Studies on Pd0-catalyzed cyclization of N-3,4-alkadienyl toluenesulfonamides with organic halides: Selective synthesis of 2,3-dihydropyrroles, 1,2,3,6-tetrahydropyrridines, and azetidines

Article abstract of DOI:10.1002/chem.200600431

The palladium-catalyzed coupling-cyclization of β-amino allenes with organic halides ranging from aryl halide to 1-alkenyl halide was studied. 2,3-Dihydro-1H-pyrroles were obtained by reaction of 3-substituted-5- unsubstituted-3,4-allenyl amides under conditions A, while the reaction of 5-substituted-3,4-allenyl amides afforded 1,2,5,6-tetrahydropyridines and/or azetidines with high de under conditions B or C. The skeleton and relative configuration of the six-membered products were established by the X-ray diffraction studies of 10ka. Allenyl amide 4q reacted with 1,4-diiodobenzene 6r to afford double cyclization product 15. The structure of its major stereoisomer was also determined by the X-ray diffraction study.

Full text of DOI:10.1002/chem.200600431

FULL PAPER
DOI: 10.1002/chem.200600431
Studies on Pd0-Catalyzed Cyclization of N-3,4-Alkadienyl
Toluenesulfonamides with Organic Halides: Selective Synthesis of
2,3-Dihydropyrroles, 1,2,3,6-Tetrahydropyrridines, and Azetidines
Shengming Ma,*[a, b] Fei Yu,[a] Jing Li,[b] and Wenzhong Gao[a]
Abstract: The palladium-catalyzed cou-
pling–cyclization of b-amino allenes
with organic halides ranging from aryl
halide to 1-alkenyl halide was studied.
2,3-Dihydro-1H-pyrroles were obtained
by reaction of 3-substituted-5-unsubsti-
tuted-3,4-allenyl amides under condi-
tions A, while the reaction of 5-substi-
tuted-3,4-allenyl
amides
afforded
uration of the six-membered products
were established by the X-ray diffrac-
tion studies of 10ka. Allenyl amide 4q
reacted with 1,4-diiodobenzene 6r to
afford double cyclization product 15.
The structure of its major stereoisomer
was also determined by the X-ray dif-
fraction study.
1,2,5,6-tetrahydropyridines and/or aze-
tidines with high de under conditions B
or C. The skeleton and relative config-
Keywords: allenes · amines · cross-
coupling · cyclization · palladium
Introduction
Recently, much attention has been paid to the chemistry of
allenes.[1,2] During the course of our systematic study on the
chemistry of allenes[3] we noted that Hiemstra, Tanaka,
Ibuke, and Kang reported on the palladium-catalyzed cou-
pling–cyclization reaction of 3,4-dienyl amide derivatives
with organic halides[4,5] or hypervalent iodonium salts[6] lead-
ing to the formation of azetidines and/or tetrahydropyri-
dines with considerable selectivity. In these reactions, amino
allenes undergo highly regioselective carbopalladation af-
fording a p-allylic palladium intermediate,[7] which was fol-
lowed by the intramolecular nucleophilic attackof the nitro-
gen group to give cyclic products (Scheme 1).
Scheme 1.
which the substituent of the allene moiety as well as the ni-
trogen atom is a decisive factor for the determination of the
reaction pathways for this intramolecular amination reac-
tion, that is, with the introduction of R1 group the reaction
afforded 2,3-dihydropyrroles (Scheme 2).[8] Since many aze-
tidines, dihydropyrroles or tetrahydropyridines show inter-
esting biological activities[9] and are important building
blocks in organic chemistry,[10] we wish to disclose our
recent detailed study on the selective synthesis of these
compounds via the Pd-catalyzed coupling cyclization of dif-
ferently substituted b-amino allenes with organic halides.
Recently, we have reported our own results on the Pd0-
catalyzed coupling–cyclization reaction of b-amino allenes
with organic halides forming five-membered products, in
[a] Prof. S. Ma, F. Yu, Dr. W. Gao
State Key Laboratory of Organometallic Chemistry
Shanghai Institute of Organic Chemistry
Chinese Academy of Sciences, 354 Fenglin Lu
Shanghai 200032 (China)
Fax : (+86)21-6416-7510
E-mail: masm@mail.sioc.ac.cn
[b] Prof. S. Ma, J. Li
Laboratory of Molecular Recognition
Department of Chemistry and Synthesis, Zhejiang University
Hangzhou 310027 (China)
Supporting information for this article is available on the WWW
under http://www.chemeurj.org/ or from the author.
Scheme 2.
Chem. Eur. J. 2007, 13, 247 – 254
ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
247

Results and Discussion
Preparation ofthe starting materials 4a–z : 3,4-Allenyl
amides 4a–z used in this study were prepared by Mitsunobu
amination of the related 3,4-allenols,[11] which were prepared
from the oxy-Cope rearrangement reaction of the corre-
sponding propargylic alcohols (Table 1).[12]
Table 1. 3,4-Allenyl amides 4a–z used in this study.
Scheme 3. i) Phthalimide, DEAD, PPh3, THF, 08C–RT; ii) N2H4·H2O,
MeOH, reflux; iii) NEt3, CH2Cl2, TsCl, 08C–RT. DEAD=diethyl azodi-
carboxylate.
4
R1
R2
R3
R4
4a
4b
4c
4d
4e
4 f
4g
4h
4i
4j
4k
4l
4m
4n
4o
4p
4q
4r
n-C4H9
n-C4H9
CH3
n-C7H15
t-C4H9
t-C4H9
n-C4H9
n-C4H9
n-C4H9
allyl
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
CH3
H
CH3
CH3
CH3
H
Ts
Ts
Ts
Ts
Ts
Ts
Ts
Ns
Bz
Ts
Ts
Ts
Ts
Ts
Ts
Ts
Ts
Ts
Ts
Ts
Ts
Ms
Ac
Bn
Ns
Bz
n-C3H7
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
C2H5
n-C3H7
C2H5
n-C3H7
CH3
CH3
CH3
CH3
CH3
CH3
H
H
n-C4H9
n-C3H7
n-C7H15
CH3
i-C3H7
t-C4H9
n-C3H7
n-C3H7
i-C3H7
i-C3H7
Bn
n-C7H15
n-C7H15
n-C7H15
n-C7H15
n-C7H15
Figure 1. Molecular structure of 5w.
DMF, 708C), which afforded five-membered product 7aa in
78% yield together with less than 3% of other isomers.[8]
This result is quite different from what was observed for N-
(2-methyl-3,4-pentadienyl)toluenesulfonamide, where a mix-
ture of the trans-four-membered and six-membered product
with a ratio of 4:96 was formed,[4,5] indicating a dramatic
effect of the substituent at the 3-position of 3,4-dienyl
amides (Scheme 4).
4s
4t
H
H
H
H
H
H
H
4u
4v
4w
4x
4y
4z
Subsequently, the Pd0-catalyzed coupling cyclization of 3-
substituted-5-unsubstituted-3,4-allenyl amides with iodoben-
zene was performed under conditions A (Table 2). All reac-
tions afforded five-membered products in good selectivity
However, when 2-methyl-3-phenyl-3,4-pentadienol (3v)
or 4-methyl-5-butyl-5,6-heptadien-3-ol (3w) were used, the
cycloisomerization products, that is, 2,3-dihydropyrroles 5v
and trans-5w were formed directly (Scheme 3). The stereo-
chemistry of trans-5w was unambiguously determined by
the single crystal X-ray diffraction study (Figure 1).[14]
Palladium-catalyzed coupling–cyclization of3-substituted-5-
unsubstituted-3,4-allenyl amides with organic halides: Our
initial study began with the reaction of N-(2-methyl-3-(n-
butyl)-3,4-pentadienyl)tol
A
(4a)
with
1.5 equiv of iodobenzene 6a under conditions A for 7.5 h
(conditions A
248
=
5 mol% [Pd
G
Scheme 4.
www.chemeurj.org
Chem. Eur. J. 2007, 13, 247 – 254

Pd0-Catalyzed Cyclizations
FULL PAPER
Table 2. Pd-Catalyzed coupling cyclization reaction of allenyl amides 4 with iodobenzene 6a.[a]
The coupling–cyclization re-
actions of 3-substituted-3,4-al-
lenyl amides with different or-
ganic halides were performed
with the results summarized in
Table 3. Both electron-donat-
ing and electron-withdrawing
aryl iodides can react with 3-
substituted-3,4-allenyl amides
to afford the corresponding
2,3-dihydropyrrole products 7
(and 2-methylenetetrahydro-
pyrroles 8) in good yields. The
Entry
R1
R2
R3
t [h]
Yield isolated 7 [%]
Yield isolated 8 [%]
[b]
1
2
3
4
5
6
7
8
n-C4H9
n-C4H9
CH3
n-C7H15
t-C4H9
t-C4H9
n-C4H9
n-C4H9
CH3
H
CH3
CH3
CH3
H
Ts
Ts
Ts
Ts
Ts
Ts
Ts
Ns
4a
4b
4c
4d
4e
4 f
4g
4h
7.5
8
78 (7aa)
55 (7ba)
66 (7ca)
77 (7da)
76 (7ea)
65 (7 f a)
74 (7ga)
55 (7ha)
–
10 (8ba)
11 (8ca)
6 (8da)
0
0
0
0
12
42
16
48
24
5
n-C3H7
CH3
steric effect of the substituent
in aryl iodides has limited in-
fluence on the outcome of the
[a] The reaction was carried out with 0.30 mmol of allenyl amides 4, 0.45 mmol of iodobenzene 6a, 1.20 mmol
of K2CO3, and 5 mol% [Pd(PPh3)4] in DMF. [b] Other isomers was isolated in less than 3% yield.
AHCTREUNG
reaction: the reactions of 2-io-
and yields. It should be noted that the reactions of 4a–d af-
forded a mixture of 2-methylenetetrahydropyrrole products
8aa–8da and 2,3-dihydropyrrole products 7aa–7da (en-
tries 1–4, Table 2). With the increased steric hindrance of R1
or R2, the regioselectivity increased affording 2,3-dihydro-
pyrroles 7ea–7ga as the only products (entries 5–7, Table 2).
However, prolonged reaction time was necessary to achieve
a high conversion due to the increased steric hindrance. Fur-
thermore, it is interesting to note that when we used 2-
methyl-3-allyl-3,4-pentadienyl amide (4j), the coupling–cyc-
lization-Heckreaction product 9ja was formed instead of
the anticipated product 7ja in 14% yield (Scheme 5). How-
ever, some of the compounds 7 are unstable.
dotoluene, 4-iodotoluene and 1-iodonaphthalene with 4a
produced the corresponding 2,3-dihydropyrroles in high
yields (entries 4–6, Table 3). When the corresponding aryl
bromides were applied, the corresponding products 7 (and
8) were also isolated in good yields (entries 13–16, Table 3).
Heteroaromatic halides, such as 2-iodothiophene, 2-bromo-
pyridine, and alkenyl iodides, could also be used in this
transformation (entries 17–21, Table 3). However, 1-alkynyl
halides and aryl chlorides failed to react with the 3,4-allenyl
amides to afford the expected products.
Palladium-catalyzed coupling–cyclization of5-substituted-
3,4-allenyl amides with organic halides: When we turned
our attention to the 5-substituted-3-unsubstituted-3,4-allenyl
amides, the reaction of the N-(2-methyl-3,4-nonadienyl)-
toluenesulfonamide (4k) with iodobenzene 6a under condi-
tions A was firstly performed to afford a mixture of six-
membered cyclic product 10ka (60% de) and four-mem-
bered cyclic 11ka in a combined 87% yield with a ratio of
10ka/11ka being 96:4 (entry 1, Table 4). Further screening
was performed in order to increase the diastereoselectivity
for 2,5-disubstituted-1,2,5,6-tetrahydropyridine 10ka.[13] In
MeOH, 10ka was formed in a good yield with a low diaster-
eoselectivity (entry 2, Table 4). When we used CH2Cl2, ace-
tonitrile, 1,4-dioxane, or THF as the solvent, better diaster-
eoselectivity was observed (entries 3–6, Table 4). It is sur-
prising that only the cis-1,2,3,5-tetrahydropyridine 10ka was
formed in triethylamine, though the yield was very low
(entry 7, Table 4). The effect of the base on the reaction in
toluene at 508C was also studied (entries 9–14, Table 4). At
last, after many screenings it was observed that 10ka was
formed in 41% yield with 97% de together with trans-Z-
11ka in 12% yield with 100% de under conditions B
Scheme 5.
Further studies showed that the protecting group of the
amine functionality can also determine the reaction path-
way. The reaction of N-Ns (Ns = 4-nitrobenzenesulfonyl)
substituted b-allenyl amide 4h afforded five-membered
product 7ha in 55% yield as the only product (compare
entry 1 with 8, Table 2) while the reaction of N-Bz substitut-
ed 3,4-allenyl amide 4i (Bz = benzoyl) afforded trans-azeti-
dine 11ia as the only product albeit in a low yield [Eq. (1)].
(5 mol% [PdACHTRE(UNG PPh3)4], 4 equiv NaOH, toluene, 808C)
(entry 15, Table 4). The stereochemistry of the major isomer
of 10ka was unambiguously determined by the single crystal
X-ray diffraction study (Figure 2).[15] The relative configura-
tion of 11ka was determined by an NOE study (Figure 3).[16]
However, the yield of this reaction was low; therefore, we
tried the reaction in some mixed solvents with NaOH as the
Chem. Eur. J. 2007, 13, 247 – 254
ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
249

S. Ma et al.
Table 3. Pd-Catalyzed coupling cyclization reaction of allenyl amides 4 with organic halides.[a]
base to improve the yield (en-
tries 18–21, Table 4). The prod-
uct 10ka was isolated in 50%
yield with 95% de and 11ka in
3% yield with 89% de under
R1
R2
RX (6)
t [h]
Yield 7 [%]
79 (7ab)
73 (7ac)
82 (7ad)
84 (7ae)
Yield 8 [%]
conditions
(PPh3)4], 4 equiv NaOH, tol-
uene/DMF 20:1, 808C)
(entry 21, Table 4).
C (5 mol% [Pd-
Entry
AHCTREUNG
1
2
3
4
5
6
7
8
n-C4H9
n-C4H9
n-C4H9
n-C4H9
n-C4H9
n-C4H9
n-C4H9
n-C4H9
t-C4H9
CH3
CH3
CH3
CH3
CH3
CH3
H
H
H
H
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
4a
4a
4a
4a
4a
4a
4b
4b
4 f
4 f
4d
4d
4d
4d
4d
4d
4a
4a
p-MeOC6H4I (6b)
p-MeO2CC6H4I (6c)
p-BrC6H4I (6d)
o-MeC6H4I (6e)
p-MeC6H4I (6 f)
1-iodonaphthalene (6g)
p-MeOC6H4I (6b)
p-MeO2CC6H4I (6c)
p-MeOC6H4I (6b)
p-MeO2CC6H4I (6c)
p-NCC6H4I (6h)
p-CH3COC6H4I (6i)
PhBr (6j)
o-ClC6H4Br (6j)
5.5
24
10
10
8
0
0
0
0
0
0
Subsequently, we studied the
reaction of different 5-substi-
tuted 3,4-allenyl amides under
conditions B or C (Table 5).
The reaction afforded the re-
lated products in relatively low
yields and high de under condi-
tions B and higher yields and
relatively low de under condi-
tions C (Table 5). However, for
R1 = iPr or tBu, the reaction
is more complicated. Interest-
ingly for R3 = Bz again only
the four-membered compound
11za was formed [compare Eq.
(1) with entry 22 in Table 5].
The reaction of 6-phenyl-sub-
stituted amide 4u afforded the
carbopalladation–b-elimination
product 12 in 38% yield as the
major product probably due to
the presence of benzylic pro-
tons for the b-H elimination
(Scheme 6).
83 (7af)
80 (7ag)
12
5.5
10
60
96
60
52
16
58
36
30
36
12
68 (7bb/8bb:86:14)[b]
77 (7bc/8bc:86:15)[b]
77 (7 f b)
9
0
0
0
0
10
11
12
13
14
15
16
17
18
t-C4H9
45 (7 f c)
61 (7dh)
77 (7di)
64 (7da)
80 (7dj)
63 (7dk)
55 (7dl)
68 (7am)
68 (7an)
n-C7H15
n-C7H15
n-C7H15
n-C7H15
n-C7H15
n-C7H15
n-C4H9
n-C4H9
10 (8da)
0
0
0
0
0
p-MeOC6H4Br (6k)
p-NO2C6H4Br (6l)
2-iodothiophene (6m)
2-bromopyridine (6n)
[a] The reaction was carried out at 708C with 0.30 mmol of allenyl amides 4, 0.45 mmol of organic halide 6,
1.20 mmol of K2CO3, and 5 mol% [Pd
(300 MHz).
(PPh3)4] in DMF. [b] Ratios were determined by 1H NMR spectra
ACHTREUNG
Table 4. Pd-Catalyzed coupling cyclization reaction of N-(2-methyl-3,4-nonadienyl)toluenesulfonamide 4k
with iodobenzene 6a.[a]
Entry Base
T
[8C]
Solvent
t
Yield 10ka
de
10ka
Yield 11ka
Recovered 4k
[h] [%]
[%][b]
[%]
When N-(2-methyl-3-buty-
locta-3,4-dienyl)-p-toluenesul-
fonamide (13)[17] was used
under conditions B, the six-
membered cyclic product 14
was isolated in 21% yield
[Eq. (2)].
Next we studied the scope
for organic halides in this reac-
tions with 3,4-allenyl amide 4l.
Iodobenzene worked better
than bromobenzene (compare
entry 1 of Table 6 with en-
tries 3 and 4 of Table 5). Both
electron-donating and elec-
tron-withdrawing aryl iodides
could react with 4l to afford
the products in moderate
yields and good de (entries 2–
12, Table 6). Heteroaromatic
halides such as 2-iodothio-
phene (entries 13 and 14,
Table 6) or the alkenyl halides
such as (E)-1-hexenyl iodide
1
2
3
4
5
6
7
8
K2CO3 70
K2CO3 70
K2CO3 70
K2CO3 70
K2CO3 70
K2CO3 70
DMF
20 84
100 76
100 64
100 68
100 67
100 58
61
65
73
71
81
89
>99:1
90
91
>99:1
97
92
89
95
97
81
89
70
3
0
7
7
8
6
0
15
11
0
0
0
CH3OH
CH2Cl2
CH3CN
1,4-dioxane
THF
trace
0
0
0
91
0
0
81
0
Et3N
70
Et3N
100
5
K2CO3 70
K2CO3 50
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
DMF
toluene/DMF
1:1
toluene/DMF
5:1
toluene/DMF
10:1
toluene/DMF
20:1
100 57
100 68
9
10
11
12
13
14
15
16
17
18
Et3N
NaH
KOH
50
50
50
100
3
100 28
100 42
100 48
100 53
100 41
100 48
48 43
48 57
7
39
6
0
Cs2CO3 50
NaOH 50
NaOH 80
NaOH 30
NaOH 80
NaOH 80
15
23
0
0
0
6
12[c]
17
0
0
0
19
20
21
NaOH 80
NaOH 80
NaOH 80
48 51
48 59
48 50
79
87
95
0
trace
3
0
0
0
[a] The reaction was carried out with 0.30 mmol of N-(2-methyl-3,4-nonadienyl)toluenesulfonamide 4k,
0.45 mmol of iodobenzene 6a, 1.20 mmol of base, and 5 mol% [Pd(PPh3)4] in solution. [b] A mixture of iso-
mers, unless otherwise stated. [c] Only the trans-Z-isomer was formed.
AHCTREUNG
250
www.chemeurj.org
ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2007, 13, 247 – 254

Pd0-Catalyzed Cyclizations
FULL PAPER
Figure 3.
Scheme 6.
Figure 2. Molecular structure of 10ka.
also smoothly reacted with 4l (entries 15 and 16, Table 6).
The results of [PdACHTREUNG(PPh3)4]-catalyzed reaction of N-(2-ethyl-
3,4-octadienyl)toluenesulfonamide (4q) with 1,4-diiodoben-
zene 6r afforded double cyclization product 15 (Scheme 7).
The stereochemistry of the
major isomer of 15 was unam-
biguously determined by the
single crystal X-ray diffraction
study (Figure 4).[18]
Table 5. Pd-Catalyzed coupling cyclization reaction of 5-monosubstituted-3,4-allenyl amides 4 with iodoben-
zene 6a.[a]
Entry R1
R2
R3
Ts
Conditions[b] Yield 10 [%] de 10 [%] Yield 11 [%] de 11 [%]
Conclusion
1
n-C4H9
CH3
4k
4l
B
C
B
C
B
C
B
B
C
B
C
B
B
C
B
C
B
B
C
B
C
B
41 (10ka)
50 (10ka)
42 (10la)
61 (10la)
35 (10ma)
45 (10ma)
63 (10na)
36 (10qa)
56 (10qa)
37 (10ra)
58 (10ra)
7 (10sa)
97
95
96
86
95
88
86
90
12 (11ka)
3 (11ka)
4 (11la)
3 (11la)
9 (11ma)
3 (11ma)
trace
13 (11qa)
7 (11qa)
17 (11ra)
6 (11ra)
12 (11sa)
8 (11ta)
7 (11ta)
trace
trace
trace
trace
trace
4 (11ya)
5 (11ya)
30 (11za)
>99:1
>99:1
>99:1
62
In summary, we have studied
the Pd0-catalyzed coupling–
cyclization reaction of b-amino
allenes with organic halides.
The reaction of 3-substituted-
3,4-allenyl amides afforded
five-membered cyclic products
while 5-substituted-3,4-allenyl
toluenesulfonamides afforded
a mixture of four- and six-
2
3
n-C3H7
CH3
Ts
Ts
4
5
n-C7H15 CH3
4m
>99:1
[c]
6
–
7
CH3
CH3
C2H5
Ts
Ts
4n
4q
–
8
n-C3H7
>99:1
71
>99:1
84
>99:1
>99:1
>99:1
–
–
–
–
–
9
82
89
88
10
11
12
13
14
15
16
17
18
19
20
21
22
n-C3H7
n-C3H7 Ts
4r
i-C3H7
i-C3H7
C2H5
n-C3H7 Ts
Ts
4s
4t
>99:1
>99:1
>99:1
>99:1
>99:1
>99:1
93
>99:1
88
84
5
A
7 (10ta)
membered
products.
The
n-C7H15 CH3
Ms 4v
38 (10va)
39 (10va)
15 (10wa)
41 (10xa)
49 (10xa)
21 (10ya)
32 (10ya)
trace
nature of the N-protecting
group may also change the re-
action pathway. The reaction
may proceed via the carbopal-
ladation forming p-allylic pal-
ladium intermediate or the nu-
cleometallation–reductive
n-C7H15 CH3
n-C7H15 CH3
Ac 4w
Bn 4x
n-C7H15 CH3
n-C7H15 CH3
Ns 4y
Bz 4z
86
89
>99:1
–
[a] The reaction was carried out with 0.30 mmol of 3,4-allenyl amides 4, 0.45 mmol of iodobenzene 6a,
1.20 mmol of NaOH, and 5 mol% [Pd(PPh3)4] in solvent (2 mL). [b] Conditions B: 5 mol% [Pd(PPh3)4],
(PPh3)4], 4 equiv of NaOH, toluene/DMF 20:1,
elimination pathway.[1c] Further
studies in this area are being
conducted in our laboratory.
A
ACHTREUNG
4 equiv of NaOH, toluene, 808C. Conditions C: 5 mol% [Pd
808C. [c] A mixture of three isomers.
ACHTREUNG
Chem. Eur. J. 2007, 13, 247 – 254
ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
251

S. Ma et al.
Table 6. Pd-Catalyzed coupling cyclization reaction of N-(2-methyl-3,4-octadienyl)toluenesulfonamide 4l with
organic halides 6.[a]
3,4-Allenoates: Compounds 2a–v
were prepared from the oxy-Cope re-
arrangement reaction of the corre-
sponding propargylic alcohols 1a–v.[9]
Ethyl 2,3-dimethylpenta-3,4-dienoate
(2c): Typical procedure I: A mixture
of
2-butyn-1-ol
(1c)
(2.969 g,
42.4 mmol), triethyl orthopropionate
(30 mL, 26.4 g, 150 mmol), and a cata-
lytic amount of propanoic acid was
heated at 1408C for 3 h. After being
cooled to room temperature, flash
chromatography on silica gel (petro-
leum ether/Et2O 3:1) produced 2c as
Entry
RX
Conditions[b]
Yield 10 [%]
de 10 [%]
Yield 11 [%]
de 11 [%])
a
liquid (2.960 g, 64%). 1H NMR
1
2
3
4
5
6
7
8
6j
6b
B
B
C
B
C
B
B
C
B
C
B
C
B
C
B
C
12 (10la)
40 (10lb)
55 (10lb)
46 (10lf)
50 (10lf)
14 (10lq)
24 (10li)
60 (10li)
28 (10lh)
62 (10lh)
19 (10lg)
31 (10lg)
37 (10lm)
61 (10lm)
29 (10lp)
53 (10lp)
94
92
85
92
88
>99:1
85
73
88
77
76
61
89
68
95
90
2 (11la)
5 (11lb)
4 (11lb)
7 (11lf)
2 (11lf)
trace
trace
trace
trace
trace
trace
trace
5 (11lg)
6 (11lm)
trace
>99:1
94
64
89
72
–
–
–
–
–
–
–
(300 MHz, CDCl3): d = 4.70–4.60 (m,
2H), 4.12–4.02 (m, 2H), 2.91–2.82 (m,
1H), 1.65 (t, J=2.7 Hz, 3H), 1.26–
1.07 (m, 6H); 13C NMR (CDCl3,
75.4 MHz): d=206.3, 174.0, 98.4, 75.8,
60.3, 42.9, 16.9, 15.4, 14.0; IR (neat):
n˜ = 1960, 1735, 1453, 1181 cmꢀ1; MS:
m/z (%): 155 (1.20) [M ++H], 139
(44.15) [M +ꢀCH3], 111 (100); EI-
HRMS: m/z: calcd for C9H14O2:
154.09938; found 154.09978.
6 f
6q
6i
9
6h
6g
6m
6p
10
11
12
13
14
15
16
>99:1
>99:1
–
–
3,4-Allenols: Compounds 3a–v were
prepared via reduction of 3,4-allen-
ates 2a–v with LiAlH4.
trace
2-Methyl-3-(n-heptyl)penta-3,4-dienol
(3d): Typical procedure II: A solution
of 2-methyl-3-(n-heptyl)penta-3,4-di-
enoate (2d) (3.820 g, 16.0 mmol) in
THF (30 mL) under cooling (ice
[a] The reaction was carried out with 0.30 mmol of N-(2-methyl-3,4-octadienyl)toluenesulfonamide 4l,
0.45 mmol of organic halide 6, 1.20 mmol of NaOH, and 5 mol% [Pd(PPh3)4] in solvent (2.0 mL). [b] Condi-
tions B: 5 mol% [Pd(PPh3)4], 4 equiv of NaOH, toluene, 808C. Conditions C: 5 mol% [Pd(PPh3)4], 4 equiv of
AHCTREUNG
G
ACHTREUNG
NaOH, toluene/DMF 20:1, 808C.
bath) to
a suspension of LiAlH4
(0.734 g, 19.3 mmol) in THF (30 mL)
was added dropwise. After addition,
the mixture was allowed to warm up
to room temperature. After the reac-
tion was complete as monitored by
TLC (petroleum ether/Et2O 10:1), it
was quenched with water, filtrated,
washed with Et2O for three times.
Then the combined organic phase
was washed with brine for three
times and dried over anhydrous
sodium sulfate. Evaporation and flash
chromatography on silica gel (petro-
leum ether/Et2O 5:1!1:1) produced
3d as
a
liquid (1.909 g, 61%).
1H NMR (300 MHz, CDCl3):
d
=
4.78–4.72 (m, 2H), 3.61–3.43 (m,
2H), 2.20–2.10 (m, 1H), 1.98–1.86
(m, 2H), 1.81 (brs, 1H), 1.57–1.18
(m, 10H), 1.03 (d, J=6.9 Hz, 3H),
0.87 (d, J=6.9 Hz, 3H); 13C NMR
(CD3Cl, 75.4 MHz): d=204.9, 105.5,
Scheme 7.
Experimental Section
77.1, 66.2, 38.8, 31.8, 30.5, 29.3, 29.1, 27.6, 22.6, 16.1, 14.0; IR (neat): n˜ =
3346, 1953, 1458, 1378, 1032 cmꢀ1; MS: m/z (%): 196 (3.56) [M +], 83
(100); elemental analysis calcd (%) for C13H24O: C 79.53, H 12.32;
found: C 79.32, H 12.06; HRMS (EI): m/z: calcd for C13H24O: 196.18272;
found 196.18175.
General methods: All the reactions were carried out under a nitrogen at-
mosphere with dry solvent under anhydrous conditions, unless otherwise
indicated. 1H and 13C NMR spectra were recorded on a Bruker AM-300
spectrometer with TMS as the internal standard. IR spectra were record-
ed on a Bruker Perkin–Elmer 983 spectrometer. MS spectra were record-
ed on a HP 5989A spectrometer. HRMS spectra were recorded on Finni-
gan MAT 8430 spectrometer. Flash-column chromatography was carried
out on silica gel H (10–40 m). Petroleum ether b.p. range 60–908C. Yields
refer to spectroscopically pure compounds, unless otherwise indicated.
5-Butyl-4-methylocta-5,6-dien-3-ol
(3w):
3-Butyl-2-methylpenta-3,4-
dienol (3a) (1.766 g, 11.5 mmol) in CH2Cl2 (10 mL) was added to a solu-
tion of the Dess–Martin reagent (7.302 g, 17.2 mmol) in CH2Cl2 (25 mL).
When the reaction was completed as monitored by TLC, the reaction
was quenched with saturated aqueous solution of Na2S2O3. Then the solu-
tion was washed subsequently with satd aq solution of Na2S2O3 and satd
252
www.chemeurj.org
ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2007, 13, 247 – 254

Pd0-Catalyzed Cyclizations
FULL PAPER
solvent, the mixture was submitted to flash chromatography on silica gel
to produce 4d as a liquid (1.801 g, 75%) (overall yield for three steps:
1
60%). H NMR (300 MHz, CDCl3): d = 7.72 (d, J=8.1 Hz, 2H), 7.28 (d,
J=8.1 Hz, 2H), 4.80–4.09 (m, 3H), 2.99–2.72 (m, 2H), 2.40 (s, 3H), 2.18–
2.00 (m, 1H), 1.84–1.66 (m, 2H), 1.35–1.13 (m, 10H), 0.95 (d, J=6.6 Hz,
3H), 0.86 (t, J=6.6 Hz, 3H); 13C NMR (CDCl3, 75.4 MHz): d=204.5,
143.2, 136.9, 129.6, 127.0, 105.5, 77.7, 47.0, 36.0, 31.7, 30.1, 29.2, 29.1, 27.4,
22.6, 21.4, 17.3, 14.0; IR (neat): n˜ = 3281, 1953, 1599, 1162 cmꢀ1; MS:
m/z (%): 349 (0.75) [M +], 194 (100); elemental analysis calcd for
C20H31NO2S (%): C 68.72, H 8.94, N 4.01; found: C 68.89, H 8.87, N 3.85.
Pd0-catalyzed coupling–cyclization reaction of3,4-allenyl amides with or-
ganic halides: Procedure IV:
(0.3 mmol), organic halide 6 (0.45 mmol), K2CO3 (1.2 mmol), and [Pd-
(PPh3)4] (5 mol%) was stirred at 708C in DMF (2 mL). When the reac-
A mixture of 3,4-allenyl amide 4
AHCTREUNG
tion was completed as monitored by TLC (petroleum ether/Et2O), the re-
action mixture was diluted with Et2O, washed with brine (3”10 mL),
dried over Na2SO4, evaporated, and purified by flash chromatography on
silica gel (petroleum ether/Et2O 5:1) to afford the pure product.
5-Benzyl-3,4-dimethyl-1-(p-toluenesulfonyl)-2,3-dihydro-1H-pyrrole
(7ca): The reaction of 4c (0.086 g, 0.32 mmol) with iodobenzene 6a
(51 mL, 0.093 g, 0.46 mmol) afforded 7ca (0.073 g, 66%), trans-8ca
(0.009 g, 8.5%) and cis-8ca (0.003 g, 2.4%). 7ca: solid; m.p. 100–1018C
(n-hexane); 1H NMR (300 MHz, CDCl3): d = 7.47 (d, J=8.4 Hz, 2H),
7.29–7.07 (m, 7H), 3.83 (s, 2H), 3.90–3.77 (m, 1H), 3.11 (dd, J=6.9,
11.7 Hz, 1H), 2.33 (s, 3H), 2.31–2.24 (m, 1H), 1.56 (s, 3H), 0.63 (d, J=
6.9 Hz, 3H); 13C NMR (CDCl3, 75.4 MHz): d=143.2, 138.8, 134.6, 134.5,
129.3, 128.5, 128.3, 127.6, 127.3, 126.1, 56.4, 38.5, 31.9, 21.5, 18.1, 11.5; IR
(neat): n˜ = 1598, 1453, 1342, 1167 cmꢀ1; MS: m/z (%): 341 (19.33) [M +],
91 (100); elemental analysis calcd for C20H23SNO2 (%): C 70.35, H 6.79,
N 4.10; found: C 70.20, H 6.79, N 3.78.
Figure 4. Molecular structure of the major stereoisomer of 15.
aq solution of NaHCO3. The combined organic extracts were dried over
anhydrous magnesium sulfate. After filtration, the Grignard reagent,
which was prepared via the reaction of EtBr (4.4 mL, 6.16 g, 56.5 mmol)
with Mg turnings (1.38 g, 57.5 mmol) in THF (60 mL), was added drop-
wise to the solution at room temperature. The resulting solution was stir-
red under reflux. When the reaction was complete as monitored by TLC,
it was quenched with water. The solution was brought to pH 3 by the ad-
dition of aqueous 1n HCl and then extracted with Et2O (3”50 mL).
After evaporation, the filtrate was purified by flash chromatography on
silica gel (petroleum ether/Et2O 10:1!3:1) to afford 3w as a liquid
(1.252 g, 60%). 1H NMR (300 MHz, CDCl3): d = 4.82–4.64 (m, 2H),
3.59–3.34 (m, 1H), 2.04–1.82 (m, 3H), 1.75 (brs, 1H), 1.52–1.26 (m, 6H),
0.99 (d, J=6.9 Hz, 3H), 0.94 (t, J=7.2 Hz, 3H), 0.88 (t, J=7.2 Hz, 3H);
13C NMR (CDCl3, 75.4 MHz): d = 205.6, 106.7, 77.2, 74.3, 40.9, 30.8,
3,4-Dimethyl-2-methylene-3-phenyl-1-(p-toluenesulfonyl)pyrrolidine
(8ca): trans-8ca: liquid; 1H NMR (300 MHz, CDCl3): d = 7.69 (d, J=
8.7 Hz, 2H), 7.21 (d, J=8.7 Hz, 2H), 7.15–6.94 (m, 5H), 5.22 (d, J=
1.5 Hz, 1H), 3.99 (d, J=1.5 Hz, 1H), 3.62 (dd, J=6.9, 9.9 Hz, 1H), 3.18
(dd, J=6.9, 9.3 Hz, 1H), 2.39 (s, 3H), 2.39–2.30 (m, 1H), 0.91 (s, 3H),
0.76 (d, J=6.9 Hz, 3H); 13C NMR (CDCl3, 75.4 MHz): d=152.3, 144.7,
144.0, 129.7, 129.4, 128.0, 127.5, 126.9, 126.4, 92.0, 54.5, 53.7, 41.1, 21.6,
20.0, 12.3; IR (neat): n˜ = 1655, 1599, 1459, 1351, 1165 cmꢀ1; MS: m/z
(%): 341 (2.01) [M +], 131 (100); EI-HRMS: m/z: calcd for C20H23SNO2:
341.14495; found 341.14258.
29.7, 27.2, 22.4, 13.9, 12.6, 10.6; IR (neat): n˜
= 3390, 1956, 1463,
cis-8ca: liquid; 1H NMR (300 MHz, CDCl3): d
= 7.88 (d, J=8.4 Hz,
1150 cmꢀ1; MS: m/z (%): 182 (1.20) [M +], 167 (39.99) [M +ꢀCH3], 139
(35.59) [M +ꢀC3H7], 67 (100); EI-HRMS: m/z: calcd for C12H22O:
182.16706; found 182.16447.
2H), 7.40 (d, J=8.4 Hz, 2H), 7.11–7.05 (m, 1H), 6.99–6.91 (m, 2H),
6.64–6.57 (m, 2H), 5.29 (d, J=1.8 Hz, 1H), 4.27 (d, J=1.8 Hz, 1H), 3.89
(dd, J=6.9, 9.6 Hz, 1H), 2.96 (dd, J=9.6, 11.1 Hz, 1H), 2.51 (s, 3H),
2.12–1.99 (m, 1H), 1.47 (s, 3H), 0.60 (d, J=6.9 Hz, 3H).
Pd0-catalyzed coupling–cyclization reaction of3,4-allenyl amides with or-
ganic halides under conditions B: Procedure V: A mixture of 3,4-allenyl
3,4-Allenyl amides: Compounds 4a–z, 5v, 5w, and 13 were prepared
from the Mitsunobu amination of the related 3,4-allenols 3a–v.
N-(2-Methyl-3-(n-heptyl)penta-3,4-dienyl)-p-toluenesulfonamide
(4d):
Procedure III: Diethyl azodicarboxylate (6.6 mL, 40% in toluene,
15.2 mmol) with cooling (ice bath) was added dropwise to a solution of
2-methylocta-2,3-dienol (3d) (1.690 g, 8.6 mmol), triphenylphosphine
(4.060 g, 15.5 mmol), and phthalimide (1.313 g, 8.9 mmol) in anhydrous
THF (40 mL). The resulting yellow solution was allowed to warm up to
room temperature overnight. The solvent was removed in vacuo followed
by the addition of ether. The resulting solid was filtered off. After evapo-
ration, the filtrate was purified by flash chromatography on silica gel to
afford the corresponding phthalimide (2.254 g).
amide
(1.2 mmol), and [PdAHCTREUNG
4
(0.3 mmol), aryl or vinyl halide
6 (0.45 mmol), NaOH
(PPh3)4] (5 mol%) was stirred at 808C in toluene
(2 mL). When the reaction was complete as monitored by TLC (petro-
leum ether/Et2O 5:1), the reaction mixture was diluted with Et2O,
washed with brine (3”10 mL), dried over Na2SO4, evaporated, and puri-
fied by flash chromatography on silica gel (petroleum ether/Et2O 5:1) to
afford the pure products.
cis-2-(n-Butyl)-5-methyl-3-phenyl-1-(p-toluenesulfonyl)-1,2,5,6-tetrahy-
dropyridine (10ka): The reaction of 4k (0.060 g, 0.20 mmol), iodobenzene
6a (34 mL, 0.062 g, 0.30 mmol), NaOH (0.033 g, 0.83 mmol) and [Pd-
A solution of the above phthalimide (2.250 g) and hydrazine hydrate
(0.80 mL, 85% purity, 13.9 mmol) in dry MeOH (30 mL) was heated
under reflux for 2 h resulting in the formation of a white precipitate.
Then concentrated HCl (2.5 mL) was added with cooling (ice bath) and
the precipitate was removed by filtration. The filtrate was brought to
pH 13 by the addition of 1n NaOH and extracted with Et2O (3”50 mL).
The combined extracts were dried over anhydrous magnesium sulfate.
After evaporation, the crude product was used without further purifica-
tion. To a solution of the above crude product and triethylamine (1.2 mL,
8.4 mmol) in dichloromethane (20 mL) was added tosyl chloride (1.541 g,
8.1 mmol) in one portion with cooling (ice bath). The mixture was al-
lowed to warm up to room temperature overnight. After removal of the
AHCTRE(UNG PPh3)4] (0.013 g, 5 mol%) afforded 10ka (0.031 g, 41%) and 11ka
1
(0.009 g, 12%). 10ka: solid; m.p. 124–1268C (Et2O); H NMR (300 MHz,
CDCl3): d = 7.68 (d, J=8.4 Hz, 2H), 7.38–7.16 (m, 5H), 7.14 (d, J=
8.1 Hz, 2H), 5.41 (s, 1H), 4.77 (t, J=2.1 Hz, 1H), 3.86 (dd, J=6.6,
14.7 Hz, 1H), 2.72 (dd, J=11.4, 14.7 Hz, 1H), 2.29 (s, 3H), 2.02–1.94 (m,
1H), 1.45–1.04 (m, 6H), 0.85 (d, J=6.9 Hz, 3H), 0.76 (t, J=7.2 Hz, 3H);
13C NMR (CDCl3, 75.4 MHz): d=143.0, 139.7, 139.2, 138.4, 129.4, 129.2,
128.6, 127.5, 126.9, 126.1, 55.1, 44.5, 32.9, 28.6, 27.8, 22.3, 21.5, 18.3, 14.0;
IR (neat): n˜ = 1600, 1494, 1332, 1165, 1152 cmꢀ1; MS: m/z (%): 326
(100) [M +ꢀC4H9]; elemental analysis calcd (%) for C23H29NO2S: C
72.02, H 7.62, N 3.65; found: C 72.12, H 7.74, N 3.48.
Chem. Eur. J. 2007, 13, 247 – 254
ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
253

S. Ma et al.
trans-3-Methyl-2-(1’-phenylhex-1’(Z)-enyl)-1-(p-toluenesulfonyl)azetidine
(11ka): liquid; H NMR (300 MHz, CDCl3): d = 7.75 (d, J=8.4 Hz, 2H),
[5] a) H. Ohno, M. Anzai, A. Toda, S. Ohishi, N. Fujii, T. Tanaka, Y.
Takemoto, T. Ibuka, J. Org. Chem. 2001, 66, 4904–4914; b) M.
Anzai, A. Toda, H. Ohno, Y. Takemoto, N. Fuji, T. Ibuka, Tetrahe-
dron Lett. 1999, 40, 7393–7397.
[6] S.-K. Kang, T.-G. Baik, A. N. Kulak, Synlett 1999, 324–326.
[7] a) I. Shimizu, J. Tsuji, Chem. Lett. 1984, 233–236; b) N. Vicart, B.
Cazes, J. Gore, Tetrahedron Lett. 1995, 36, 5015–5018.
1
7.46–7.10 (m, 7H), 5.78 (t, J=7.5 Hz, 1H), 3.98 (d, J=7.2 Hz, 1H), 3.61
(t, J=8.1 Hz, 1H), 3.13 (t, J=7.8 Hz, 1H), 2.46 (s, 3H), 2.30–2.22 (m,
1H), 1.89–1.80 (m, 2H), 1.31–1.17 (m, 4H), 0.81 (t, J=7.2 Hz, 3H), 0.72
(d, J=6.6 Hz, 3H); 13C NMR (CDCl3, 75.4 MHz): d=143.8, 138.5, 137.6,
132.5, 131.9, 129.6, 128.4, 128.0, 126.9, 75.7, 54.3, 31.7, 31.1, 29.7, 28.3,
22.2, 21.6, 17.6, 14.0; IR (neat): n˜ = 1347, 1162, 1090 cmꢀ1; MS: m/z (%):
384 (3.51) [M ++H], 326 (38.62) [M +ꢀC4H9], 91 (100); elemental analy-
sis calcd (%) for C23H29NO2S: C 72.02, H 7.62, N 3.65; found: C 71.63, H
7.63, N 3.52.
[8] S. Ma, W. Gao, Org. Lett. 2002, 4, 2989–2992.
[9] a) M. W. Hollady, J. T. Wasicak, N. H. Lin, Y. He, K. B. Ryther,
A. W. Bannon, M. J. Buckley, D. J. B. Kim, M. W. Decker, D. J. An-
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Kaplan, C. A. Briggs, M. Williams, S. P. Arneric, J. Med. Chem.
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Acknowledgements
Financial supports from National Natural Science Foundation of China
(20121202, and 20332060) and Shanghai Municipal Committee of Sci-
ence and Technology are greatly appreciated. We thankMr. Gu Zhenhua
and Mr. Zhao Jinbo for repeating the results of entry 4, Table 1 and
Equation (2).
[10] a) C. Shu, A. Alcudia, J. Yin, L. S. Liebeskind, J. Am. Chem. Soc.
2001, 123, 12477–12487.
[11] W. R.; Roush, J. A. Straud, R. T. Brown, J. Org. Chem. 1987, 52,
5127–5136.
[12] G. Lai, W. K. Anderson, Synth. Commun. 1995, 25, 4087–4091.
[13] S. D. Larsen, P. A. Grieco, J. Am. Chem. Soc. 1985, 107, 1768–1769.
[14] Crystal data for trans-5w: C19H19NO2S, MW =335.49, monoclinic,
space group P2(1)/c, MoKa, final R indices [I>2s(I)], R1=0.0681,
wR2=0.1573, a=14.976(10), b=11.866(8), c=10.692(7) Š, a=90,
b=93.804(12), g=908, V=1896(2) Š3, T=293(2) K, Z=4, reflec-
tions collected/unique: 9398/3514 (Rint =0.1893), no observation [I>
2s(I)] 3514, parameters 221. CCDC-602381 contains the supplemen-
tary crystallographic data for this paper. These data can be obtained
free of charge from The Cambridge Crystallographic Data Centre
via www.ccdc.cam.ac.uk/data_request/cif.
[1] For reviews, see: a) The Chemistry ofAllenes (Ed.: S. R. Landor),
Vol. 1, Academic, London, 1982; b) Modern Allene Chemistry (Eds.:
N. Krause, A. S. K. Hashmi), Vol. 1, 2, Wiley-VCH, Weinheim, 2004;
c) S. Ma, Palladium-Catalyzed Two- or Three-Component Cycliza-
tion ofFunctionalized Allenes in Palladium in Organic Synthesis
(Ed.: J. Tsuji), pp. 183–210, Spring, Berlin, Heidelberg, 2005; d) R.
Zimmer, C. U. Dinesh, E. Nandanan, F. A. Khan, Chem. Rev. 2000,
100, 3067–3125; e) S. Ma, Chem. Rev. 2005, 105, 2829–2872; f) S.
Ma, Acc. Chem. Res. 2003, 36, 701–712; g) L. K. Sydnes, Chem. Rev.
2003, 103, 1133–1150; h) D. Lentz, J. Fluorine Chem. 2004, 125,
853–861; i) N. Krause, A. Hoffmann-Rçder, Tetrahedron 2004, 60,
11671–11694.
[15] Crystal data for 10ka: C23H29NO2S, MW =383.53, triclinic, space
¯
group P1, MoKa, final R indices [I>2s(I)], R1=0.0509, wR2=
0.0900, a=9.9649(7), b=14.2504(10), c=15.9793(11) Š, a=
79.8620(10), b=83.890(2), g=72.9800(10)8, V=2132.2(3) Š3, T=
[2] For some of the most recent publications, see: a) H. Ohno, H. Ha-
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293(2) K, Z=4, reflections collected/unique: 13129/9453 (Rint
=
0.0390), no observation [I>2s(I)] 3877, parameters 585. CCDC-
602380 contains the supplementary crystallographic data for this
paper. These data can be obtained free of charge from The Cam-
bridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_
request/cif.
[16] a) D. Enders, J. Gries, Z. Kim, Eur. J. Org. Chem. 2004, 4471–4482;
b) D. Enders, J. Gries, Synthesis 2005, 3508–3516.
[17] N-(2-Methyl-3-butylocta-3,4-dienyl)-p-toluenesulfonamide (13) was
synthesized according to Procedure I, II, and III.
[18] Crystal data for 15: C40H52N2O4S2, Ms =688.96, triclinic, space group
¯
P1, MoKa, final R indices [I>2s(I)], R1=0.0558, wR2=0.0751, a=
10.3409(16), b=11.5838(18), c=16.899(3) Š, a=81.636(3), b=
89.226(3), g=81.647(3)8, V=1981.4(5) Š3, T=293(2) K, Z=2, re-
flections collected/unique: 11715/8394 (Rint =0.0912), no observation
[I>2s(I)] 8394, parameters 455. CCDC-600503 contains the supple-
mentary crystallographic data for this paper. These data can be ob-
tained free of charge from The Cambridge Crystallographic Data
Centre via www.ccdc.cam.ac.uk/data_request/cif.
[4] F. P. J. T. Rutjes, K. C. M. F. Tjen, L. B. Wolf, W. F. J. Karstens, H. E.
Schoemaker, H. Hiemstra, Org. Lett. 1999, 1, 717–720.
Received: March 29, 2006
Published online: September 27, 2006
254
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