Lewis acid catalyzed cascade reactions of 1,6-diynes and 1,6-enynes with vinylidenecyclopropanes

Article abstract of DOI:10.1002/chem.200802284

Lewis acid catalyzed reactions of N-(4-hydroxy-4,4-diarylbut-2-ynyl)-4- methyl-N-prop-2-ynylbenzenesulfonamides or 1,1-diphenyl-4-prop-2-ynyloxybut-2- yn-l-ol (1,6-diynes) 1 and N-allyl-N-(4-hydroxy-4,4-diarylbut-2-ynyl)-4- methylbenzenesulfonamides (1,6-

Full text of DOI:10.1002/chem.200802284

FULL PAPER
DOI: 10.1002/chem.200802284
Lewis Acid Catalyzed Cascade Reactions of 1,6-Diynes and 1,6-Enynes with
Vinylidenecyclopropanes
Liang-Feng Yao and Min Shi*[a]
Abstract: Lewis acid catalyzed reac-
tions of N-(4-hydroxy-4,4-diarylbut-2-
ynyl)-4-methyl-N-prop-2-ynylbenzene-
sulfonamides or 1,1-diphenyl-4-prop-2-
ynyloxybut-2-yn-1-ol (1,6-diynes) 1 and
N-allyl-N-(4-hydroxy-4,4-diarylbut-2-
ynyl)-4-methylbenzenesulfonamides
(1,6-enynes) 2 with vinylidenecyclopro-
panes 3 selectively produce polycyclic
compounds 4, 5 and 10 as well as iso-
propylidene-3,3-diarylcyclobut-1-enyl-
methyl derivatives 6 or 7 in good to
high yields depending on the substitu-
ents on the benzene ring of 3 under
mild conditions. An interesting PtCl2-
catalyzed cyclization of 6 and a Cu-
AHCTUNGTERG(NNUN OAc)2·H2O catalyzed Eglinton cou-
pling reaction of 5 and 10 to produce
methyl-1-(toluene-4-sulfonyl)-7-vinyl-
1,2,3,4,5,8-hexahydroazocine
deriva-
tives 8 and the coupling products 9 and
11 in good yields have been disclosed,
respectively. Plausible mechanisms of
these processes have been proposed
that belong to a cascade rearrangement
followed by the Friedel–Crafts reac-
tion, an intramolecular proton transfer-
ring and a cyclization reaction.
the corresponding 5-isopropylidene-6-
Keywords: cyclization
· cyclopro-
panes · Friedel–Crafts reaction ·
Lewis acids · platinum
Introduction
For example, previously, we reported that arylmethylenecy-
clopropanes can react with 3-methoxy-1,3,3-triarylprop-1-
yne or 1,1,3-triarylprop-2-yn-1-ol to give the corresponding
functionalized methylenecyclobutene, cyclobutane, and cy-
clopropane derivatives in the presence of Lewis acid
BF3·OEt2 under mild conditions as well as vinylidenecyclo-
propanes can react with 1,1,3-triarylprop-2-yn-1-ols or their
methyl ethers to produce 4-dihydro-1H-cyclopenta[b]naph-
thalene derivatives and 1,2,3,8-tetrahydrocyclopenta[a]in-
dene derivatives in good to high yields in the presence of
Lewis acid, respectively, depending on the substituents on
the cyclopropane (Scheme 1).[5] These results inspired us to
investigate the intermolecular reactions of 1,6-diynes and
1,6-enynes with VDCPs in the presence of metal catalysts.
On the basis of above results, we envisaged that a diphenyl-
methanol containing 1,6-diyne or 1,6-enyne would produce
cationic intermediate A similarly in the presence of Lewis
acids via an allenyl cationic rearrangement; this intermedi-
ate is anticipated to react with VDCPs to afford very useful
polycyclic compounds through a tandem reaction pathway
(Scheme 2). Moreover, it is conceivable that through the
Metal-catalyzed reactions of 1,6-diynes and 1,6-enynes have
emerged as efficient and useful methods for the construction
of cyclic or polycyclic organic skeletons from rather simple
substrates under mild conditions.[1] Recently, we have been
investigating the Lewis acid catalyzed skeletal conversions
of vinylidenecyclopropanes (VDCPs) and methylenecyclo-
propanes (MCPs), two kinds of highly strained and readily
accessible molecules, into various cyclic compounds under
mild conditions through the formation of cationic intermedi-
ates.[2–4] Thus far, a number of interesting intramolecular
and intermolecular skeletal conversions of VDCPs and
MCPs into cyclic functional compounds have been explored.
[a] L.-F. Yao, Prof. Dr. M. Shi
State Key Laboratory of Organometallic Chemistry
Shanghai Institute of Organic Chemistry
Chinese Academy of Sciences
354 Fenglin Lu, Shanghai, 200032 (China)
Fax : (+86)21-64166128
E-mail: mshi@mail.sioc.ac.cn
ꢀ
extra C=C double bond or C C triple bond in 1,6-diyne or
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/chem.200802284: The spectroscopic
data (1H and 13C NMR spectroscopic data) and analytic data of the
compounds shown in Tables 1–3 and Scheme 2, the X-ray crystal
structures of 4a, 6a, 8a and 10a and the detailed description of ex-
perimental procedures
1,6-enyne, the further transformation could be realized.
Polysubstituted aromatic compounds have played an impor-
tant role in the chemical and pharmaceutical industries as
well as in the fields of optical and electronic materials. Re-
cently, there has been a considerable interest in synthesizing
Chem. Eur. J. 2009, 15, 3875 – 3881
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3875

the resulting products depend
on the substituents on the ben-
zene rings of 3 along with an in-
teresting PtCl2-catalyzed cycli-
zation and
a CuACHTNUTGERNUN(G OAc)2·H2O
catalyzed Eglinton coupling re-
action.
Results and Discussion
Initial examinations using N-(4-
hydroxy-4,4-diphenylbut-2-
ynyl)-4-methyl-N-prop-2-ynyl-
benzenesulfonamide (1,6-diyne)
(1a,
R1 =C6H5,
0.1
or
0.12 mmol) or N-allyl-N-(4-hy-
droxy-4,4-diphenylbut-2-ynyl)-
4-methylbenzenesulfonamide
(1,6-enyne) (2a, R1 =C6H5, 0.1
or 0.12 mmol) and diphenylvi-
nylidenecyclopropane (3a, R2 =
C6H5, 0.1 or 0.2 mmol) having
four methyl groups at the cyclo-
propane ring as the substrates
in the presence of various
Lewis acids in a variety of sol-
Scheme 1. Lewis acid catalyzed reactions of arylmethylenecyclopropanes with 3-methoxy-1,3,3-triarylprop-1-
yne or 1,1,3-triarylprop-2-yn-1-ol.
vents were aimed at determining the optimal conditions.
The results of these experiments are provided in the Sup-
porting Information as Tables S1 and S2. We found that the
corresponding polycyclic compounds 4a or 5a were formed
in the presence of SnACHTNUGTRNEUNG(OTf)2 (10 mol% for the formation of
4a) and BF3·OEt2 (10 mol% for the formation of 5a) in 1,2-
dichloroethane (DCE) at room temperature (208C), which
serves as the best condition for the following experiments.
Under this optimal condition, we next carried out this re-
action using a variety of starting materials 1 (1,6-diynes) or
2 (1,6-enyne) and 3 (diarylvinylidenecyclopropanes) at-
tached by different aromatic groups. The selected results are
summarized in Table 1. As can be seen in Table 1, the corre-
sponding polycyclic compounds 4 and 5 were obtained in
good to high yields (50 to 99%, Table 1, entries 1–15). Sub-
stituents on the aromatic ring of 1, 2 and 3 have little influ-
ence on the reaction outcomes. As for unsymmetrical 1,6-
enyne 2c (R1 =C6H5. R1 =Me), the corresponding polycyclic
product 5 f was obtained in 50% yield (Table 1, entry 15). In
the case of unsymmetrical vinylidenecyclopropanes 3e and
3 f, polycyclic products 4h and 4i were produced stereospe-
cifically in 75 and 70% yield with E/Z or Z/E > 99:1 on the
basis of their NMR spectroscopic data (see Supporting In-
formation), respectively (Table 1, entries 8 and 9). Product
structures were determined by 1H and 13C NMR spectro-
scopic data, HRMS and microanalysis. Furthermore, the X-
ray crystal structure of 4a was determined and its CIF data
are presented in the Supporting Information (Figure 1).[9]
Using 1,1-diphenyl-4-prop-2-ynyloxy-but-2-yn-1-ol (1a’)
to replace 1a in the reaction with 3a afforded the corre-
Scheme 2. Proposal on the intermolecular reactions of 1,6-diyne and 1,6-
enyne with VDCPs in the presence of Lewis acid.
naphthalene, indene derivatives and other extended aromat-
ic systems, which are extremely useful benzenoid com-
pounds for biological studies and material applications.[6]
The most important methods for these compounds include
annulation via Fischer carbene (the Dçtz reaction)[7] and
palladium-catalyzed cyclization of alkynes with arylsilyl tri-
flate via highly reactive benzynes (generated in situ).[8]
Herein, we wish to report highly efficient Lewis acid cata-
lyzed cascade intermolecular reactions of N-(4-hydroxy-4,4-
diarylbut-2-ynyl)-4-methyl-N-prop-2-ynylbenzenesulfonami-
des or 1,1-diphenyl-4-prop-2-ynyloxybut-2-yn-1-ol (1,6-
diynes) 1 and N-allyl-N-(4-hydroxy-4,4-diarylbut-2-ynyl)-4-
methylbenzenesulfonamides (1,6-enynes) 2 with VDCPs 3
that selectively produce polycyclic derivatives 4 and 5 as
well as isopropylidene-3,3-diarylcyclobut-1-enylmethyl de-
rivatives 6 or 7 in good to high yields under mild conditions;
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Lewis Acid Catalyzed Reactions
FULL PAPER
Table 1. SnACHTUNGTRENNUNG(OTf)2 or BF3·OEt2-catalyzed reactions of 1 or 2 with VDCPs
3.
sponding polycyclic product 4j in 76% yield under identical
conditions, rendering the significant diversity of this interest-
ing reaction (Scheme 3).
Entry[a]
R1/R1
R2/R2
Yield of
4 or 5 [%][b]
1
2
3
4
5
6
7
8
9
C6H5/
C6H5/
C6H5, 3a
3a
4a, 80[c]
4b, 80[c]
4c, 93[c]
4d, 95[c]
4e, 91[c]
4 f, 99[c]
4g, 94[c]
4h, 75[e]
4i, 70[e]
C6H5, 1a
p-ClC6H4/
p-ClC6H4, 1b
p-MeC6H4/
p-MeC6H4, 1c
p-FC6H4/
p-FC6H4, 1d
1a
Scheme 3. SnACTHUNRGTNEUNG(OTf)2-catalyzed reaction of 1a’ with 3a.
3a
3a
A plausible mechanism based on a cascade rearrangement
is outlined in Scheme 4.[10] In the presence of a Lewis acid
(LA), a cationic intermediate A is produced from 1 or 2,
which adds to the central carbon in allenic moiety of 3 to
afford cationic intermediate B.[10] Cyclization of intermedi-
ate B produces cationic intermediate C, which affords cat-
ionic intermediate D via the intramolecular Friedel–Crafts
reaction with the adjacent aromatic R1 group. Aromatiza-
tion of intermediate D produces polycyclic compounds 4
and 5.
p-FC6H4/
p-FC6H4, 3b
p-MeC6H4/
p-MeC6H4, 3c
p-ClC6H4/
p-ClC6H4, 3d
p-ClC6H4/
C6H5, 3e
m,p-Cl2C6H3/
C6H5, 3 f
3a
1a
1a
C6H5/
C6H5, 2a
2a
10
11
12
13
14
2a
2a
2a
2a
5a, 97[d]
5b, 86[d]
5c, 85[d]
5d, 90[d]
5e, 88[d]
3d
3b
3c
3a
p-MeC6H4/
p-MeC6H4, 2b
p-MeC6H4/
Me, 2c
15
3a
5 f, 50[d]
[a] All reactions were carried out using 1 or 2 (0.4 mmol), 3 (0.2 mmol)
and catalyst (10 mol%) in DCE (2 mL). [b] Isolated yields. [c] Sn(OTf)2
AHCTUNGTRENNUNG
was used a Lewis acid. [d] BF3·OEt2 was used as a Lewis acid. [e] E/Z or
Z/E > 99:1.
Scheme 4. Plausible reaction mechanism.
Interestingly, we found that as for the reaction of 1e or
2d, bearing two p-methoxyphenyl groups, with 3a, isopropyl-
idene-3,3-diphenylcyclobut-1-enylmethyl derivative 6a or 7
was formed in 75 or 92% yield, respectively, rather than
polycyclic derivative 4 or 5 (Table 2, entry 1 and Scheme 5).
The generality of this reaction was found to be satisfactory
for a variety of VDCPs 3 under the standard condition
(Table 2). The structure of 6a was unambiguously disclosed
by X-ray diffraction and its CIF data are also provided in
the Supporting Information (Figure 2).[9] This might be due
to the fact that the formed cationic intermediate E produces
intermediate F via an intramolecular proton transferring,
which can be stabilized by two electron-rich aromatic
groups (two p-methoxyphenyl groups). The subsequent in-
tramolecular cyclization and deprotonation afford 6 or 7
(Scheme 6).
Figure 1. ORTEP drawing of 4a.
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M. Shi and L.-F. Yao
Table 2. BF3·OEt2-catalyzed reaction of 1e with VDCPs 3.
To clarify other strongly electron-donating substituents
that can provide such isopropylidene-3,3-diphenylcyclobut-
1-enylmethyl derivative 6, a variety of 1,6-diynes 1 f–1i con-
taining electron-donating alkoxy groups on the benzene
rings were prepared and successively employed in this reac-
tion and the results of these experiments are summarized in
Table 3. As can be seen, the corresponding isopropylidene-
3,3-diphenylcyclobut-1-enylmethyl derivatives 6g and 6h
were formed in 67 and 52% yield, respectively, although O-
benzyl group substituted 1,6-diyne 1 f afforded the corre-
sponding isopropylidene-3,3-diphenylcyclobut-1-enylmethyl
derivative 6 f in trace along with other complex product
mixtures presumably due to the lability of O-benzyl group
under identical conditions (Table 3, entries 1–3). As for 1,1-
Entry
R2/R2
Yield of 6 [%][a]
1
2
3
4
5
3a
3d
3c
3b
6a, 75
6b, 84
6c, 88
6d, 97
6e, 82
p-MeOC6H4/p-MeOC6H4, 3e
[a] Isolated yields.
bis(4-methoxyphenyl)-4-prop-2-ynyloxybut-2-yn-1-ol 1i,
a
similar result was obtained, affording 6i in 77% yield under
the standard conditions (Table 3, entry 4).
Next, we attempted to utilize PtCl2 as a catalyst for the
cyclization of 6[12] to construct another series of useful buta-
diene derivatives.[13,14] As shown in Table 4, the correspond-
ing 5-isopropylidene-6-methyl-1-(toluene-4-sulfonyl)-7-vinyl-
1,2,3,4,5,8-hexahydroazocine derivatives 8 were obtained in
good yields of 77 to 96% in toluene within 5 h at 608C
(Table 4, entries 1–3). The structure of 8a has been con-
firmed by X-ray diffraction (Figure 3).[9]
Scheme 5. BF3·OEt2-catalyzed reaction of 2d with 3a.
Table 3. BF3·OEt2-catalyzed reaction of a variety of electron-rich 1 with
3a.
Entry
X
R1/R2
Yield of 6 [%][a]
1
2
TsN
TsN
p-BnOC6H4/p-BnOC6H4, 1 f
p-EtOC6H4/p-EtOC6H4, 1g
6 f, trace[b]
6g, 67
3
4
TsN
O
6h, 52
6i, 77
p-MeOC6H4/p-MeOC6H4, 1i
[a] Isolated yields. [b] Complex product mixture.
Figure 2. ORTEP drawing of 6a.
Table 4. PtCl2-catalyzed cyclization of 6.
Entry
R2/R2
Yield of 8 [%][a]
1
2
3
C6H5/C6H5, 6a
p-MeC6H4/p-MeC6H4, 6c
p-MeOC6H4/p-MeOC6H4, 6e
8a, 80
8b, 77
8c, 96
Scheme 6. Plausible reaction mechanism.
[a] Isolated yields.
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Lewis Acid Catalyzed Reactions
FULL PAPER
Scheme 8. Lewis acid catalyzed reaction of 1a with VDCP 3g and 2e
with VDCP 3a.
On the other hand, the BF3·OEt2-catalyzed reaction of 1a
with VDCPs 3h–l having two phenyl groups at one carbon
of cyclopropane produced the corresponding 2-benzhydryl-
AHCTUNGERTGiNNUN dene-4,4,9-triphenyl-2,4-dihydro-1H-cyclopenta[b]naphtha-
lene derivatives 10, another type of interesting polycyclic
compounds, in moderate yields, indicating the interesting re-
action diversity depending on the substituents at the cyclo-
propane in 1 (Table 5). The structure of 10a has been con-
Figure 3. ORTEP drawing of 8a.
Furthermore, we attempted to use ruthenium–carbene
catalyst (Grubbs 1st-generation catalyst) instead of PtCl2 in
this interesting cyclization. However, it was found that no
reaction occurred along with the recovery of the starting
materials.
Table 5. BF3·OEt2-catalyzed reaction of 1a with VDCPs 3h–l.
Moreover, the Eglinton coupling reaction of 5a catalyzed
by CuII in pyridine afforded 1,3-diyne 9 in 61% yield
(Scheme 7).[15] This is because product 9 contains diyne
moiety, which is extremely useful for organometallic studies.
The most important utility of this compound is to form zir-
conocene complexes via cyclization with Cp2ZrPh2.[16] There-
fore, the polycyclic products 5 and 6 derived from the reac-
tion of VDCPs with 1,6-enyne 2 can be transformed into
more interesting products via the PtCl2-catalyzed cyclization
and the Eglinton coupling reaction with another free triple
bond.
Entry[a]
R1/R2R3
T [8C]
Yield of 10 [%][b]
1
2
3
4
5
3h, C6H5/C6H5/H
0
À10
À10
0
10a, 58
10b, 51
10c, 60
10d, 58
10e, 58
3i, p-MeC6H4/p-MeC6H4/H
3j, p-ClC6H4/p-ClC6H4/H
3k, p-FC6H4/p-FC6H4/H
3 L, C6H5/C6H5/Me
0
[a] All reactions were carried out in DCE (2 mL) using 1 (0.2 mmol), 2a
(0.24 mmol) and BF3·OEt2 (10 mol%). [b] Isolated yields.
firmed by X-ray diffraction and the CIF data have been pre-
sented in the Supporting Information (Figure 4).[9] A plausi-
ble reaction mechanism is indicated in Scheme 9. Similarly,
intermediates A, B, and C are formed in the Lewis acid cat-
alyzed reaction of 1a with VDCPs 3h–l. The allylic rear-
rangement of cationic intermediate C gives cationic inter-
mediate D, which is stabilized by two aromatic groups and
undergoes intramolecular Friedel–Crafts reaction with the
adjacent phenyl ring to produce the corresponding product
10. The intramolecular Friedel–Crafts reaction with the ad-
jacent phenyl ring in intermediate D can take place more
easily than that of intermediate C since the cyclic cation in
intermediate C is a sterically tight species which should be
more difficult to go through an intramolecular Friedel–
Crafts reaction. This is the reason why 2-benzhydrylidene-
4,4,9-triphenyl-2,4-dihydro-1H-cyclopenta[b]naphthalene de-
rivatives 10 are formed in the BF3·OEt2-catalyzed reaction
of 1a with VDCPs 3h–l.
Scheme 7. Eglinton coupling reaction of compound 5a to produce 9.
As for the BF3·OEt2-catalyzed reaction of 1a with dime-
thylvinylidenecyclopropane 3g, complex product mixtures
were obtained under the standard conditions, suggesting
that two aromatic groups in substrate 3 are required
(Scheme 8). Moreover, it was found that no reaction oc-
curred at room temperature or at 608C between enyne 2e
containing dimethylmethylmethanol moiety and 3a, indicat-
ing that one aromatic group is essential for the generation
of a cationic intermediate (Scheme 8).
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M. Shi and L.-F. Yao
Conclusion
We have established a new Lewis acid catalyzed intermolec-
ular reaction in which N-(4-hydroxy-4,4-diarylbut-2-ynyl)-4-
methyl-N-prop-2-ynyl-benzenesulfonamides or 1,1-diphenyl-
4-prop-2-ynyloxybut-2-yn-1-ol (1,6-diynes) 1 and N-allyl-N-
(4-hydroxy-4,4-diarylbut-2-ynyl)-4-methylbenzenesulfona-
mides (1,6-enynes) 2 react with VDCPs 3 to provide poly-
cyclic compounds 4, 5, and 10 as well as isopropylACTHNUTRGENUGiN dene-3,3-
diarylcyclobut-1-enylmethyl derivatives 6 or 7 selectively
and efficiently along with an interesting PtCl2-catalyzed cyc-
lization of 6 and a CuACHTNUTRGNEUNG(OAc)2·H2O catalyzed Eglinton cou-
pling reaction of 5 and 10 to produce the corresponding 5-
isopropylidene-6-methyl-1-(toluene-4-sulfonyl)-7-vinyl-
1,2,3,4,5,8-hexahydroazocine derivatives 8 and the coupling
products 9 and 11 in good yields. Plausible mechanisms of
these processes have been proposed that belong to a cascade
rearrangement followed by the Friedel–Crafts reaction, an
intramolecular proton transferring and a cyclization reac-
tion. Using this method, a series of novel polycyclic and iso-
propylidene-3,3-diarylcyclobut-1-enylmethyl derivatives can
be conveniently obtained by starting with easily available re-
agents under mild conditions. Further studies regarding the
mechanistic details and scope of this process are in progress.
Figure 4. ORTEP drawing of 10a.
Experimental Section
General remarks: 1H and 13C NMR spectra were recorded on a Bruker
AM-300 spectrometer for solution in CDCl3 with tetramethylsilane
(TMS) as an internal standard; J values are in Hz. Mass spectra were re-
corded by EI and MALDI methods, and HRMS was measured on a Fin-
nigan MA+ mass spectrometer. CHN microanalyses were recorded on a
Carlo-Erba 1106 analyzer. THF and toluene were distilled from sodium
(Na) under argon (Ar) atmosphere. CH3CN and 1,2-dichloroethane were
distilled from CaH2 under argon (Ar) atmosphere. Commercially ob-
tained reagents were used without further purification. All reactions
were monitored by TLC with Huanghai GF254 silica gel coated plates.
Flash column chromatography was carried out using 300–400 mesh silica
gel at increased pressure.
General procedure for the Lewis acid catalyzed reaction of arylvinylidi-
enecyclopropanes with 1,6-diynes-ols: Under an argon atmosphere, aryl-
vinylidenecyclopropane 3 (0.4 mmol), 1,6-diynes-ols 1 (0.2 mmol), Sn-
Scheme 9. Plausible reaction mechanism.
AHCTUNGRTEG(NNNU OTf)2 (10 mol%) were added into a Schlenk tube. The reaction mixture
was stirred at room temperature for 6 h in DCE, then the solvent was re-
moved under reduced pressure and the residue was purified by a flash
column chromatography.
Product 4a: A white solid, m.p. 144–1468C; 1H NMR (CDCl3, 300 MHz,
TMS): d=1.27 (s, 3H, CH3), 1.30 (s, 3H, CH3), 1.60 (s, 3H, CH3), 1.88 (t,
1H, J=2.1 Hz, CH), 1.93 (s, 3H, CH3), 2.36 (s, 3H, CH3), 3.49 (dd, 1H,
J=2.1, 18.3 Hz, CH2), 3.73 (dd, 1H, J=2.1, 18.3 Hz, CH2), 3.91 (d, 1H,
J=13.8 Hz, CH2), 4.39 (d, 1H, J=
Similarly, the Eglinton coupling reaction of 10e catalyzed
by CuII in pyridine afforded 1,3-diyne 11 in 73% yield
(Scheme 10).
13.8 Hz, CH2), 5.86 (d, 1H, J=8.1 Hz,
Ar), 6.44–6.50 (m, 2H, Ar), 6.90–7.19
(m, 8H, Ar), 7.18 (d, 2H, J=8.1 Hz,
Ar), 7.27–7.57 (m, 9H, Ar), 7.68 ppm
(d, 1H, J=7.5 Hz, Ar); 13C NMR
(CDCl3, 75 MHz, TMS): d=21.0, 21.5,
25.3, 27.7, 30.2, 37.0, 41.3, 50.4, 67.9,
73.8, 77.4, 119.4, 124.1, 126.0, 126.1,
127.2, 127.4, 128.0, 128.2, 128.3, 129.1,
Scheme 10. Eglinton coupling reaction of compound 10e to produce 11.
129.4, 129.6, 130.2, 130.9, 131.1, 135.8,
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Chem. Eur. J. 2009, 15, 3875 – 3881

Lewis Acid Catalyzed Reactions
FULL PAPER
136.4, 137.0, 138.6, 139.5, 142.4, 143.2, 144.1, 145.0, 145.1, 146.9,
160.0 ppm; IR (CH2Cl2): n˜ =3095, 3058, 3024, 2969, 2926, 2853, 1629,
1596, 1568, 1490, 1456, 1442, 1348, 1330, 1307, 1288, 1266, 1162, 1118,
1103, 1090, 1073, 1059, 1031, 1019, 973, 893, 879, 815, 800, 778, 764, 750,
702, 683, 662, 635, 603, 579, 563, 545, 531 cmÀ1; MS (MALDI): m/z: 708
[M++Na]; elemental analysis calcd (%) for C47H43NO2SNa+: 708.2918;
found: 708.2907.
M. Shi, Synlett 2005, 1869–1872; c) Y.-P. Zhang, J.-M. Lu, G.-C. Xu,
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Acknowledgements
We thank the Shanghai Municipal Committee of Science and Technology
(06XD14005, 08dj1400100-2), National Basic Research Program of China
ACHTUNGTRENNUNG(973)-2009CB825300, and the National Natural Science Foundation of
China for financial support (20872162, 20672127, and 20732008).
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Received: November 4, 2008
Published online: February 16, 2009
Chem. Eur. J. 2009, 15, 3875 – 3881
ꢀ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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