Synthesis of N-protected allylic amines from allyl ethers

Article abstract of DOI:10.1016/S0040-4020(01)00822-5

A synthetic method for N-protected allylic amines from allyl ethers using chlorosulfonyl isocyanate (CSI) is presented. The reaction of 4-phenylbut-2-enyl methyl ether (1i) with CSI afforded methyl N-(1-benzylallyl)carbamate (2i) and methyl N-(4-phenylbut

Full text of DOI:10.1016/S0040-4020(01)00822-5

TETRAHEDRON
Pergamon
Tetrahedron 57 +2001) 8257±8266
Synthesis of N-protected allylic amines from allyl ethers
Ji Duck Kim, Min Hee Lee, Gyoonhee Han, Hyunju Park, Ok Pyo Zee and Young Hoon Jungp
College of Pharmacy, Sungkyunkwan University, Suwon 440-746, South Korea
Received 13 June 2001; accepted 2 August 2001
AbstractÐA synthetic method for N-protected allylic amines from allyl ethers using chlorosulfonyl isocyanate +CSI) is presented. The
reaction of 4-phenylbut-2-enyl methyl ether +1i) with CSI afforded methyl N-+1-benzylallyl)carbamate +2i) and methyl N-+4-phenylbut-2-
enyl)carbamate +3i) in a 1:1.1 ratio. On the other hand, 1-benzylallyl methyl ether +1k) afforded the same products in a 4.6:1 ratio. The
reactions of 1,4-diphenylbut-2-enyl methyl ether +1p) and +1-benzylcinnamyl) methyl ether +1q) with CSI gave only one product, methyl
N-+1-benzylcinnamyl)carbamate +2p), due to the steric hindrance of the phenyl ring and the formation of a stable conjugated product. We
also examined the reactions of diene ethers +4) with CSI. q 2001 Elsevier Science Ltd. All rights reserved.
1. Introduction
According to their structure, allylic amines are classi®ed
into internal and terminal types. The internal allylic amines
are of practical value, because they can be transformed into
a range of products, such as a- and b-amino acids, by func-
tionalization, reduction, or oxidation of the double bond.13
Considerable attention has been focused on the develop-
ment of methods for the preparation of internal allylic
amines,14 which allow the facile incorporation of functional
groups and structural variability.
The synthesis of allylic amines has been an area of intense
research in synthetic and industrial ®elds, because of their
important roles in organic synthesis as fundamental building
blocks and their occurrence in a number of natural products.
General methods for the synthesis of these compounds can
be divided into two large categories; nucleophilic allylic
substitution and direct allylic amination.1 Of these two
methods, the former has been used widely and ef®ciently
so far, including metal-catalyzed nucleophilic substitutions.
Examples include the Mitsunobu reaction of allyl alcohols,2
the thermal [3,3]-sigmatropic rearrangement of allylic
trichloroacetimidates,3 the Gabriel amination of allyl
halides,4 and palladium-,5 copper-,6 iron-,7 rhodium-8 cata-
lyzed allylic aminations. The direct allylic amination
methods involve the nitrene addition9 and the ene reaction10
of diimido and aza compounds. Besides the reactions
mentioned above, indirect approaches have been developed,
such as the rearrangement of aziridines11 and the reduction
of a,b-unsaturated imines and oximes.12
Recently we reported a novel synthetic method for N-allyl-
carbamates from cinnamyl alkyl ethers, using chlorosulfo-
nyl isocyanate +CSI).15 To date, CSI has been used in the
[212] cycloaddition reactions of various substituted
alkenes, especially enol ethers, to synthesize the b-lactam
moiety of carbapenem antibiotics and b-amino acids.16
Recently, chiral enol ethers have been used as the precursors
of chiral b-lactam compounds and chiral b-amino acids.17
As part of a program aimed at producing various amino
acids to be used as versatile building blocks, benzyl cinna-
myl ether was reacted with CSI to obtain a b-lactam with a
Scheme 1.
Keywords: chlorosulfonyl isocyanate; allylic amine; N-allylcarbamate; allyl ether.
Corresponding author. Fax: 182-31-292-8800; e-mail: yhjung@skku.ac.kr
p
0040±4020/01/$ - see front matter q 2001 Elsevier Science Ltd. All rights reserved.
PII: S0040-4020+01)00822-5

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J. D. Kim et al. / Tetrahedron 57 '2001) 8257±8266
Scheme 2.
benzyloxy methyl moiety, which can be readily converted to
the acid moiety.
which the reactions of unsaturated oxiranes or acetal
moieties in sugars with CSI were studied.18 Similar results
of the conversion of tertiary or allyl alcohols to the corre-
sponding amines using CSI were also reported.19
However, instead of obtaining the expected b-lactam
products arising from the formal [212] annulation, the
corresponding N-allylcarbamates were obtained as the sole
products +Scheme 1). Early examples of N-allylcarbamate
formation using CSI were reported by several groups, in
In connection with these studies, we now report the results
of the regioselective N-protected allylic amination of
various allyl ethers. Especially, we tried to increase the
Table 1. Conversions of allyl ethers to the corresponding N-protected allylic amines with CSI
Allyl ethers Allylic amines
Yield +%)a
ratio
All reactions were carried out at 208C.
a
Isolated yield of pure material.
b Isomer ratio determined from the H NMR spectrum of the mixture after column chromatography.
1

J. D. Kim et al. / Tetrahedron 57 '2001) 8257±8266
8259
Table 2. Conversions of allyl ethers to the corresponding N-protected allylic amines with CSI
Allyl ethers
Allylic amines
Yield +%)a
ratio
All reactions were carried out at 208C, except for entries 12±16 +2788C).
Isolated yield of pure material.
a
b
Isomer ratio determined from the 1H NMR spectrum of the mixture after column chromatography.
formation of internal allylic amines in the reaction of
various allyl ethers with CSI. We also report the results of
the CSI reaction with diene ethers.
terminal allylic amine as major product +1:2.7 ratio), and
1-phenylallyl methyl ether +1b)22 yielded a similar result to
1a +1:2.6 ratio). In the cases of cinnamyl benzyl ether +1c)23
and 1-phenylallyl benzyl ether +1d), the results were similar
to that obtained in the methyl case, except for the decrease
of the internal allylic amine due to the steric hindrance of
the benzyl group +entries 3 and 4). However, entries 5±8
reveal that the substitution mainly occurred where the
alkoxy moiety was attached, to afford the corresponding
allylic amines. The results are summarized in Table 1.
2. Results and discussion
Our initial studies examined the reaction of regioisomeric
allyl ethers +1) with CSI to afford an internal allylic amine
+2) and a terminal one +3) +Scheme 2).20
In the cases of entries 1±4, the identical, stable allylic cation
may be formed from 1a±1d to afford the similar ratio of
Our previous report +entries 1 and 2) showed that the CSI
reaction of cinnamyl methyl ether +1a)21 produced the

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J. D. Kim et al. / Tetrahedron 57 '2001) 8257±8266
Figure 1.
allylic amines such as entries 1 and 2and entries 3 and 4, in
which the ratio was controlled by the steric effect of the
phenyl ring to give the terminal one as the main product.
However, in the cases of entries 5 and 6 and entries 7 and 8,
each isomer of the allyl ethers gave a different ratio of
allylic amines. These results were rather intriguing, since
it implied that these reactions were not proceeding through
the same allylic carbocation intermediate.
mixture of regioisomers and a 11.6:1 mixture of geometric
isomers in favor of the cis-terminal allylic amine +3j) +entry
10). However, the isomeric secondary allyl ether +1k),22
under the same reaction conditions, gave an inversed
product ratio +4.6:1) in favor of the internal allylic amine
+2i), similar to the case of entry 6 +entry 11). With the benzyl
ethers, the results were quite similar to that obtained in the
methyl case, except for the increase in the ratio +entries 12
and 13).
Further studies examined the reaction of 4-phenylbut-2-enyl
methyl ether +1i) and its derivatives with CSI. The results
are summarized in Table 2.
One plausible mechanism for these regioselective allylic
aminations is shown in Fig. 1. As soon as the unstable
primary allylic carbocation is formed from the terminal
ether 1i, it is rapidly converted to the stable allylic carbo-
cation hybrid, and then slightly more 3i than 2i is formed,
according to the steric hindrance. In the case of the internal
ether 1k, on the other hand, the stable secondary allylic
carbocation is formed and is rapidly attacked by the nucleo-
phile, instead of being converted to the hybrid to form the
more substituted allylic amine. Namely, the nucleophilic
Treatment of 4-phenylbut-2-enyl methyl ether +1i) with CSI
furnished methyl N-+1-benzylallyl)carbamate +2i) and
methyl N-+4-phenylbut-2-enyl)carbamate +3i) as a 1:1.1
mixture of regioisomers, in which the formation of the
internal isomer was slightly increased as compared to the
case of 1a, due to the reduced steric hindrance +entry 9).
Also, the cis-primary allyl ether +1j) afforded a 1:1.4
Table 3. Conversions of diene ethers to the corresponding N-protected allylic amines with CSI
Diene ethers
Allylic amines
Yield +%)a
ratio
All reactions were carried out at 2788C.
Isolated yield of pure material.
a

J. D. Kim et al. / Tetrahedron 57 '2001) 8257±8266
8261
attack rapidly occurs where the alkoxy moiety was attached,
before the formation of the allylic carbocation hybrid.
+7.26 ppm) and CDCl3 dC +77.0 ppm) as internal standards.
Resonance patterns are reported with the notations s
+singlet), d +doublet), t +triplet), q +quartet), and m +multi-
plet). In addition, the notation br is used to indicate a broad
signal. Coupling constants +J) are reported in Hertz +Hz). IR
spectra were recorded on a Nicolet 205 Infrared spectro-
photometer and are reported as cm21. Thin layer chroma-
tography was carried out using plates coated with Kieselgel
60F254 +Merck). For ¯ash column chromatography, E.
Merck Kieselgel 60 +230±400 mesh) was used. Elemental
analyses were performed with an the EA 1110 analyzer, and
high-resolution mass spectra +HRMS) were recorded on a
JEOL, JMS-AX505WA spectrometer using the chemical
ionization +CI) method.
In order to improve the isomer ratio of the internal allylic
amine, we introduced the phenyl ring at the allylic position
in the same direction as that of the alkoxy moiety. The
reactions of 1,4-diphenylbut-2-enyl methyl ether +1p)24
and 1-benzylcinnamyl methyl ether +1q) with CSI gave
only one product, methyl N-+1-benzylcinnamyl)carbamate
+2p), due to the steric hindrance of the phenyl ring and the
formation of a stable conjugated product +entries 16 and 17).
In the benzyl ether case +1r), the results were also quite
similar to that obtained in the methyl ether case +entry
18). No product derived from an attack at the benzylic
position was observed.
4.2. General procedure for preparation of methyl ether
We also examined the reaction of diene ethers +4) with CSI.
The results are summarized in Table 3. The treatment of the
terminal diene ether 4a and the internal diene ether 4b with
CSI afforded only the terminal allylic amine 5a, due to the
steric hindrance of the phenyl ring and the stability of the
product +conjugation of diene), as in entries 16 and 18
+entries 19 and 20). However, the reaction of 4c with CSI
afforded 5c and 6c as a 1:2.4 mixture of regioisomers +entry
21). In the cases of entries 20 and 21, no product derived
from an attack on the position where the alkoxy moiety was
attached was observed due to avoidance of the destruction
of the conjugated diene.
To a solution of alcohol +5 mmol) in THF +20 ml) was added
NaH +7.5 mmol, 60% in mineral oil) and methyl iodide
+7.5 mmol). The reaction mixture was stirred at 45±508C
for 1 h under N2, quenched with H2O +20 ml), then extracted
with EtOAc +20 ml). The organic layer was washed with
H2O and brine, dried over MgSO4 and concentrated in
vacuo. The residue was puri®ed by column chromatography
+n-Hex/EtOAc) to afford methyl ether.
4.2.1. )E)-1-Methoxy-4-phenylbut-2-ene )1i). +E)-4-
Phenylbut-2-en-1-ol25 was converted to +E)-1-methoxy-4-
phenylbut-2-ene 1i as a colorless oil in 82% yield. 1H
NMR +500 MHz, CDCl3):d 3.34 +s, 3H), 3.41 +dd, 2H, Jˆ
6.5, 1 Hz), 3.92+dd, 2H, Jˆ7, 1 Hz), 5.64 +ddt, 1H, Jˆ14, 7,
1 Hz), 5.88 +ddt, 1H, Jˆ14, 6.5, 1 Hz), 7.20±7.32 +m, 5H);
13C NMR +125 MHz, CDCl3):d 39.45, 58.56, 73.70, 126.81,
128.32, 129.15, 129.30, 133.80, 140.69; IR +neat):2926,
From the results in Tables 1±3, it appears that the regio-
selectivity of these reactions by the attack of the nucleophile
+N2 moiety of CSI) profoundly depends upon the substi-
tution patterns and the positions of the alkoxy moiety.
2897, 1603, 1495, 1463, 1382, 1196, 1119, 1091 cm21
;
HRMS +CI) Calcd for C11H14O1H +M1H)1 163.1123.
Found: 163.1128.
3. Conclusion
We have demonstrated that the reactions of various allyl
ethers with CSI afforded regioselective N-protective allylic
amines via the stable allylic carbocation and the allylic
rearrangement in one pot. We also found that steric and
electronic factors affect the regioselectivity, in terms of
the ratios of internal and terminal allylic amines. We are
actively pursuing further applications of these reactions,
including a more re®ned de®nition of its reaction mecha-
nism with an eye toward stereoselectivity.
4.2.2. )Z)-1-Methoxy-4-phenylbut-2-ene )1j). +Z)-4-
Phenylbut-2-en-1-ol25 was converted to +Z)-1-methoxy-4-
phenylbut-2-ene 1j as a colorless oil in 78% yield. H
NMR +500 MHz, CDCl3): d 3.38 +s, 3H), 3.45 +d, 2H, Jˆ
7.5 Hz), 4.09 +d, 2H, Jˆ6.5 Hz), 5.70 +dt, 1H, Jˆ9, 6.5 Hz),
5.78 +dt, 1H, Jˆ9, 7.5 Hz), 7.19±7.32+m, 5H); 13C NMR
+125 MHz, CDCl3): d 34.51, 58.78, 68.79, 126.79, 127.68,
129.05, 129.21, 132.47, 140.92; IR +neat): 2916, 1627,
1455, 1351, 1101 cm21; HRMS +CI) Calcd for C11H14O1
H +M1H)1 163.1123. Found: 163.1126.
1
4. Experimental
4.1. General
4.2.3. 2-Methoxy-5-phenylpent-3-ene )1n). 5-Phenylpent-
3-en-2-ol26 was converted to 2-methoxy-5-phenylpent-3-
ene 1n as a colorless oil in 87% yield. H NMR +500
1
Commercially available reagents were used without
additional puri®cation, unless otherwise stated. All
anhydrous solvents were distilled over CaH2 or P2O5 or
Na/benzophenone prior to reaction. All reactions were
performed under an inert atmosphere of nitrogen or argon.
Melting points were measured on a Gallenkamp melting
point apparatus and were not corrected. Nuclear magnetic
resonance spectra +1H and 13C NMR) were recorded on a
Varian Unity Inova 500 MHz spectrometer for CDCl3
solutions and chemical shifts are reported as parts per
million +ppm) relative to, respectively, residual CHCl3 dH
MHz, CDCl3): d 1.25 +d, 3H, Jˆ6 Hz), 3.27 +s, 3H), 3.39
+d, 2H, Jˆ6.5 Hz), 3.73 +dq, 1H, Jˆ6.5, 6 Hz), 5.44 +dd, 1H,
Jˆ15.5, 6.5 Hz), 5.79 +dt, 1H, Jˆ15.5, 6.5 Hz), 7.19±7.32
+m, 5H); 13C NMR +125 MHz, CDCl3): d 22.08, 39.38,
56.53, 78.54, 126.80, 129.15, 129.23, 132.24, 133.90,
140.89; IR +neat): 2929, 1654, 1605, 1452, 1354, 1188,
1097 cm21; HRMS +CI) Calcd for C12H16O±H +M2H)1
175.1123. Found: 175.1126.
4.2.4. 1-Phenyl-2-methoxypent-3-ene )1o). 1-Phenylpent-
3-en-2-ol27 was converted to 1-phenyl-2-methoxypent-3-

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J. D. Kim et al. / Tetrahedron 57 '2001) 8257±8266
ene 1o as a colorless oil in 82% yield. 1H NMR +500 MHz,
CDCl3): d 1.66 +dd, 3H, Jˆ6.5, 1.5 Hz), 2.72 +dd, 1H, Jˆ14,
6.5 Hz), 2.88 +dd, 1H, Jˆ14, 7 Hz), 3.21 +s, 3H), 3.68 +ddd,
1H, Jˆ7, 6.5, 1 Hz), 5.31 +ddd, 1H, Jˆ15, 6.5, 1.5 Hz), 5.53
+ddq, 1H, Jˆ15, 6.5, 1 Hz), 7.15±7.26 +m, 5H); 13C NMR
+125 MHz, CDCl3): d 18.37, 43.06, 56.73, 84.05, 126.72,
128.77, 129.77, 130.24, 131.78, 139.34, 140.89; IR +neat):
2929, 1721, 1603, 1455, 1351, 1098 cm21; HRMS +CI)
Calcd for C12H16O±H +M2H)1 175.1123. Found:
175.1126.
+dd, 1H, Jˆ15.5, 7 Hz), 6.62+d, 1H, Jˆ15.5 Hz), 7.25±7.44
+m, 5H); 13C NMR +125 MHz, CDCl3): d 27.05, 56.75,
83.88, 117.60, 127.27, 128.49, 129.29, 129.47, 132.74,
137.32, 138.30; IR +neat): 2939, 2845, 1709, 1617, 1448,
1307, 1179, 1085 cm21; HRMS +CI) Calcd for C12H14O1H
+M1H)1 175.1123. Found: 175.1120.
4.2.8. 3-Methoxy-6-phenylhexa-1,4-diene )4c). 6-Phenyl-
hexa-1,4-dien-3-ol. To a solution of 4-phenylbut-2-enal31
+7 mmol) in THF +14 ml) was added vinylmagnesium
bromide +8.4 mmol, 1.0 M in THF) at 2788C under N2.
The reaction mixture was stirred at 0±58C for 1 h, quenched
with saturated NH4Cl +20 ml) aqueous solution, then
extracted with ether +20 ml). The organic layer was washed
with H2O and brine, dried over MgSO4 and concentrated in
vacuo. The residue was puri®ed by column chromatography
+n-Hex/EtOAcˆ6:1) to afford 6-phenylhexa-1,4-dien-3-ol
4.2.5. 1,4-Diphenyl-2-methoxybut-3-ene )1q). 1,4-Di-
phenylbut-3-en-2-ol28 was converted to 1,4-diphenyl-2-
methoxybut-3-ene 1q as a colorless oil in 71% yield. H
1
NMR +500 MHz, CDCl3): d 2.89 +dd, 1H, Jˆ14, 6 Hz),
3.04 +dd, 1H, Jˆ14, 7 Hz), 3.30 +s, 3H), 3.97 +ddd, 1H,
Jˆ7.5, 7, 6 Hz), 6.12+dd, 1H, Jˆ16, 7.5 Hz), 6.49 +d, 1H,
Jˆ16 Hz), 7.21±7.39 +m, 10H); 13C NMR +125 MHz,
CDCl3): d 43.22, 57.23, 84.08, 126.93, 127.21, 128.43,
128.92, 129.30, 130.29, 133.18, 137.27, 138.93; IR +neat):
3037, 2928, 1700, 1609, 1460, 1337, 1093 cm21; HRMS
+CI) Calcd for C17H18O±H +M2H)1 237.1280. Found:
237.1278.
1
as a pale yellow oil in 83% yield. H NMR +500 MHz,
CDCl3): d 3.40 +d, 2H, Jˆ6.5 Hz), 4.63 +dd, 1H, Jˆ6.5,
6.5 Hz), 5.15 +dd, 1H, Jˆ10.5, 1.5 Hz), 5.28 +dd, 1H, Jˆ
17, 1.5 Hz), 5.60 +dd, 1H, Jˆ15.5, 6.5 Hz), 5.88 +dt, 1H,
Jˆ15.5, 6.5 Hz), 5.93 +ddd, 1H, Jˆ17, 10.5, 6.5 Hz), 7.19±
7.32+m, 5H); 13C NMR +125 MHz, CDCl3): d 39.35, 74.30,
115.71, 126.88, 129.18, 129.30, 131.89, 133.07, 140.30,
140.59; IR +neat): 3354, 3032, 2898, 1623, 1424, 1272,
1097 cm21; HRMS +CI) Calcd for C12H14O±H +M2H)1
173.0967. Found: 173.0963.
4.2.6. 1-Methoxy-5-phenylpenta-2,4-diene )4a). 5-Phenyl-
penta-2,4-dien-1-ol. To a solution of ethyl 5-phenylpenta-
2,4-dienoate29 +7 mmol) in benzene +20 ml) was added
DIBAL-H +14 mmol, 1.5 M in toluene) at 08C under N2.
The reaction mixture was stirred at room temperature for
1 h, and 1N HCl +50 ml) was added at 08C. The reaction
mixture was stirred at 08C for 1 h, then extracted with ether
+20 ml). The organic layer was washed with H2O and brine,
dried over MgSO4 and concentrated in vacuo. The residue
was puri®ed by column chromatography +n-Hex/EtOAcˆ
3:1) to afford 5-phenylpenta-2,4-dien-1-ol as a white solid
in 84% yield. 1H NMR +500 MHz, CDCl3): d 1.58±1.69 +br,
1H), 4.25 +d, 2H, Jˆ6 Hz), 5.96 +dt, 1H, Jˆ15, 6 Hz), 6.42
+dd, 1H, Jˆ15, 11 Hz), 6.57 +d, 1H, Jˆ15.5 Hz), 6.81 +dd,
1H, Jˆ15.5, 11 Hz), 7.22±7.41 +m, 5H); 13C NMR
+125 MHz, CDCl3): d 64.13, 127.10, 128.34, 128.85,
129.33, 132.33, 133.20, 133.49, 137.82; IR +CH2Cl2):
3334, 3023, 2926, 1671, 1619, 1449, 1395, 1267, 1125,
1083 cm21; mp: 67±698C; Anal. Calcd for C11H12O: C,
82.46; H, 7.55. Found: C, 82.44; H, 7.49.
3-Methoxy-6-phenylhexa-1,4-diene +4c). 6-Phenylhexa-1,4-
dien-3-ol was converted to 3-methoxy-6-phenylhexa-1,4-
diene 4c as a pale yellow oil in 89% yield. 1H NMR
+500 MHz, CDCl3): d 3.33 +s, 3H), 3.43 +d, 2H, Jˆ
6.5 Hz), 4.09 +dd, 1H, Jˆ7, 7 Hz), 5.21 +dd, 1H, Jˆ9.5,
1.5 Hz), 5.26 +dd, 1H, Jˆ17, 1.5 Hz), 5.52+dd, 1H, Jˆ15,
7 Hz), 5.83 +ddd, 1H, Jˆ17, 9.5, 7 Hz), 5.87 +dt, 1H, Jˆ15,
6.5 Hz), 7.20±7.33 +m, 5H); 13C NMR +125 MHz, CDCl3):
d 39.49, 56.56, 83.66, 117.25, 126.84, 129.17, 129.31,
131.39, 133.13, 138.57, 140.68; IR +neat): 2929, 1703,
1607, 1441, 1304, 1091 cm21; HRMS +CI) Calcd for
C13H16O1H +M1H)1 189.1279. Found: 189.1279.
4.3. General procedure for preparation of benzyl ether
To a solution of alcohol +5 mmol) in THF +28 ml) and DMF
+7 ml) was added NaH +7.5 mmol, 60% in mineral oil) and
benzyl bromide +7.5 mmol). The reaction mixture was
stirred at room temperature for 15 h under N2, quenched
with H2O +20 ml), then extracted with EtOAc +20 ml). The
organic layer was washed with H2O and brine, dried over
MgSO4 and concentrated in vacuo. The residue was puri®ed
by column chromatography +n-Hex/EtOAc) to afford benzyl
ether.
1-Methoxy-5-phenylpenta-2,4-diene +4a). 5-Phenylpenta-
2,4-dien-1-ol was converted to 1-methoxy-5-phenylpenta-
1
2,4-diene 4a as a colorless oil in 94.3% yield. H NMR
+500 MHz, CDCl3): d 3.40 +s, 3H), 4.05 +dd, 2H, Jˆ6,
1 Hz), 5.91 +dt, 1H, Jˆ15.5, 6 Hz), 6.46 +ddd, 1H, Jˆ
15.5, 11, 1 Hz), 6.59 +d, 1H, Jˆ16 Hz), 6.83 +dd, 1H, Jˆ
16, 11 Hz), 7.25±7.45 +m, 5H); 13C NMR +125 MHz,
CDCl3): d 58.69, 73.53, 127.15, 128.34, 128.98, 129.36,
130.75, 133.45, 133.64, 137.90; IR +neat): 3012, 2913,
1701, 1603, 1460, 1331, 1109 cm21; HRMS +CI) Calcd
for C12H14O1H +M1H)1 175.1123. Found: 175.1133.
4.3.1. 1-Benzyloxy-1-phenylprop-2-ene )1d). 1-Phenyl-
prop-2en-1-ol32 was converted to 1-benzyloxy-1-phenyl-
prop-2-ene 1d as a colorless oil in 71% yield. H NMR
1
4.2.7. 1-Phenyl-3-methoxypenta-1,4-diene )4b). 1-Phenyl-
+500 MHz, CDCl3): d 4.54 +s, 2H), 4.85 +s, 1H, Jˆ
6.5 Hz), 5.25 +dd, 1H, Jˆ10.5, 1.5 Hz), 5.32+dd, 1H, Jˆ
17, 1.5 Hz), 5.99 +ddd, 1H, Jˆ17, 10.5, 6.5 Hz), 7.29±7.40
+m, 10H); 13C NMR +125 MHz, CDCl3): d 70.78, 82.71,
117.15, 127.70, 128.22, 128.40, 129.08, 129.14, 129.21,
139.19, 139.61, 141.69; IR +neat): 2925, 2836, 1631,
penta-1,4-dien-3-ol30 was converted to 1-phenyl-3-methoxy-
1
penta-1,4-diene 4b as a pale yellow oil in 72% yield. H
NMR +500 MHz, CDCl3): d 3.39 +s, 3H), 4.27 +dd, 1H, Jˆ7,
6.5 Hz), 5.28 +dd, 1H, Jˆ10.5, 1.5 Hz), 5.33 +dd, 1H, Jˆ
17.5, 1.5 Hz), 5.89 +ddd, 1H, Jˆ17.5, 10.5, 6.5 Hz), 6.17

J. D. Kim et al. / Tetrahedron 57 '2001) 8257±8266
8263
1451, 1356, 1196, 1090 cm21; HRMS +CI) Calcd for
4.3.7. 1,4-Diphenyl-1-benzyloxybut-2-ene )1r). 1,4-Di-
phenylbut-2-en-1-ol. To a solution of 4-phenylbut-2-enal31
+7 mmol) in ether +14 ml) was added phenylmagnesium
bromide +8.4 mmol, 3.0 M in ether) at 2788C under N2.
The reaction mixture was stirred at 0±58C for 1 h, quenched
with saturated NH4Cl +20 ml) aqueous solution, then
extracted with ether +20 ml). The organic layer was washed
with H2O and brine, dried over MgSO4 and concentrated in
vacuo. The residue was puri®ed by column chromatography
+n-Hex/EtOAcˆ6:1) to afford 1,4-diphenylbut-2-en-1-ol as
a white solid in 90% yield. 1H NMR +500 MHz, CDCl3): d
2.19±2.25 +br, 1H), 3.44 +d, 2H, Jˆ6.5 Hz), 5.21 +d, 1H,
Jˆ6 Hz), 5.78 +dd, 1H, Jˆ15, 6 Hz), 5.85 +dt, 1H, Jˆ15,
6.5 Hz), 7.22±7.42 +m, 10H); 13C NMR +125 MHz, CDCl3):
d 39.36, 75.64, 126.93, 126.99, 128.34, 129.25, 129.27,
129.35, 131.64, 134.41, 140.70, 143.88; IR +CH2Cl2):
C16H16O±H +M2H)1 223.1123. Found: 223.1126.
4.3.2. )E)-1-Benzyloxybut-2-ene )1e). +E)-Crotyl alcohol
was converted to +E)-1-benzyloxybut-2-ene 1e as a colorless
oil in 59% yield. H NMR +500 MHz, CDCl3): d 1.77 +dd,
1
3H, Jˆ6.5, 1.5 Hz), 4.01 +dd, 2H, Jˆ6, 1.5 Hz), 4.55 +s,
2H), 5.69 +dtq, 1H, Jˆ15.5, 6, 1.5 Hz), 5.78 +dtq, 1H, Jˆ
15.5, 6.5, 1.5 Hz), 7.31±7.40 +m, 5H); 13C NMR +125 MHz,
CDCl3): d 18.58, 71.66, 72.66, 128.28, 128.32, 128.52,
129.10, 130.39, 139.22; IR +neat): 2926, 2858, 1602,
1452, 1363, 1291, 1233, 1091 cm21; HRMS +CI) Calcd
for C11H14O±H +M2H)1 161.0967. Found: 161.0963.
4.3.3. 2-Benzyloxybut-3-ene )1f). But-3-en-2-ol was
converted to 2-benzyloxybut-3-ene 1f as a colorless oil in
50% yield. H NMR +500 MHz, CDCl3): d 1.32+d, 3H,
1
3355, 3029, 2899, 1602, 1494, 1452, 1195, 1006 cm21
;
Jˆ6.5 Hz), 3.94 +dq, 1H, Jˆ6.5, 6.5 Hz), 4.42+d, 1H, Jˆ
12Hz), 4.60 +d, 1H, Jˆ12Hz), 5.24 +dd, 1H, Jˆ10.5, 1 Hz),
5.26 +dd, 1H, Jˆ17, 1 Hz), 5.83 +ddd, 1H, Jˆ17, 10.5,
6.5 Hz), 7.28±7.40 +m, 5H); 13C NMR +125 MHz, CDCl3):
d 22.13, 70.67, 76.95, 116.85, 128.23, 128.51, 129.13,
139.52, 140.97; IR +neat): 3044, 2919, 1711, 1619, 1453,
1362, 1256, 1086 cm21; HRMS +CI) Calcd for C11H14O±H
+M2H)1 161.0967. Found: 161.0969.
mp: 40±418C; Anal. Calcd for C16H16O: C, 85.68; H,
7.19. Found: C, 85.67; H, 7.22.
1,4-Diphenyl-1-benzyloxybut-2-ene +1r). 1,4-Diphenylbut-
2-en-1-ol was converted to 1,4-diphenyl-1-benzyloxybut-
2-ene 1r as a colorless oil in 68% yield. 1H NMR
+500 MHz, CDCl3): d 3.41 +d, 2H, Jˆ6.5 Hz), 4.52+d,
2H, Jˆ5 Hz), 4.84 +d, 1H, Jˆ7 Hz), 5.74 +dd, 1H, Jˆ16,
7 Hz), 5.85 +dt, 1H, Jˆ16, 6.5 Hz), 7.17±7.39 +m, 15H); 13C
NMR +125 MHz, CDCl3): d 39.43, 70.67, 82.17, 126.81,
127.61, 128.17, 128.25, 128.43, 129.05, 129.15, 129.29,
132.71, 132.96, 139.19, 140.72, 142.17; IR +neat): 3030,
4.3.4. 1-Benzyloxy-4-methylpent-2-ene )1g). 4-Methyl-
pent-2-en-1-ol33 was converted to 1-benzyloxy-4-methyl-
pent-2-ene 1g as a colorless oil in 66% yield. H NMR
1
+500 MHz, CDCl3): d 1.01 +d, 3H, Jˆ7 Hz), 1.02+d, 3H,
Jˆ7 Hz), 2.33 +dq, 1H, Jˆ7, 6.5 Hz), 3.99 +d, 2H, Jˆ
6.5 Hz), 4.52+s, 2H), 5.57 +dt, 1H, Jˆ16.5, 6.5 Hz), 5.70
+dd, 1H, Jˆ16.5, 6.5 Hz), 7.29±7.38 +m, 5H); 13C NMR
+125 MHz, CDCl3): d 22.92, 31.51, 71.79, 72.62, 123.92,
128.24, 128.55, 129.07, 139.18, 142.51; IR +neat): 2945,
2867, 1621, 1456, 1363, 1091 cm21; HRMS +CI) Calcd
for C13H18O±H +M2H)1 189.1280. Found: 189.1282.
2864, 1695, 1602, 1495, 1452, 1311, 1203, 1067 cm21
;
HRMS +CI) Calcd for C23H22O±H +M2H)1 313.1593.
Found: 313.1598.
4.4. General procedure for reaction of allyl ether with
chlorosulfonyl isocyanate )CSI)
A suspension of Na2CO3 +6.75 mmol) in anhydrous CH2Cl2
+12ml) was adjusted to 20 8C or 2788C, then CSI
+4.5 mmol) and allyl ether +3 mmol) was added under N2.
The reaction mixture was stirred at 208C or 2788C.
quenched with H2O +10 ml) when the reaction was
completed +TLC monitoring), then extracted with EtOAc
+10 ml£2). The organic layer was added to an aqueous
solution of Na2SO3 +25%) and KOH +10%), and the reaction
mixture was stirred at room temperature overnight. The
organic layer was washed with H2O and brine, dried over
MgSO4 and concentrated in vacuo. The residue was puri®ed
by column chromatography +n-Hex/EtOAc) to afford
N-protected allylic amine.
4.3.5. 1-Benzyloxy-4-phenylbut-2-ene )1l). 4-Phenylbut-2-
en-1-ol25 was converted to 1-benzyloxy-4-phenylbut-2-ene
1l as a colorless oil in 71% yield. H NMR +500 MHz,
1
CDCl3): d 3.45 +d, 2H, Jˆ7 Hz), 4.06 +d, 2H, Jˆ6 Hz),
4.56 +s, 2H), 5.73 +dt, 1H, Jˆ16.5, 6 Hz), 5.95 +dt, 1H, Jˆ
16.5, 7 Hz), 7.23±7.44 +m, 10H); 13C NMR +125 MHz,
CDCl3): d 39.59, 71.43, 72.81, 126.96, 127.52, 128.48,
128.67, 129.22, 129.34, 129.49, 134.01, 139.05, 140.79;
IR +neat): 3039, 2875, 1683, 1609, 1454, 1354,
1086 cm21; HRMS +CI) Calcd for C17H18O1H +M1H)1
239.1436. Found: 239.1440.
4.3.6. 1-Phenyl-2-benzyloxybut-3-ene )1m). 1-Phenylbut-
3-en-2-ol34 was converted to 1-phenyl-2-benzyloxybut-3-
ene 1m as a colorless oil in 95% yield. 1H NMR
+500 MHz, CDCl3): d 2.83 +dd, 1H, Jˆ14, 6 Hz), 2.99
+dd, 1H, Jˆ14, 7 Hz), 3.99 +ddd, 1H, Jˆ7, 6.5, 6 Hz),
4.35 +d, 1H, Jˆ12Hz), 4.50 +d, 1H, Jˆ12Hz), 5.21 +dd,
1H, Jˆ10, 1 Hz), 5.23 +dd, 1H, Jˆ16.5, 1 Hz), 5.80 +ddd,
1H, Jˆ16.5, 10, 6.5 Hz), 7.20±7.39 +m, 10H); 13C NMR
+125 MHz, CDCl3): d 43.07, 70.93, 82.15, 118.14, 126.87,
128.05, 128.27, 128.81, 128.97, 130.42, 139.09, 139.30; IR
4.4.1. Benzyl N-)1-phenylallyl)carbamate )2c). White
solid; H NMR +500 MHz, CDCl3): d 5.12+s, 2H), 5.15
1
+dd, 1H, Jˆ5.5, 5 Hz), 5.24 +dd, 1H, Jˆ9.5, 1.5 Hz), 5.25
+dd, 1H, Jˆ18, 1.5 Hz), 5.33±5.40 +br, 1H), 6.01 +ddd, 1H,
Jˆ18, 9.5, 5.5 Hz), 7.21±7.38 +m, 10H); 13C NMR +125
MHz, CDCl3): d 57.81, 67.65, 116.54, 126.79, 127.74,
128.42, 128.87, 129.23, 129.46, 137.06, 138.27, 141.32,
156.25; IR +CH2Cl2): 3322, 3045, 2934, 1707, 1515, 1242,
1042cm 21
; mp: 46±478C; HRMS +CI) Calcd for
C17H17NO21H +M1H)1 268.1337. Found: 268.1343.
+neat): 2909, 2879, 1606, 1449, 1334, 1212, 1081 cm21
;
HRMS +CI) Calcd for C17H18O1H +M1H)1 239.1436.
Found: 239.1440.
4.4.2. Benzyl N-)3-phenylprop-2-enyl)carbamate )3c).
White solid; H NMR +500 MHz, CDCl3): d 3.99 +dd, 2H,
1

8264
J. D. Kim et al. / Tetrahedron 57 '2001) 8257±8266
Jˆ6, 4.5 Hz), 4.88±4.97 +br, 1H), 5.15 +s, 2H), 6.17 +dt, 1H,
Jˆ16, 6 Hz), 6.53 +d, 1H, Jˆ16 Hz), 7.23±7.39 +m, 10H);
13C NMR +125 MHz, CDCl3): d 43.88, 67.54, 126.52,
127.11, 128.41, 128.85, 129.10, 129.25, 129.29, 132.49,
137.25, 156.98; IR +KBr): 3319, 2832, 1686, 1543, 1451,
1261, 1248, 1138 cm21; mp: 62±638C; Anal. Calcd for
C17H17NO2: C, 76.38; H, 6.41; N, 5.24. Found: C, 76.52;
H, 6.46; N, 5.22.
1255 cm21; HRMS +CI) Calcd for C12H15NO21H +M1
H)1 206.1181. Found: 206.1182.
4.4.7. )E)-Methyl N-)4-phenylbut-2-enyl)carbamate )3i).
White solid; H NMR +500 MHz, CDCl3): d 3.36 +d, 2H,
1
Jˆ6.5 Hz), 3.73 +s, 3H), 3.78 +dd, 2H, Jˆ6, 4.5 Hz), 4.70±
4.78 +br, 1H), 5.54 +dt, 1H, Jˆ15, 6 Hz), 5.77 +dt, 1H, Jˆ15,
6.5 Hz), 7.16±7.31 +m, 5H); 13C NMR +125 MHz, CDCl3):
d 39.30, 43.48, 52.82, 126.87, 128.22, 129.18, 129.24,
132.34, 140.64, 157.58; IR +nujol): 3352, 2954, 2850,
1696, 1515, 1463, 1377, 1260, 1234, 1055 cm21; mp: 60±
618C; HRMS +CI) Calcd for C12H15NO21H +M1H)1
206.1181. Found: 206.1182.
4.4.3. Benzyl N-)1-methylallyl)carbamate )2e) and ben-
zyl N-)but-2-enyl)carbamate )3e). Benzyl N-'1-methyl-
allyl)carbamate +2e). H NMR +500 MHz, CDCl3): d 1.24
1
+d, 3H, Jˆ6.5 Hz), 4.27±4.35 +br, 1H), 4.72±4.79 +br,
1H), 5.10 +dd, 1H, Jˆ10, 1 Hz), 5.11 +s, 2H), 5.17 +dd,
1H, Jˆ17, 1 Hz), 5.84 +ddd, 1H, Jˆ17, 10, 5 Hz), 7.30±
7.40 +m, 5H); 13C NMR +125 MHz, CDCl3): d 21.35,
49.39, 67.36, 114.72, 128.64, 128.81, 129.23, 137.26,
140.40, 159.30.
4.4.8. )Z)-Methyl N-)4-phenylbut-2-enyl)carbamate )3j).
1H NMR +500 MHz, CDCl3): d 3.46 +d, 2H, Jˆ7.5 Hz), 3.69
+s, 3H), 3.95 +dd, 2H, Jˆ6.5, 4.5 Hz), 4.82±4.90 +br, 1H),
5.55 +dt, 1H, Jˆ10.5, 6.5 Hz), 5.75 +dt, 1H, Jˆ10.5, 7.5 Hz),
7.18±7.32+m, 5H); 13C NMR +125 MHz, CDCl3): d 34.24,
38.81, 52.87, 126.85, 127.28, 129.01, 129.26, 132.19,
140.82, 157.72; IR +CH2Cl2): 3323, 3035, 2969, 1701,
1634, 1457, 1265, 1031 cm21; HRMS +CI) Calcd for
C12H15NO21H +M1H)1 206.1181. Found: 206.1185.
1
Benzyl N-'but-2-enyl)carbamate +3e). H NMR +500 MHz,
CDCl3): d 1.68 +d, 3H, Jˆ6.5 Hz), 3.74 +dd, 2H, Jˆ5.5,
5.5 Hz), 4.75±4.85 +br, 1H), 5.11 +s, 2H), 5.48 +dt, 1H,
Jˆ16, 5.5 Hz), 5.61 +dq, 1H, Jˆ16, 6.5 Hz), 7.30±7.40
+m, 5H); 13C NMR +125 MHz, CDCl3): d 16.36, 43.71,
67.36, 127.85, 128.64, 128.74, 128.81, 129.23, 140.48,
156.92; IR +neat): 3410, 3331, 3033, 2971, 2937, 1729,
1769, 1691, 1531, 1454, 1334, 1293, 1241, 1134,
4.4.9. Benzyl N-)1-benzylallyl)carbamate )2l). White
1
solid; H NMR +500 MHz, CDCl3): d 2.88 +d, 2H, Jˆ
5.5 Hz), 4.50±4.58 +br, 1H), 4.76±4.85 +br, 1H), 5.10 +s,
2H), 5.13 +dd, 1H, Jˆ10.5, 1.5 Hz), 5.15 +dd, 1H, Jˆ16.5,
1.5 Hz), 5.82+ddd, 1H, Jˆ16.5, 10.5, 5.5 Hz), 7.18±7.39
+m, 10H); 13C NMR +125 MHz, CDCl3): d 42.03, 54.74,
67.40, 115.79, 127.34, 128.82, 128.94, 129.13, 129.24,
130.25, 137.24, 137.82, 138.43, 156.39; IR +CH2Cl2):
3326, 3031, 2927, 1700, 1629, 1504, 1454, 1335, 1246,
1053 cm21
;
HRMS +CI) Calcd for C12H15NO21H
+M1H)1 206.1181. Found: 206.1178.
4.4.4. Benzyl N-)1-isopropylallyl)carbamate )2g). White
1
solid; H NMR +500 MHz, CDCl3): d 0.89 +d, 3H, Jˆ
6.5 Hz), 0.90 +d, 3H, Jˆ6.5 Hz), 1.81 +dq, 1H, Jˆ6.5,
6.5 Hz), 4.04±4.11 +br, 1H), 4.70±4.78 +br, 1H), 5.11 +s,
2H), 5.14 +dd, 1H, Jˆ10, 1.5 Hz), 5.16 +dd, 1H, Jˆ17,
1.5 Hz), 5.75 +ddd, 1H, Jˆ17, 10, 6 Hz), 7.31±7.37 +m,
5H); 13C NMR +125 MHz, CDCl3): d 18.71, 19.38, 32.88,
59.33, 67.45, 116.21, 128.86, 129.26, 137.26, 137.64,
156.73; IR +CH2Cl2): 3327, 3049, 2942, 1707, 1517, 1246,
1077 cm21
; mp: 67±708C; HRMS +CI) Calcd for
C18H19NO21H +M1H)1 282.1494. Found: 282.1491.
4.4.10. Benzyl N-)4-phenylbut-2-enyl)carbamate )3l).
White solid; H NMR +500 MHz, CDCl3): d 3.37 +d, 2H,
1
Jˆ7 Hz), 3.81 +dd, 2H, Jˆ6.5, 4.5 Hz), 4.78±4.87 +br, 1H),
5.17 +s, 2H), 5.56 +dt, 1H, Jˆ15, 6.5 Hz), 5.77 +dt, 1H, Jˆ
15, 7 Hz), 7.17±7.39 +m, 10H); 13C NMR +125 MHz,
CDCl3): d 39.30, 43.53, 67.45, 126.89, 127.35, 128.09,
128.84, 129.20, 129.26, 129.30, 132.51, 137.24, 140.62,
156.90; IR +CH2Cl2): 3332, 3042, 2925, 1706, 1521, 1434,
1251, 1114, 1017 cm21; mp: 85±888C; Anal. Calcd for
C18H19NO2: C, 76.84; H, 6.81; N, 4.98. Found: C, 76.93;
H, 6.78; N, 4.80.
1081, 1016 cm21
; mp: 48±508C; Anal. Calcd for
C14H19NO2: C, 72.07; H, 8.21; N, 6.00. Found: C, 72.31;
H, 8.22; N, 5.89.
4.4.5. Benzyl N-)4-methylpent-2-enyl)carbamate )3g).
Colorless oil; H NMR +500 MHz, CDCl3): d 0.96 +d, 3H,
1
Jˆ7 Hz), 0.99 +d, 3H, Jˆ7 Hz), 2.27 +dq, 1H, Jˆ7, 6.5 Hz),
3.76 +dd, 2H, Jˆ6, 5.5 Hz), 4.73±4.82+br, 1H), 5.11 +s, 2H),
5.41 +dt, 1H, Jˆ15.5, 6.5 Hz), 5.59 +dd, 1H, Jˆ15.5,
6.5 Hz), 7.30±7.38 +m, 5H); 13C NMR +125 MHz, CDCl3):
d 22.93, 31.39, 43.76, 67.37, 123.62, 128.61, 128.84,
129.22, 137.31, 141.11, 156.78; IR +neat): 3334, 2947,
1707, 1524, 1349, 1246, 1126, 1025 cm21; HRMS +CI)
Calcd for C14H19NO21H +M1H)1 234.1484. Found:
234.1492.
4.4.11. Methyl N-)1-methyl-4-phenylbut-2-enyl)carba-
mate )3n). Colorless oil; H NMR +500 MHz, CDCl3): d
1
1.23 +d, 3H, Jˆ6.5 Hz), 3.37 +d, 2H, Jˆ6.5 Hz), 3.67 +s,
3H), 4.24±4.33 +br, 1H), 4.61±4.70 +br, 1H), 5.50 +dd,
1H, Jˆ15.5, 5.5 Hz), 5.77 +dt, 1H, Jˆ15.5, 6.5 Hz), 7.17±
7.32+m, 5H); 13C NMR +125 MHz, CDCl3): d 21.87, 39.26,
48.72, 52.71, 126.82, 129.15, 129.25, 133.70, 140.78,
157.50; IR +neat): 3326, 2963, 1707, 1522, 1419, 1339,
1245, 1075 cm21; HRMS +CI) Calcd for C13H17NO21H
+M1H)1 220.1337. Found: 220.1340.
4.4.6. Methyl N-)1-benzylallyl)carbamate )2i). Colorless
oil; 1H NMR +500 MHz, CDCl3): d 2.86 +d, 2H, Jˆ6.5 Hz),
3.66 +s, 3H), 4.40±4.48 +br, 1H), 4.57±4.65 +br, 1H), 5.11
+dd, 1H, Jˆ10.5, 1.5 Hz), 5.12+dd, 1H, Jˆ17, 1.5 Hz), 5.81
+ddd, 1H, Jˆ17, 10.5, 5.5 Hz), 7.18±7.32+m, 5H); 13C
NMR +125 MHz, CDCl3): d 42.06, 52.83, 54.62, 115.72,
127.33, 129.11, 130.21, 137.77, 138.45, 157.01; IR
+nujol): 3330, 2954, 2861, 1693, 1539, 1459, 1376,
4.4.12. Methyl N-)1-benzyl-3-phenylprop-2-enyl)carba-
mate )2p). White solid; H NMR +500 MHz, CDCl3): d
1
2.96 +d, 2H, Jˆ6.5 Hz), 3.68 +s, 3H), 4.61±4.70 +br, 1H),
4.71±4.80 +br, 1H), 6.15 +dd, 1H, Jˆ16, 6 Hz), 6.47 +dd, 1H,

J. D. Kim et al. / Tetrahedron 57 '2001) 8257±8266
8265
Jˆ16, 1 Hz), 7.21±7.39 +m, 10H); 13C NMR +125 MHz,
References
CDCl3): d 42.49, 52.92, 54.39, 127.13, 127.39, 128.34,
129.20, 129.26, 130.26, 130.30, 131.07, 137.32, 137.73,
156.99; IR +CH2Cl2): 3318, 3027, 1691, 1638, 1537, 1493,
1448, 1321, 1264, 1061 cm21; mp: 113±1158C; HRMS +CI)
Calcd for C18H19NO21H +M1H)1 282.1494. Found:
282.1492.
1. +a) Ricci, A. Modern Amination Methods; WILEY-VCH:
Weinheim, 2000. +b) For a recent review of synthetic
approaches to allylic amines, see: Johannsen, M.; Jùrgensen,
K. A. Chem. Rev. 1998, 98, 1689.
2. +a) Mitsunobu, O. Synthesis 1981, 1. +b) Sen, S. E.; Roach,
S. L. Synthesis 1995, 756.
4.4.13. Benzyl N-)1-benzyl-3-phenylprop-2-enyl)carba-
mate )2r). White solid; H NMR +500 MHz, CDCl3): d
3. +a) Overman, L. E. J. Am. Chem. Soc. 1976, 98, 2901.
+b) Calter, M.; Hollis, T. K.; Overman, L. E.; Ziller, J.;
Zipp, G. G. J. Org. Chem. 1997, 62, 1449.
1
2.97 +d, 2H, Jˆ6.5 Hz), 4.62±4.70 +br, 1H), 4.77±4.87
+br, 1H), 5.10 +s, 2H), 6.14 +dd, 1H, Jˆ16, 6 Hz), 6.47 +d,
1H, Jˆ16 Hz), 7.20±7.34 +m, 15H); 13C NMR +125 MHz,
CDCl3): d 42.47, 54.46, 67.47, 127.13, 127.39, 128.34,
128.83, 129.20, 129.25, 129.94, 130.27, 131.24, 137.17,
137.29, 137.68, 156.32; IR +CH2Cl2): 3324, 3029, 1693,
1531, 1496, 1451, 1256, 1049 cm21; mp: 102±1048C;
Anal. Calcd for C24H23NO2: C, 80.64; H, 6.49; N, 3.92.
Found: C, 80.62; H, 6.52; N, 3.79.
4. +a) Gibson, M. S.; Bradshaw, R. W. Angew. Chem. 1968, 80,
986. +b) Osby, J. O.; Martin, M. G.; Ganem, B. Tetrahedron
Lett. 1984, 25, 2093.
5. +a) Togni, A.; Burckhardt, U.; Gramlich, V.; Pregosin, P. S.;
Salzmann, R. J. Am. Chem. Soc. 1996, 118, 1031. +b) Tsuji, J.;
Takahashi, H.; Morikawa, M. Tetrahedron Lett. 1965, 6, 4387.
+c) Lei, A.; Lu, X. Org. Lett. 2000, 2, 2357. +d) Trost, B. M.;
Krueger, A. C.; Bunt, R. C.; Zambrano, J. J. Am. Chem. Soc.
1996, 118, 6520.
4.4.14. Methyl N-)5-phenylpenta-2,4-dienyl)carbamate
)5a). White solid; H NMR +500 MHz, CDCl3): d 3.70 +s,
6. +a) Baruah, J. B.; Samuelson, A. G. Tetrahedron 1991, 47,
9449. +b) Germon, C.; Alexakis, A.; Normant, J. F.
Tetrahedron Lett. 1980, 21, 3763.
1
3H), 3.86±3.95 +br, 1H), 4.75±4.83 +br, 1H), 5.80 +dt, 1H,
Jˆ15.5, 6 Hz), 6.34 +dd, 1H, Jˆ15.5, 10.5 Hz), 6.53 +d, 1H,
Jˆ15.5 Hz), 6.76 +dd, 1H, Jˆ15.5, 10.5 Hz), 7.21±7.40 +m,
5H); 13C NMR +125 MHz, CDCl3): d 43.57, 52.95, 127.07,
128.31, 128.65, 129.32, 130.53, 132.80, 133.35, 137.78,
157.60; IR +CH2Cl2): 3332, 2831, 1695, 1541, 1449, 1279,
1125, 1049 cm21; mp: 78±808C; HRMS +CI) Calcd for
C13H15NO21H +M1H)1 218.1181. Found: 218.1174.
7. +a) Srivastava, R. S.; Nicholas, M. Tetrahedron Lett. 1994, 35,
9739. +b) Enders, D.; Jandeleit, B.; von Berg, S. Synlett 1997,
421. +c) Silverman, G. S.; Strickland, S.; Nicholas, K. M.
Organometallics 1986, 5, 2117.
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2000, 2, 2319.
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1995, 36, 8295. +b) Chanda, B. M.; Vyas, R.; Bedekar, A. V.
J. Org. Chem. 2001, 66, 30.
4.4.15. Methyl N-)6-phenylhexa-2,4-dienyl)carbamate
)5c). Colorless oil; H NMR +500 MHz, CDCl3): d 3.42
1
+d, 2H, Jˆ7 Hz), 3.68 +s, 3H), 3.81 +dd, 2H, Jˆ6.5, 5 Hz),
4.73±4.80 +br, 1H), 5.60 +dt, 1H, Jˆ15, 6.5 Hz), 5.82+dt,
1H, Jˆ15, 7 Hz), 6.07 +dd, 1H, Jˆ15, 10 Hz), 6.16 +dd, 1H,
Jˆ15, 10 Hz), 7.17±7.32+m, 5H); 13C NMR +125 MHz,
CDCl3): d 39.65, 43.45, 52.88, 126.85, 128.52, 129.17,
129.28, 131.10, 132.52, 134.06, 140.69, 157.61; IR +neat):
10. +a) Matsumoto, M.; Kitano, Y.; Kobayashi, H.; Ikawa, H.
Tetrahedron Lett. 1996, 37, 8191. +b) SchoÄnberger, N.;
Kresze, G. Liebigs Ann. Chem. 1975, 5, 1725.
11. +a) Dickinson, J. M.; Murphy, J. A. Tetrahedron 1992, 48,
1317. +b) Penkett, C. S.; Simpson, I. D. Tetrahedron Lett.
2001, 42, 3029.
3340, 3017, 2936, 1708, 1526, 1447, 1257, 1004 cm21
;
HRMS +CI) Calcd for C14H17NO21H +M1H)1 232.1337.
Found: 232.1339.
12. +a) Hayashi, T.; Ishigedani, M. Tetrahedron 2001, 57, 2589.
+b) Moody, C. J.; Gallagher, P. T.; Lightfoot, A. P.; Salwin,
A. M. Z. J. Org. Chem. 1999, 64, 4419.
13. +a) Bower, J. F.; Jumnah, R.; Williams, A. C.; Williams, J. M. J.
J. Chem. Soc., Perkin Trans. 1 1997, 1411. +b) Bates, R. B.;
Gangwar, S. Tetrahedron: Asymmetry 1993, 4, 69.
+c) Burgess, K.; Liu, L. T.; Pal, B. J. Org. Chem. 1993, 58,
4758. +d) Hayashi, T.; Yamamoto, A.; Ito, Y.; Nishioka, E.;
Miura, H.; Yanagi, K. J. Am. Chem. Soc. 1989, 111, 6301.
14. For ef®cient methods in this area, see: +a) Overman, L. E.;
Zipp, G. G. J. Org. Chem. 1997, 62, 2288. +b) Metz, P.; Mues,
C.; Schoop, A. Tetrahedron 1992, 48, 1071. +c) Xu, Q.;
Dittmer, D. C. Tetrahedron Lett. 1999, 40, 2255. +d) Aguilar,
E.; Joglar, J.; Merino, I.; Olano, B.; Palacios, F.; Fustero, S.
Tetrahedron 2000, 56, 8179.
4.4.16. Methyl N-)1-benzylpenta-2,4-dienyl)carbamate
)6c). White solid; H NMR +500 MHz, CDCl3): d 2.87 +d,
1
2H, Jˆ6.5 Hz), 3.63 +s, 3H), 4.51±4.59 +br, 1H), 4.75±4.85
+br, 1H), 5.07 +dd, 1H, Jˆ10, 1.5 Hz), 5.18 +dd, 1H, Jˆ17,
1.5 Hz), 5.65 +dd, 1H, Jˆ15, 6 Hz), 6.13 +dd, 1H, Jˆ15,
6 Hz), 6.30 +ddd, 1H, Jˆ17, 10, 6 Hz), 7.21±7.40 +m,
5H); 13C NMR +125 MHz, CDCl3): d 42.26, 52.83, 53.95,
118.25, 127.28, 129.21, 130.26, 131.90, 134.05, 136.86,
137.80, 156.98; IR +CH2Cl2): 3324, 3029, 2949, 1728,
1692, 1604, 1535, 1452, 1355, 1258 cm21; mp: 30±318C;
HRMS +CI) Calcd for C14H17NO21H +M1H)1 232.1337.
Found: 232.1329.
15. +a) Kim, J. D.; Lee, M. H.; Lee, M. J.; Jung, Y. H. Tetrahedron
Lett. 2000, 41, 5073. +b) Jung, Y. H.; Kim, J. D. Arch. Pharm.
Res. 2000, 23, 574.
Acknowledgements
16. +a) Kobayashi, Y.; Ito, Y.; Terashima, S. Tetrahedron 1992,
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B.; Ugalde, J. M. J. Am. Chem. Soc. 1995, 117, 12306.
17. +a) Clauû, K.; Grimm, D.; Prossel, G. Liebigs Ann. Chem.
The authors wish to acknowledge the ®nancial support of
the Korea Research Foundation made in the program year of
1998.

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