous solid; yield: 7.4 mg (22%); E/Z 0.9:1 mix-
ture; mp 61–63 °C; Rf = 0.21 (silica gel, PE–Et2O, 7:3).
IR: 2921, 1739, 1681, 1228, 1092, 1072, 696 cm–1.
1H NMR (500 MHz, CDCl3): d = 7.77 (d, J = 8.0 Hz, 2 H, Z), 7.67
(d, J = 8.0 Hz, 2 H, E), 7.34–7.28 (m, 11 H, E and Z), 7.21–7.20 (m,
3 H, E and Z), 6.98 (d, J = 8.5 Hz, 2 H, Z), 6.87 (d, J = 9.0 Hz, 2 H,
E), 6.77–6.75 (m, 4 H, E and Z), 5.54 (t, J = 7.0 Hz, 1 H, Z), 5.42 (t,
J = 7.0 Hz, 1 H, E), 4.67 (s, 2 H, Z), 4.56 (s, 2 H, E), 4.37 (s, 2 H,
Z), 4.22 (s, 2 H, E), 4.02 (d, J = 7.0 Hz, 2 H, Z), 3.79 (s, 3 H, Z), 3.78
(s, 3 H, E), 3.75 (d, J = 6.5 Hz, 2 H, E), 2.45 (s, 3 H, Z), 2.43 (s, 3
H, E), 1.95 (s, 3 H, Z), 1.92 (s, 3 H, E).
3C NMR (125 MHz, CDCl3): d = 170.6, 170.4, 159.2, 159.1, 143.4,
143.2, 138.8, 137.2, 137.1, 136.6, 136.4, 135.9, 131.8, 129.8, 129.7,
129.5, 128.6, 128.4, 128.3, 127.9, 127.6, 127.3, 127.2, 126.8, 124.2,
113.1, 67.4, 60.3, 55.3, 55.2, 51.6, 51.1, 45.3, 21.5, 20.7.
1H NMR (500 MHz, CDCl3): d = 8.04 (m, 4 H, E and Z), 7.94–7.91
(m, 4 H, E and Z), 7.72 (m, 4 H, E and Z), 7.52–7.26 (m, 8 H, E and
Z), 6.27 (t, J = 6.5 Hz, 1 H, Z), 6.06 (t, J = 6.5 Hz, 1 H, E), 5.01 (s,
2 H, Z), 4.83 (s, 2 H, E), 4.59 (s, 2 H, Z), 4.43 (s, 2 H, E), 4.34 (d,
J = 6.0 Hz, 2 H, Z), 3.98 (d, J = 7.0 Hz, 2 H, E), 2.65 (s, 2 H, E),
2.61 (s, 2 H, Z), 2.02 (s, 3 H, E), 1.98 (s, 3 H, Z).
13C NMR (125 MHz, CDCl3): d = 197.6, 170.7, 170.5, 144.3, 144.2,
141.8, 138.2, 137.8, 136.5, 136.4, 136.2, 136.1, 132.6, 128.6, 128.4,
128.3, 128.2, 127.8, 127.7, 127.6, 127.4, 126.4, 72.8, 72.6, 67.4,
66.7, 66.5, 60.7, 26.6, 26.5, 20.8, 20.7.
MS (EI): m/z = 479 (M+), 405, 324, 264, 207, 91.
MS (EI): m/z = 323 (M+ – CH3), 278 (M+ – AcOH), 205, 187, 129,
HRMS (ESI): m/z [M + Na]+ calcd for C27H29NNaO5S: 502.16586;
91, 43.
found: 502.16531.
HRMS (ESI): m/z [M + Na]+ calcd for C21H22NaO4: 361.14103;
found: 361.14065.
(E/Z)-4-[Benzyl(tosyl)amino]-2-phenylbut-2-enyl Acetate (6c)
Flash chromatography (silica gel, PE–Et2O, 5:3) afforded the prod-
uct (28.3 mg, 63%, E/Z 1:1 mixture) as a yellow oil; Rf = 0.24 (silica
gel, PE–Et2O, 5:3).
4g
Light-yellow amorphous solid; yield: 3.0 mg (9%); mp 63–67 °C;
Rf = 0.24 (silica gel, PE–Et2O, 7:3).
IR: 1732, 1339, 1156, 1026, 764, 698 cm–1.
IR: 2920, 1738, 1682, 1362, 1228, 1026, 734 cm–1.
1H NMR (500 MHz, CDCl3): d = 7.77 (d, J = 8.5 Hz, 2 H, Z), 7.66
(d, J = 8.0 Hz, 2 H, E), 7.34–7.19 (m, 18 H, E and Z), 7.09–7.03 (m,
4 H, E and Z), 6.95–6.93 (m, 2 H, E and Z), 5.62 (t, J = 6.5 Hz, 1 H,
Z), 5.48 (t, J = 6.5 Hz, 1 H, E), 4.70 (s, 2 H, Z), 4.59 (s, 2 H, E), 4.38
(s, 2 H, Z), 4.22 (s, 2 H, E), 4.03 (d, J = 7.0 Hz, 2 H, Z), 3.73 (d,
J = 6.5 Hz, 2 H, E), 2.44 (s, 3 H, Z), 2.42 (s, 3 H, E), 1.95 (s, 3 H,
Z), 1.93 (s, 3 H, E).
13C NMR (125 MHz, CDCl3): d = 170.6, 170.4, 143.5, 143.2, 139.5,
139.1, 137.2, 137.1, 137.0, 136.1, 136.0, 135.8, 129.8, 129.7, 128.6,
128.5, 128.4, 128.3, 128.2, 127.9, 127.7, 127.6, 127.3, 127.2, 126.1,
124.7, 67.4, 60.4, 51.6, 51.2, 45.3, 45.2, 21.5, 20.7.
1H NMR (500 MHz, CDCl3): d = 7.91 (d, J = 8.0 Hz, 2 H), 7.51 (d,
J = 9.0 Hz, 2 H), 7.32–7.23 (m, 5 H), 5.92 (m, 1 H), 5.46 (s, 1 H),
5.44 (s, 1 H), 4.53–4.46 (m, 2 H), 3.62–3.52 (m, 2 H), 2.60 (s, 3 H),
2.15 (s, 3 H).
13C NMR (125 MHz, CDCl3): d = 197.6, 170.2, 144.9, 143.8, 137.7,
136.5, 129.0, 128.5, 128.4, 127.7, 127.5, 127.4, 127.0, 116.5, 73.8,
73.1, 70.8, 26.6, 21.2.
MS (EI): m/z = 323 (M+ – CH3), 278 (M+ – AcOH), 247, 190, 175,
91, 43.
HRMS (ESI): m/z [M + H]+ calcd for C21H23O4: 339.15909; found:
339.15781.
MS (EI): m/z = 389 (M+ – AcOH), 274, 234, 155, 129, 91.
HRMS (ESI): m/z [M + H]+ calcd for C26H28NO4S: 450.17336;
found: 450.17238.
(E/Z)-4-[Benzyl(tosyl)amino]-2-p-tolylbut-2-enyl Acetate (6a)
Flash chromatography (silica gel, PE–Et2O, 5:3) afforded the prod-
uct (29.6 mg, 64%, E/Z 1:1 mixture) as a yellow oil; Rf = 0.24 (silica
gel, PE–Et2O, 5:3).
(E/Z)-2-{2-[Benzyl(tosyl)amino]ethylidene}-3-(methoxymeth-
yl)but-3-enyl Acetate (8)
Flash chromatography (silica gel, PE–Et2O, 1:1) afforded the prod-
uct (32.3 mg, 73%, E/Z 2.5:1 mixture) as a yellow oil; Rf = 0.37 (sil-
ica gel, PE–Et2O, 1:1).
IR: 3030, 2922, 1739, 1455, 1227, 1028, 926 cm–1.
1H NMR (500 MHz, CDCl3): d = 7.77 (d, J = 8.0 Hz, 2 H, Z), 7.66
(d, J = 8.0 Hz, 2 H, E), 7.33–7.05 (m, 18 H, E and Z), 6.94 (d,
J = 8.0 Hz, 2 H, Z), 6.84 (d, J = 8.0 Hz, 2 H, E), 5.58 (t, J = 7.0 Hz,
1 H, Z), 5.44 (t, J = 6.5 Hz, 1 H, E), 4.68 (s, 2 H, Z), 4.57 (s, 2 H,
E), 4.37 (s, 2 H, Z), 4.21 (s, 2 H, E), 4.02 (d, J = 7.0 Hz, 2 H, Z), 3.75
(d, J = 6.5 Hz, 2 H, E), 2.44–2.43 (m, 6 H, E and Z), 2.32–2.31 (m,
6 H, E and Z), 1.95 (s, 3 H, Z), 1.92 (s, 3 H, E).
13C NMR (125 MHz, CDCl3): d = 170.6, 170.3, 143.4, 143.2, 139.0,
137.5 (2 C), 137.2, 137.1, 137.0, 136.5, 136.0, 135.9, 133.1, 129.8,
129.6, 129.0, 128.9, 128.6, 128.4, 128.3, 128.2, 128.1, 127.8, 127.6,
127.5, 127.2 (2 C), 125.9, 124.4, 67.4, 60.3, 51.5, 51.1, 45.3, 45.2,
21.5, 21.1, 21.0, 20.8.
IR: 1737, 1338, 1226, 1026, 923, 815, 656 cm–1.
1H NMR (500 MHz, CDCl3): d = 7.76–7.71 (m, 4 H, E and Z), 7.34–
7.26 (m, 14 H, E and Z), 5.48 (t, J = 7.0 Hz, 1 H, E), 5.31 (t, J = 6.5
Hz, 1 H, E), 5.22 (s, 1 H, Z), 5.14 (s, 1 H, E), 5.08 (s, 1 H, E), 4.74
(s, 1 H, Z), 4.49 (s, 2 H, E), 4.40 (s, 2 H, Z), 4.32 (s, 2 H, E), 4.30 (s,
2 H, Z), 3.98 (d, J = 7.0 Hz, 2 H, E), 3.90 (d, J = 6.5 Hz, 2 H, Z),
3.76 (s, 2 H, E), 3.74 (s, 2 H, Z), 3.24 (s, 3 H, Z), 3.22 (s, 3 H, E),
2.44 (m, 6 H, E and Z), 1.98 (s, 3 H, Z), 1.96 (s, 3 H, E).
13C NMR (125 MHz, CDCl3): d = 170.6, 143.4, 143.3, 142.5, 140.9,
137.9, 137.2, 137.0, 136.2, 136.1, 134.8, 129.8, 129.7, 128.6, 128.5,
128.4, 128.3, 128.2, 127.8, 127.7, 127.3, 126.3, 117.4, 115.0, 73.9,
73.5, 66.3, 58.9, 58.2, 57.9, 51.6, 51.1, 45.6, 45.3, 29.7, 21.5, 20.8.
MS (EI): m/z = 403 (M+ – AcOH), 308, 274, 248, 207, 128, 91, 43.
HRMS (ESI): m/z [M + Na]+ calcd for C27H29NNaO4S: 486.17095;
MS (EI): m/z = 444 (M+ + 1), 196, 181, 155, 123, 108, 91, 77.
HRMS (ESI): m/z [M + K]+ calcd for C24H29KNO5S: 482.13980;
found: 486.17057.
found: 482.13915.
(E/Z)-4-[Benzyl(tosyl)amino]-2-(4-methoxyphenyl)but-2-enyl
Acetate (6b)
Flash chromatography (silica gel, PE–Et2O, 5:3) afforded the prod-
uct (32.6 mg, 68%, E/Z 1:1.1 mixture) as a yellow oil; Rf = 0.22 (sil-
ica gel, PE–Et2O, 5:3).
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S. Husinec et al.
PAPER
(E/Z)-3-[Benzyl(tosyl)amino]-2-(4-methoxyphenyl)allylAcetate
(11a) and 1-[Benzyl(tosyl)amino]-2-(4-methoxyphenyl)allyl
Acetate (12a)
Flash chromatography (silica gel, PE–Et2O, 1:1) afforded 11a and
12a in 48% combined yield.
IR: 1739, 1515, 1358, 1153, 1019, 699 cm–1.
1H NMR (500 MHz, CDCl3): d = 7.72 (s, 1 H), 7.32–7.24 (m, 5 H),
7.12–7.06 (m, 2 H), 6.92–6.85 (m, 2 H), 5.18 (s, 1 H), 4.93 (s, 1 H),
3.81 (s, 3 H), 2.90 (s, 3 H), 2.27 (s, 3 H).
13C NMR (125 MHz, CDCl3): d = 168.7, 159.7, 141.5, 137.9, 131.1,
129.6, 129.1, 128.7, 127.8, 120.7, 114.8, 113.8, 81.9, 55.3, 39.7,
21.0.
11a
Yellow oil; yield: 8.4 mg (18%); E/Z 2:1 mixture; Rf = 0.48 (silica
gel, PE–Et2O, 1:1).
IR: 1733, 1514, 1247, 1163, 1027, 728, 698 cm–1.
MS (EI): m/z = 376 (M+ + 1), 316 (M+ – AcOH), 236, 206, 193, 165,
121.
1H NMR (500 MHz, CDCl3): d = 7.71 (d, J = 8.5 Hz, 2 H, Z), 7.34
(d, J = 8.0 Hz, 2 H, E), 7.26–6.70 (m, 22 H, E and Z), 6.34 (s, 1 H,
E), 5.52 (s, 1 H, Z), 4.94 (s, 2 H, Z), 4.62 (s, 2 H, E), 4.31 (s, 2 H,
Z), 4.15 (s, 2 H, E), 3.79 (s, 3 H, Z), 3.78 (s, 3 H, E), 2.47 (s, 3 H,
E), 2.45 (s, 3 H, Z), 1.92 (s, 3 H, E), 1.81 (s, 3 H, Z).
HRMS (ESI): m/z [M + K]+ calcd for C19H21KNO5S: 414.07720;
found: 414.07690.
(E/Z)-4-[Benzyl(tosyl)amino]-2-(4-methoxyphenyl)but-2-enyl
Pent-4-enoate (13)
Flash chromatography (silica gel, PE–Et2O, 4:1) afforded the prod-
uct (17.1 mg, 33%, E/Z 1.7:1 mixture) as a yellow oil; Rf = 0.38 (sil-
ica gel, PE–Et2O, 4:1).
IR: 1733, 1608, 1340, 1247, 1157, 733 cm–1.
13C NMR (125 MHz, CDCl3): d = 170.5, 170.4, 159.8, 159.3, 143.9,
142.2, 141.9, 135.2, 134.7, 129.8, 129.1, 128.9, 128.5, 128.0, 127.9,
127.7, 125.1, 113.8, 67.1, 60.4, 55.3, 55.2, 53.4, 51.5, 21.6, 20.8.
MS (EI): m/z = 466 (M+ + 1), 406, 311, 251, 236, 160, 91.
1H NMR (500 MHz, CDCl3): d = 7.77 (d, J = 8.0 Hz, 2 H, Z), 7.66
(d, J = 8.0 Hz, 2 H, E), 7.34–7.19 (m, 12 H, E and Z), 7.08 (m, 2 H,
E), 6.97 (d, J = 9.0 Hz, 2 H, Z), 6.87 (d, J = 9.0 Hz, 2 H, E), 6.77 (m,
4 H, E and Z), 5.78–5.66 (m, 2 H, E and Z), 5.54 (t, J = 7.0 Hz, 1 H,
Z), 5.44 (t, J = 6.5 Hz, 1 H, E), 5.02–4.91 (m, 4 H, E and Z), 4.69 (s,
2 H, Z), 4.58 (s, 2 H, E), 4.37 (s, 2 H, Z), 4.21 (s, 2 H, E), 4.01 (d,
J = 7.0 Hz, 2 H, Z), 3.89 (s, 3 H, Z), 3.78 (s, 3 H, E), 3.75 (d, J = 6.5
Hz, 2 H, E), 2.45 (s, 3 H, Z), 2.43 (s, 3 H, E), 2.30–2.25 (m, 8 H, E
and Z).
13C NMR (125 MHz, CDCl3): d = 172.6, 172.4, 159.2, 159.1, 143.4,
143.2, 138.8, 137.2, 137.1, 136.6, 136.5, 136.4, 136.1, 135.9,
131.84, 129.8, 129.7, 129.6, 129.5, 128.7, 128.6, 128.4, 128.3 (2 C),
127.9, 127.8, 127.6, 127.3 (2 C), 127.2, 126.8, 124.3, 115.5 (2 C),
113.7, 113.6, 67.4, 60.3, 55.3, 55.2, 51.6, 51.1, 45.3, 33.4, 33.3,
29.7, 28.7, 21.5.
HRMS (ESI): m/z [M + K]+ calcd for C26H27KNO5S: 504.12415;
found: 504.12477.
12a
Yellow oil; yield: 13.9 mg (30%); Rf = 0.51 (silica gel, PE–Et2O,
1:1).
IR: 1743, 1512, 1337, 1167, 1026, 669 cm–1.
1H NMR (500 MHz, CDCl3): d = 7.57 (d, J = 8.0 Hz, 2 H), 7.50 (s,
1 H), 7.24–7.20 (m, 2 H), 7.14–7.05 (m, 7 H), 6.72 (d, J = 8.5 Hz, 2
H), 5.29 (s, 1 H), 5.17 (s, 1 H), 4.49 (d, J = 11.0 Hz, 1 H), 4.34 (d,
J = 11.5 Hz, 1 H), 3.80 (s, 3 H), 2.42 (s, 3 H), 1.81 (s, 3 H).
13C NMR (125 MHz, CDCl3): d = 168.6, 159.5, 143.6, 142.5, 136.8,
136.7, 129.5, 129.3, 128.2, 127.8, 127.7, 127.6, 126.8, 114.4, 113.5,
81.1, 55.2, 47.6, 21.5, 21.4.
MS (EI): m/z = 520 (M+ + 1), 503, 415, 341, 326, 299, 281, 225,
149.
HRMS (ESI): m/z [M + NH4]+ calcd for C30H37N2O5S: 537.24177;
found: 537.24219.
MS (EI): m/z = 466 (M+ + 1), 406, 311, 250, 236, 220, 160, 91.
HRMS (ESI): m/z [M + Na]+ calcd for C26H27NNaO5S: 488.15021;
found: 488.14965.
(E/Z)-3-[Mesyl(phenyl)amino]-2-(4-methoxyphenyl)allyl Ace-
tate (11b) and 1-[Mesyl(phenyl)amino]-2-(4-methoxyphenyl)al-
lyl Acetate (12b)
Flash chromatography (silica gel, PE–Et2O, 2:3) afforded 11b and
12b in 61% combined yield.
Diethyl 4-(Acetoxymethyl)-3-(4-methoxybenzyl)cyclopent-3-
ene-1,1-dicarboxylate (18a)
Flash chromatography (silica gel, PE–Et2O, 4:1) afforded the prod-
uct (20.6 mg, 51%) as a light-yellow oil; Rf = 0.18 (silica gel, PE–
Et2O, 4:1).
IR: 1728, 1510, 1243, 1177, 1021 cm–1.
11b
Yellow oil; yield: 7.5 mg (20%); E/Z 1.3:1 mixture; Rf = 0.37 (silica
gel, PE–Et2O, 2:3).
IR: 1733, 1513, 1348, 1244, 1159, 730 cm–1.
1H NMR (500 MHz, CDCl3): d = 7.44–6.83 (m, 18 H, E and Z), 6.39
(d, J = 8.5 Hz, 2 H, E), 4.78 (s, 2 H, Z), 4.76 (s, 2 H, E), 3.82 (s, 3
H, Z), 3.72 (s, 3 H, E), 2.99 (s, 3 H, Z), 2.89 (s, 3 H, E), 2.03 (s, 3 H,
E), 1.77 (s, 3 H, Z).
1H NMR (200 MHz, CDCl3): d = 7.01 (d, J = 8.4 Hz, 2 H), 6.81 (d,
J = 8.4 Hz, 2 H), 4.71 (s, 2 H), 4.13 (q, J = 7.0 Hz, 4 H), 3.79 (s, 3
H), 3.40 (s, 2 H), 3.10 (s, 2 H), 2.89 (s, 2 H), 2.08 (s, 3 H), 1.20 (t,
J = 7.0 Hz, 6 H).
13C NMR (50 MHz, CDCl3): d = 171.8, 171.0, 158.1, 138.3, 130.3,
129.4, 128.4, 113.9, 61.5, 59.9, 57.2, 55.2, 43.4, 42.2, 33.3, 20.8,
13.9.
13C NMR (125 MHz, CDCl3): d = 170.7, 170.5, 159.7, 158.7, 140.9,
139.1, 136.7, 132.2, 129.7, 129.6, 129.5, 128.7, 127.9, 127.7, 127.6,
127.4, 127.3, 127.2, 125.3, 113.9, 113.3, 67.4, 60.3, 55.2, 55.1,
37.6, 37.5, 20.9, 20.6.
MS (EI): m/z = 344 (M+ – OAc), 270, 225, 197, 165, 121, 91.
HRMS (ESI): m/z [M + K]+ calcd for C22H28KO7: 443.14666;
found: 443.14686.
MS (EI): m/z = 376 (M+ + 1), 236, 221, 208, 193, 178, 162.
HRMS (ESI): m/z [M + NH4]+ calcd for C19H25N2O5S: 393.14787;
Diethyl 3-(Acetoxymethyl)-4-benzylcyclopent-3-ene-1,1-dicar-
boxylate (18b)
Flash chromatography (silica gel, PE–EtOAc, 4:1) afforded the
product (8.2 mg, 22%) as a light-yellow oil; Rf = 0.48 (silica gel,
PE–EtOAc, 4:1).
IR: 1729, 1225, 1181, 1019, 700 cm–1.
found: 393.14774.
12b
Yellow oil; yield: 15.4 mg (41%); Rf = 0.40 (silica gel, PE–Et2O,
2:3).
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Synthesis of Allyl Acetates
407
1H NMR (200 MHz, CDCl3): d = 7.40–7.09 (m, 5 H), 4.72 (s, 2 H),
4.17 (q, J = 7.5 Hz, 4 H), 3.47 (s, 2 H), 3.11 (s, 2 H), 2.91 (s, 2 H),
2.08 (s, 3 H), 1.20 (t, J = 7.5 Hz, 6 H).
13C NMR (50 MHz, CDCl3): d = 171.8, 171.0, 138.3, 137.9, 128.8,
128.5, 126.3, 61.5, 59.9, 57.3, 43.4, 42.2, 34.3, 20.8, 13.9.
13C NMR (125 MHz, CDCl3): d = 170.9, 155.4, 144.2, 126.7, 124.8,
122.9, 119.8, 115.9, 111.6, 56.6, 20.9.
MS (EI): m/z = 190 (M+), 148, 119, 102, 91, 77, 43.
HRMS (ESI): m/z [M + Na]+ calcd for C11H10NaO3: 213.05222;
found: 213.05421.
MS (EI): m/z = 314 (M+ – OAc), 268, 240, 195, 167, 91.
(1,2-Dihydro-1-tosylquinolin-4-yl)methyl Acetate (15c)
Flash chromatography (silica gel, PE–Et2O, 5:3) afforded the prod-
uct (17.1 mg, 48%) as a yellow amorphous solid; mp 115–117 °C;
Rf = 0.39 (silica gel, PE–Et2O, 5:3).
HRMS (ESI): m/z [M + Na]+ calcd for C21H26NaO6: 397.16216;
found: 397.16197.
Diethyl 4-(Acetoxymethyl)-3-(3,4-dimethylbenzyl)cyclopent-3-
ene-1,1-dicarboxylate (18c)
IR: 1732, 1338, 1235, 1029, 1019, 822, 753, 681 cm–1.
Flash chromatography (silica gel, PE–EtOAc, 9:1) afforded the
product (16.1 mg, 40%) as a light-yellow oil; Rf = 0.27 (silica gel,
PE–EtOAc, 9:1).
IR: 1729, 1226, 1182 cm–1.
1H NMR (200 MHz, CDCl3): d = 7.02 (d, J = 8.0 Hz, 1 H), 6.87 (s,
1 H), 6.84 (d, J = 8.0 Hz, 1 H), 4.72 (s, 2 H), 4.15 (q, J = 7.2 Hz, 4
H), 3.39 (s, 2 H), 3.10 (s, 2 H), 2.91 (s, 2 H), 2.21 (s, 6 H), 2.08 (s,
3 H), 1.20 (t, J = 7.2 Hz, 6 H).
13C NMR (50 MHz, CDCl3): d = 171.8, 170.9, 138.3, 136.5, 135.6,
134.3, 129.8, 129.7, 128.4, 125.7, 61.5, 59.9, 57.2, 43.4, 42.2, 33.8,
20.8, 19.7, 19.2, 13.9.
1H NMR (200 MHz, CDCl3): d = 7.74 (d, J = 8.0 Hz, 1 H), 7.39–
7.20 (m, 4 H), 7.14–7.04 (m, 3 H), 5.66 (t, J = 4.0 Hz, 1 H), 4.45–
4.42 (m, 4 H), 2.34 (s, 3 H), 2.01 (s, 3 H).
13C NMR (50 MHz, CDCl3): d = 170.3, 143.4, 136.1, 135.2, 130.6,
129.0, 128.7, 128.4, 127.5, 127.3, 126.9, 123.8, 123.1, 62.7, 44.9,
21.4, 20.8.
MS (EI): m/z = 357 (M+), 297, 202, 248, 159, 142, 115, 91.
HRMS (ESI): m/z [M + H]+ calcd for C19H20NO4S: 358.11076;
found: 358.11000.
(1,2-Dihydro-2-methyl-1-oxoisoquinolin-4-yl)methyl Acetate
(15d)
MS (EI): m/z = 342, 268, 223, 195, 165, 119.
Flash chromatography (silica gel, PE–Et2O, 2:3) afforded the prod-
uct (10.6 mg, 46%) as a yellow amorphous solid; mp 89–92 °C;
Rf = 0.23 (silica gel, PE–Et2O, 2:3).
HRMS (ESI): m/z [M + K]+ calcd for C23H30KO6: 441.16740;
found: 441.16741.
Allyl Acetates via Initial Cyclisation; General Procedure
A mixture of allene (0.1 mmol), Pd(OAc)2 (10 mol%), Ph3P (20
mol%), and NaOAc (0.5 mmol, 5 equiv) in DMSO (2 mL) was heat-
ed at 90 °C (oil bath temperature) or stirred at r.t. under N2 atmo-
sphere for 12 h. The reaction was monitored by TLC and when
completed the mixture was allowed to cool to r.t. (if necessary).
Et2O (20 mL) was then added and the mixture washed with H2O
(3 × 5 mL). The ethereal layer was dried (Na2SO4), filtered and the
filtrate evaporated under reduced pressure. The crude residue was
purified by column chromatography (silica gel, PE–Et2O) to afford
the product.
IR: 1731, 1652, 1627, 1244, 937, 761, 694 cm–1.
1H NMR (200 MHz, CDCl3): d = 8.47 (d, J = 8.0 Hz, 1 H), 7.71–
7.69 (m, 2 H), 7.58–7.49 (m, 1 H), 7.24 (s, 1 H), 5.20 (s, 2 H), 2.61
(s, 3 H), 2.08 (s, 3 H).
13C NMR (50 MHz, CDCl3): d = 171.0, 162.4, 135.8, 134.4, 132.4,
128.2, 127.1, 125.9, 122.7, 110.6, 61.9, 36.9, 21.0.
MS (EI): m/z = 231 (M+), 172, 144, 131, 115, 103.
HRMS (ESI): m/z [M + Na]+ calcd for C13H13NaO3: 254.07876;
found: 254.07766.
2,3-Dihydro-3-methylenebenzofuran-2-yl Acetate (16)
Flash chromatography (silica gel, PE–Et2O, 85:15) afforded the
product (5.9 mg, 31%, 61% combined yield of 15b and 16) as a
light-yellow oil; Rf = 0.52 (silica gel, PE–Et2O, 85:15).
(1-Tosyl-1H-indol-3-yl)methyl Acetate (15a)
Flash chromatography (silica gel, PE–Et2O, 5:3) afforded the prod-
uct (17.8 mg, 52%) as a yellow amorphous solid; mp 77–80 °C;
Rf = 0.44 (silica gel, PE–Et2O, 5:3).
IR: 1732, 1339, 1239, 1163, 1021, 825, 771, 682, 653 cm–1.
1H NMR (200 MHz, CDCl3): d = 7.98 (d, J = 7.0 Hz, 1 H), 7.78 (d,
J = 8.5 Hz, 2 H), 7.62 (s, 1 H), 7.56 (d, J = 7.0 Hz, 1 H), 7.39–7.20
(m, 4 H), 5.23 (s, 2 H), 2.33 (s, 3 H), 2.08 (s, 3 H).
13C NMR (50 MHz, CDCl3): d = 170.8, 145.1, 135.1, 129.9, 129.4,
126.8, 125.6, 125.0, 123.4, 119.7, 117.2, 113.7, 57.7, 21.5, 20.8.
MS (EI): m/z = 343 (M+), 301, 284, 204, 146, 118, 91.
HRMS (ESI): m/z [M + K]+ calcd for C18H17KNO4S: 382.05099;
IR: 1756, 1464, 1216, 1194, 972, 896, 746 cm–1.
1H NMR (500 MHz, CDCl3): d = 7.44 (d, J = 7.5 Hz, 1 H), 7.26 (d,
J = 8.0 Hz, 1 H), 7.04 (t, J = 7.5 Hz, 1 H), 6.99 (t, J = 7.5 Hz, 1 H),
6.93 (d, J = 8.0 Hz, 1 H), 5.74 (s, 1 H), 5.40 (s, 1 H), 2.15 (s, 3 H).
13C NMR (125 MHz, CDCl3): d = 170.2, 160.8, 142.5, 130.9, 123.5,
122.0, 121.1, 110.8, 108.2, 97.7, 21.2.
MS (EI): m/z = 190 (M+), 148, 131, 119, 91, 77, 43.
HRMS (ESI): m/z [M + Na]+ calcd for C11H10NaO3: 213.05222;
found: 213.05426.
found: 382.04994.
Dimethyl 4-(Acetoxymethyl)-3-{[benzyl(tosyl)amino]methyl}-
5-(methoxymethyl)cyclohexa-1,4-diene-1,2-dicarboxylate (9)
A mixture of diene 8 (56.0 mg, 0.141 mmol) and DMAD (22.0 mg,
0.155 mmol, 1.2 equiv) in toluene (3 mL) was heated at 110 °C (oil
bath temperature) under N2 atmosphere for 36 h. The mixture was
allowed to cool to r.t. and solvent was evaporated under reduced
pressure. Flash chromatography (silica gel, PE–Et2O, 1:1) afforded
the product (40.4 mg, 48%) as a yellow oil; Rf = 0.18 (silica gel,
PE–Et2O, 1:1).
(Benzofuran-3-yl)methyl Acetate (15b)
Flash chromatography (silica gel, PE–Et2O, 85:15) afforded the
product (8.9 mg, 47%) as a light-yellow oil; Rf = 0.48 (silica gel,
PE–Et2O, 85:15).
IR: 1738, 1452, 1223, 1188, 1023, 814, 744, 682 cm–1.
1H NMR (500 MHz, CDCl3): d = 7.67 (s, 1 H), 7.64 (d, J = 7.0 Hz,
1 H), 7.49 (d, J = 7.0 Hz, 1 H), 7.32 (t, J = 7.0 Hz, 1 H), 7.27 (d,
J = 7.0 Hz, 1 H), 5.26 (s, 2 H), 2.08 (s, 3 H).
IR: 1721, 1266, 1228, 1156, 1091, 1022, 815, 767, 735, 656 cm–1.
© Thieme Stuttgart · New York
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PAPER
1H NMR (200 MHz, CDCl3): d = 7.65 (d, J = 8.5 Hz, 2 H), 7.30–
7.18 (m, 5 H, E), 7.02 (m, 2 H), 4.79 (d, J = 13.0 Hz, 1 H), 4.56 (d,
J = 13.0 Hz, 1 H), 4.34 (s, 2 H), 3.95 (s, 2 H), 3.91–3.87 (m, 1 H),
3.76 (s, 3 H), 3.71 (s, 3 H), 3.66–3.60 (m, 2 H), 3.27 (s, 3 H), 3.25–
3.21 (m, 2 H), 2.43 (s, 3 H), 1.99 (s, 3 H).
13C NMR (50 MHz, CDCl3): d = 170.7, 168.1, 166.8, 143.5, 137.7,
136.4, 135.2, 134.4, 133.5, 130.0, 129.7, 128.9, 128.5, 127.8, 127.4,
70.3, 61.7, 58.0, 52.9, 52.3, 50.3, 40.3, 30.4, 21.5, 20.9.
824. (c) Sheng, S.-R.; Huang, X. J. Chem. Res., Synop. 2002,
184.
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Lett. 2009, 11, 5518. (b) Covell, D. J.; White, M. C. Angew.
Chem. Int. Ed. 2008, 47, 6448. (c) Chen, M. S.; Prabagaran,
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1998, 4, 1083. (e) Yang, H.; Khan, M. A.; Nicholas, K. M.
J. Mol. Catal. 1994, 91, 319.
MS (EI): m/z = 586 (M+), 569, 537, 525, 509, 493, 465, 449, 437.
HRMS (ESI): m/z [M + H]+ calcd for C30H36NO9S: 586.21053;
(6) Su, Y.; Jiao, N. Org. Lett. 2009, 11, 2980.
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Acknowledgment
Financial support from the Serbian Ministry of Science (grant no.
172009) is greatly appreciated. We thank Faculties of Pharmacy
and Chemistry, Belgrade University for their assistance. We would
also like to thank Dr A. E. A. Porter for fruitful discussions.
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