A simple and easy access to 3-N-alkyl-5-vinyloxazolidinones mediated by palladium-phosphine catalysts

Article abstract of DOI:10.1016/S0040-4020(03)00548-9

A new entry for the synthesis of 3-alkyl substituted 5-vinyloxazolidin-2-one derivatives 2 from cis-2-butenylene-1,4-dicarbonate 1 and primary amines mediated by palladium-phosphine catalysts is described. The scope and limitation, a plausible mechanism, and an asymmetric version of the reaction are also discussed.

Full text of DOI:10.1016/S0040-4020(03)00548-9

Tetrahedron 59 (2003) 3745–3751
A simple and easy access to 3-N-alkyl-5-vinyloxazolidinones
mediated by palladium–phosphine catalysts
*
Shinji Tanimori, Ushio Inaba, Yoshihiro Kato and Mitsunori Kirihata
Department of Applied Biological Chemistry, Graduate School of Agriculture and Life Sciences, Osaka Prefecture University,
1-1 Gakuen-cho, Sakai, Osaka 599-5851, Japan
Received 27 February 2003; accepted 31 March 2003
Abstract—A new entry for the synthesis of 3-alkyl substituted 5-vinyloxazolidin-2-one derivatives 2 from cis-2-butenylene-1,4-dicarbonate
1 and primary amines mediated by palladium–phosphine catalysts is described. The scope and limitation, a plausible mechanism, and an
asymmetric version of the reaction are also discussed. q 2003 Elsevier Science Ltd. All rights reserved.
1. Introduction
presence of p-allylpalladium(II) chloride dimer and
diphenylphosphinoferrocene (dppf) in THF, dichloro-
methane or chloroform at room temperature to 508C gave
5-vinyloxazolidin-2-one 2 in moderate to good yield
(Scheme 1).
In our previous report, we briefly communicated the
palladium-catalyzed formation of 5-vinyloxazolidin-2-
ones 2 starting from cis-2-butenylene dicarbonate 1 with
mainly simple amines and also a plausible mechanism of the
reaction pathway.1 This paper deals with the full details of
the work which involves the use of more complex amines
such as diamines and amino alcohols for expanding the
applicability of the reaction to the synthesis of biologically
important class of compounds. We also describe the scope
and limitations, another possible mechanism, and an
asymmetric construction of 5-vinyloxazolidin-2-one
mediated by chiral palladium–phosphine catalysts.
Especially, the efficiency of the reaction depended on the
ligand used (Table 1).
For instance, as shown in Table 1, though dppe, dppb,
triphenylphosphine, and BINAP gave low yields of the
product, dppf provided acceptable yields considering the
fact the reaction proceeded via a tandem pathway. Both
[Pd(h3-C3H5)Cl]2 and Pd2(dba)3·CHCl3 were good sources
of palladium(0) for this reaction. Additives such as a base
(carbonates, amines, metal hydrides, and alkoxides) had no
effect on the efficiency of this reaction.
2. Results and discussion
It was found that more complex amines such as diamines
and amino alcohols were also acceptable for this reaction
(Table 2). We believe that these materials obtained as
shown in Table 2 would be new useful building blocks for
the purpose of drug discovery because these materials have
an easily functionalizable double bond.
Oxazolidinone is well known to be an important class of
compounds for pharmaceutical usage2 and a chiral building
block for organic synthesis.3 For instance, toloxatone 3
(Fig. 1) is known to be a reversible monoamine oxidase
inhibitor.2a Some chiral oxazolidinones such as 4 are
commercially available.† Although there is extensive
literature concerning the synthesis of oxazolidinone deriva-
tives,2,4 for instance, derivation from epichlorohydrin,5
most of the methods need multi-step manipulations.
Surprisingly, no diastereo-discrimination was observed in
the reaction using chiral amines as nucleophiles (entry 5 and
6) to give the corresponding oxazolidinones 2f and 2g in
As mentioned in our previous report,1 the reaction of cis-2-
butenylene dicarbonate 1 with simple amines in the
Keywords: tandem allylic substitution; oxazolidinone; palladium catalyst;
asymmetric synthesis.
*
Corresponding author. Tel.: þ81-72-254-9469; fax: þ81-72-254-9918;
e-mail: tanimori@biochem.osakafu-u.ac.jp
Synthon Chiragenics.
†
Figure 1.
0040–4020/03/$ - see front matter q 2003 Elsevier Science Ltd. All rights reserved.
doi:10.1016/S0040-4020(03)00548-9

3746
S. Tanimori et al. / Tetrahedron 59 (2003) 3745–3751
Scheme 1.
Table 1. Reaction of dicarbonate 1 with benzylamine under various conditions
Entry
1 (equiv.)
Catalyst
Ligand
Solvent
Base
Temperature (8C)
Time (h)
Yield (%)a
1
2
3
4
5
6
7
1
1
2
2
2
Pd2dba3·CHCl3
[Pd(h3-C3H5)Cl]2
[Pd(h3-C3H5)Cl]2
[Pd(h3-C3H5)Cl]2
[Pd(h3-C3H5)Cl]2
[Pd(h3-C3H5)Cl]2
Pd2dba3·CHCl3
dppe
dppb
PPh3
BINAP
dppf
THF
Cs2CO3
TMGc
None
None
None
None
None
50
Reflux
RT
RT
RT
O/Nb
O/Nb
1.5
26
3
20
0
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
THF
17
40
47
58
60
61
1.5
1.5
dppf
dppf
RT
RT
CH2Cl2
32
a
Isolated yield.
O/N: overnight.
TMG: tetramethylguanidine.
b
c
Table 2. Reaction of 1 with bifunctional and chiral amines
Entry
1
Amine
Product
Yields (%)a
61
2
74
3
4
26
16
5
6
57b
41c
a
Isolated yield.
A separable 1:1 mixture of diastereomers was obtained.
An unseparable 1:1 mixture of diastereomers was obtained.
b
c

S. Tanimori et al. / Tetrahedron 59 (2003) 3745–3751
3747
Figure 2.
almost 1:1 mixtures of diastereomers, respectively, under
various conditions such as low temperature (0 and 2208C).
Application of aromatic amines (aniline derivatives) to this
process seems to be especially important because many
pharmaceutically important oxazolidinones have an
aromatic ring directly attached to the nitrogen atom such
as toloxatone 32a and linezolide.2b Disappointingly, reaction
of aniline and derivatives such as p-bromoaniline, p-nitro-
aniline, 1-aminonaphthalene, p-chloroaniline and
m-toluidine with 1 under various conditions gave only the
starting material recovered and/or a complex mixture.
Moreno-Man˜as et al. recently reported that a similar
reaction catalyzed by Pd(dba)2 and dppf employing acidic
aniline such as 3,5-dinitroaniline as nucleophile in THF at
room temperature produced N-aryl-4-vinyloxazolidin-2-
ones,4d regioisomers of 2. The mechanism of the process
was explained by first amidation of the substrate with
amines followed by intramolecular nucleophilic amination
of the p-allyl intermediate.4d
hindrance by the additional methyl group. Other symmetri-
cal substrates possessing two reaction sites such as
diacetates 6 and 8, dibenzoate 9, and dichloride 10 did not
react with amines under the same reaction conditions and
gave no noticeable product (Fig. 2).
In our previous report, we described the mechanistic
consideration for the formation of oxazolidinone via
seven-membered intermediate 12 (Scheme 2).1 But, this
pathway seems to be unlikely because of the formation of
relatively unstable seven-membered ring and also olefinic
trans–cis isomerization. The heat of formation of hypo-
thetical intermediates 11, 12, and 14 (R¼Me) was 2120.6,
253.6 and 2115.3 kcal/mol, respectively, by the AM1
calculations.6 As mentioned above, the results of no
enantio-selection observed in the reaction using chiral
amine and amino alcohol as nucleophile suggests that the
stage of nucleophilic attack is not an enantio-discrimination
step. Allylic rearrangement of the p-allyl intermediate 13
generated from the first amination product 11 would
produce secondary vinyl carbonate 14 (path B). The new
C–O bond formation would occur by the attack of carbonyl
oxygen of 13 to the more substituted terminus (electron
deficient site) of allyl system to produce carbonate 14.
Intramolecular amide formation by nucleophilic attack of
nitrogen to the carbonyl group should give oxazolidinone 2.
Other nucleophiles such as amino acids (e.g. phenyl-
alanine), amino acid esters (e.g. phenylglycine methyl
ester hydrochloride) and hydrazide (e.g. p-toluenesulfon-
hydrazide) gave no desired product in the same manner.
Another diallylcarbonate ester such as 5 or 7 also gave no
corresponding oxazolidinone, probably due to steric
Scheme 2.

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S. Tanimori et al. / Tetrahedron 59 (2003) 3745–3751
Table 3. Asymmetric synthesis of oxazolidinone using chiral ligands
Entry
Amine
(equiv.)
Pd catalyst
(mol%)
Ligand
(mol%)
Solvent
Temperature
(8C)
Time
(h)
Recovery 1
(%)
Yield
(%)a
Selectivityb
(de. %)
1
2
3
4
5
6
7
S (1.5)
S (1.5)
S (1.5)
R (1.5)
R (1.5)
R (1.5)
S (1.5)
[Pd(h3-C3H5)Cl]2 (0.25)
[Pd(h3-C3H5)Cl]2 (0.25)
[Pd(h3-C3H5)Cl]2 (0.5)
Pd2dba3·CHCl3 (0.25)
[Pd(h3-C3H5)Cl]2 (0.25)
Pd2dba3·CHCl3 (0.25)
Pd2dba3·CHCl3 (0.25)
(R)-(þ)-BINAP (0.64)
(S)-(R)-BPPFOH (0.64)
(R)-(S)-BPPFA (1.3)
(S)-(R)-BPPFOAc (0.64)
(S)-(R)-BPPFOAc (0.64)
(S)-(R)-BPPFOAc (0.64)
(S)-(R)-BPPFOAc (0.64)
THF
RT
RT
RT
40
RT
RT
40
3.5
19.5
21.5
20
1.5
1.5
0
0
0
52
53
32
56:46 (8)
44:56 (12)
39:61 (22)
83:17 (66)
85:15 (70)
95:5 (90)
8:92 (84)
CH2Cl2
CH2Cl2
THF
CH2Cl2
CH2Cl2
THF
0
67
68
80
0
13 (41)c
13 (66)c
23
39.5
a
Isolated yield.
Less polar/more polar.
Yield based on consumed starting material.
b
c
Formation of pyrrole 16 and aziridine 17 from p-allyl
intermediate 15 would also be possible,4d but we could not
detect such compounds. To determine the exact mechanism,
it should be necessary to synthesize hypothetical inter-
mediates such as 11, 12 and 14 to subject them to the same
reaction conditions. Such approach is now under
investigation.
on the double stereo-differentiation of the chirality of the
ligand and nucleophilic amines was observed (entry 4 vs 7).
Determination of the absolute stereochemistry of products
was conducted as follows (Scheme 3). Oxidative cleavage
of the double bond of oxazolidinone 2h from (S)-
phenethylamine with OsO4/NaIO4 gave aldehyde 18
which was reduced with NaBH4 to provide known alcohol
(10S,5S)-197 in 62% yield. The sign and absolute value of
the optical rotation of 19 ([a]2D9¼230.6 (c 0.5, CHCl3))
were nearly coincident with literature values ([a]D¼228.4
(c 5, CHCl3)).7 On the other hand, the more polar isomer of
2h should be (10S, 5R)-form and also oxazolidinone 2i from
(R)-phenethylamine possessimg the same Rf value with 2h
in the same solvent system (hexane/EtOAc¼2.5:1) should
be the enantiomer of 2h (Fig. 3). Thus, all four
stereoisomers of 3-(10-phenylethy)-5-vinyloxazolidin-2-
one 2 h and 2i have been assigned. To the best of our
knowledge, this is the first example of catalytic asymmetric
synthesis of 5-vinyloxazolidin-2-one.
As described above, the reaction using chiral amine and
achiral catalyst gave oxazolidinone as a 1:1 mixture of
diastereomers (Table 2, entry 5 and 6). Fortunately, in the
case using simple and inexpensive chiral 1-phenylethyl-
amine, each diastereomer was easily separable on simple
silica gel chromatography to give diastereomerically pure
(which means enantiomerically pure) oxazolidinone, which
would be advantageous for the practical production of
optically pure materials in laboratory scale. The results
prompted us to investigate the influence of chiral phosphine
ligands in this reaction. The results using various chiral
ligands are summarized in Table 3. (S)-N,N-Dimethyl-1-
[(R)-2-(diphenylphosphino)ferrocenyl]ethylamine (PPFA),
(1R, 2R)-(þ)-1,2-diaminocyclohexane-N,N0-bis(20-di-
phenylphosphinobenzoyl) (Trost ligand), and (R)-(þ)-2-
[2-(dihenylphosphino)phenyl]-4-(1-methylethyl)-4,5-di-
hydrooxazole gave no reaction product. As a result,
BPPFOAc gave a good selectivity, though the yields were
low (entry 4–7). Although elongation of the reaction time
and also elevating the temperature provided a good yield,
selectivity was decreased (entry 4 vs 5 and 6). Notable effect
3. Conclusion
In summary, we have developed a new simple protocol for
the preparation of various functionalized 5-vinyl-2-oxazo-
lidinone derivatives mediated by palladium-phosphine
catalyst even in enantiomerically pure forms. Further
work directed toward the synthesis of biologically active
Scheme 3.

S. Tanimori et al. / Tetrahedron 59 (2003) 3745–3751
3749
Figure 3.
compounds starting from the obtained products and
mechanistic investigations including the asymmetric
induction pathway are now in progress.
4.2.2. 3-[1-Benzyl(4-piperidyl)]-5-vinyl-1,3-oxazolidin-2-
one (2b). Yield: 61%. Colorless oil. Rf¼0.36 (hexane/
EtOAc¼1:1). IR (KBr): 3467, 2919, 1749, 1428, 1252,
1029, 737 cm21. 1H NMR (270 MHz, CDCl3): d 1.57–1.83
(4H, m), 2.07 (2H, dt, J¼3.9, 11.6 Hz), 2.94 (2H, d,
J¼11.6 Hz), 3.21 (1H, dd, J¼7.0, 8.5 Hz), 3.50 (2H, s), 3.64
(1H, t, J¼8.5 Hz), 3.60–3.82 (1H, m), 4.90 (1H, dd, J¼7.0,
15.0 Hz), 5.30 (1H, d, J¼10.4 Hz), 5.41 (1H, d, J¼17.1 Hz),
5.88 (1H, ddd, J¼7.0, 10.4, 17.1 Hz), 7.18–7.42 (5H, m).
13C NMR (67.5 MHz, CDCl3): d 29.0, 29.4, 45.9, 50.8, 52.4,
52.5, 62.8, 73.9, 118.5, 126.9, 128.0, 128.9, 134.3, 137.9,
156.9. EI MS m/z (%) 286 (1, Mþ), 195 (4), 149 (5), 132
(13), 91 (47), 82 (100). HRMS calcd for C17H22O2N2 (Mþ)
286.3759; found 286.3741.
4. Experimental
4.1. General
Infrared (IR) spectra were recorded on a Perkin–Elmer FT-
IR 1760X spectrometer. NMR spectra were recorded on a
JEOL JNM-GX 270 spectrometer, operating at 270 MHz for
1H NMR and 67.5 MHz for 13C NMR. Chemical shifts in
CDCl3 are reported on the d scale relative to CHCl3
(7.26 ppm for 1H NMR and 77.00 ppm for 13C NMR) as an
internal reference. The following abbreviations are used to
multiplicities: ‘s’ (singlet), ‘d’ (doublet), ‘t’ (triplet), ‘m’
(multiplet), ‘br’ (broad). Optical rotations were measured on
a JASCO DIP-360 polarimeter. Mass spectra were measured
on a JEOL JNM-AX 500 mass spectrometer. Column
chromatography were carried out with silica gel Merck 60
(230–400 mesh ASTM). Reactions were carried out in dry
solvents under an argon atmosphere. Tetrahydrofuran
(THF) was distilled from sodium benzophenone ketyl.
Dichloromethane (CH2Cl2) was distilled from calcium
hydride. Other reagents were purified by usual methods.
4.2.3. 3-(2-Indol-3-ylethyl)-5-vinyl-1,3-oxazolidin-2-one
(2c). Yield: 74%. Colorless crystal. Mp: 888C. Rf¼0.57
(hexane/EtOAc¼1:1.5). IR (KBr): 3241, 3059, 2924, 2863,
1
1729, 1486, 1438, 1335, 1251, 1099, 1016, 746 cm21. H
NMR (270 MHz, CDCl3): d 3.01 (1H, d, J¼7.0 Hz), 3.11
(1H, dd, J¼6.7, 8.5 Hz), 3.49 (2H, t, J¼7.0 Hz), 3.55 (1H,
dd, J¼6.7, 7.0 Hz), 4.79 (1H, ddd, J¼6.7, 7.0, 8.5 Hz), 5.21
(1H, d, J¼10.4 Hz), 5.36 (1H, d, J¼17.1 Hz), 5.75 (1H, ddd,
J¼6.7, 10.4, 17.1 Hz), 7.01–7.60 (5H, m), 8.39 (1H, s). 13C
NMR (67.5 MHz, CDCl3): d 23.5, 44.4, 50.3, 73.8, 111.3,
112.0, 118.3, 118.6, 119.2, 121.8, 121.9, 127.1, 134.3,
136.1, 157.7. EI MS m/z (%) 256 (8, Mþ), 143 (100), 130
(95), 115 (5), 103 (10), 77 (13), 55 (24). HRMS calcd for
C17H22O2N2 (Mþ) 256.3060; found 256.3034.
4.2. General procedure for the synthesis of oxazolidones
A degassed solution of 2-butenylene dicarbonate 1 (0.27 g,
1.31 mmol, 1.5 equiv.), amine (0.88 mmol, 1 equiv.),
[Pd(h3-C3H5)Cl]2 (2 mg, 0.0054 mmol, 0.62 mol%), and
dppf (7.6 mg, 0.014 mmol, 1.6 mol%) in dichloromethane
(1.5 ml) was stirred at room temperature for 15 h. The
mixture was filtered through a pad of silica gel and the
solvent evaporated in vacuo. The residue was then subjected
to preparative TLC.
4.2.4. 3-[(4-Aminophenyl)methyl]-5-vinyl-1,3-oxazoli-
din-2-one (2d). Yield: 26%. Colorless oil. Rf¼0.15
(hexane/EtOAc¼1:1). IR (neat): 3359, 2926, 1740, 1626,
1
1515, 1433, 1260 cm21. H NMR (270 MHz, CDCl3): d
3.09 (1H, dd, J¼7.8, 8.9 Hz), 3.51 (1H, dd, J¼8.6, 8.9 Hz),
4.31 (2H, ABq, J¼15.0, 24.1 Hz), 4.88 (1H, ddd, J¼7.6,
7.8, 8.6 Hz), 5.29 (1H, d, J¼10.4 Hz), 5.41 (1H, d,
J¼16.2 Hz), 5.81 (1H, ddd, J¼7.6, 10.4, 16.2 Hz), 6.63–
7.26 (4H, m). 13C NMR (67.5 MHz, CDCl3): d 47.8, 49.1,
73.8, 115.1, 118.6, 125.2, 129.4, 134.4, 146.1, 162.0. EI MS
m/z (%) 218 (20, Mþ), 164 (100), 119 (70), 106 (71), 77
(23), 53 (19). HRMS calcd for C17H22O2N2 (Mþ) 218.2568;
found 218.2571.
4.2.1. 3-Benzyl-5-vinyl-1,3-oxazolidin-2-one (2a). Yield:
61%. Colorless oil. Rf¼0.42 (hexane/EtOAc¼2:1). IR
1
(neat): 2922, 1752, 1426, 1253, 1025, 704 cm21. H NMR
(270 MHz, CDCl3): d 3.13 (1H, dd, J¼7.3, 8.5 Hz, one of
CH2N), 3.55 (1H, dd, J¼6.4, 8.5 Hz, one of CH2N), 4.43
(2H, ABq, J¼15.0, 24.1 Hz, CH2Ph), 4.90 (1H, dd, J¼6.4,
7.3 Hz, CH–O), 5.29 (1H, d, J¼10.4 Hz, CHvCHH (cis)),
5.40 (1H, d, J¼17.1 Hz, CHvCHH (trans)), 5.86 (1H, ddd,
J¼6.4, 10.4, 17.1 Hz, CHvCH2), 7.20–7.43 (5H, m). 13C
NMR (67.5 MHz, CDCl3): d 48.2, 49.2, 73.8, 118.7, 127.8,
127.9, 128.6, 134.2, 135.4, 157.6. EI MS m/z (%) 203 (15,
Mþ), 153 (10), 136 (7), 120 (5), 104 (9), 91 (23), 85 (66), 83
(100), 77 (18), 54 (18). HRMS calcd for C17H22O2N2 (Mþ)
203.0946; found 203.0742.
4.2.5. 3-(2-Hydroxy-1,1-dimethylethyl)-5-vinyl-1,3-oxa-
zolidin-2-one (2e). Yield: 16%. Colorless oil. Rf¼0.46
(hexane/EtOAc¼1:1). IR (neat): 3418, 2977, 1731, 1413,
1239, 1034, 768 cm21. 1H NMR (270 MHz, CDCl3): d 1.30
(6H, s), 3.38 (1H, dd, J¼7.3, 7.6 Hz), 3.77 (2H, s), 3.83–
3.73 (1H, m), 4.90 (1H, dd, J¼7.3, 7.6 Hz), 5.33 (1H, d,
J¼10.1 Hz), 5.43 (1H, d, J¼17.4 Hz), 5.91 (1H, ddd,
J¼17.4, 10.1, 7.6 Hz). 13C NMR (67.5 MHz, CDCl3): d
22.6, 23.3, 49.0, 57.8, 69.0, 73.9, 118.9, 134.1, 157.3.

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S. Tanimori et al. / Tetrahedron 59 (2003) 3745–3751
4.2.6. 3-((1S,2R)-2-Hydroxy-1-methyl-2-phenylethyl)-5-
vinyl-1,3-oxazolidin-2-one (2f). A 1:1 mixture of dia-
stereomers. Yield: 57%. Colorless solid. Rf¼0.32
(hexane/EtOAc¼3:1). IR (KBr): 3411, 2939, 1720, 1448,
45.5, 51.4, 73.9, 118.6, 126.8, 127.7, 128.5, 134.4, 139.3,
157.1. EI MS m/z (%) 217 (56, Mþ), 202 (36), 163 (24), 153
(21), 131 (46), 105 (100), 77 (69). HRMS calcd for
C17H22O2N2 (Mþ) 217.1103; found 217.1074. More polar
isomer (10S,5S)-2h: colorless liquid. Rf¼0.33 (hexane/
EtOAc¼2.5:1). [a]D22¼265.8 (c 1.1, CHCl3). 1H NMR
(270 MHz, CDCl3): d 1.58 (1H, d, J¼7.3 Hz), 2.85 (1H, dd,
J¼7.6, 8.5 Hz), 3.61 (1H, dd, J¼7.6, 8.5 Hz), 4.90 (1H, dt,
J¼7.3, 7.6 Hz), 5.22 (1H, q, J¼7.3 Hz), 5.23 (1H, d,
J¼10.7 Hz), 5.35 (1H, d, J¼17.1 Hz), 5.75 (1H, ddd, J¼7.6,
10.4, 17.1 Hz), 7.14–7.48 (5H, m). 13C NMR (67.5 MHz,
CDCl3): d 16.5, 45.3, 51.2, 73.9, 118.5, 126.8, 127.7, 128.5,
134.3, 139.1, 157.1.
1
1260, 998, 762, 702 cm21. H NMR (270 MHz, CDCl3): d
1.16 (3H, d, J¼7.0 Hz), 1.18 (3H, d, J¼7.0 Hz), 3.15 (1H,
dd, J¼7.3, 8.9 Hz), 3.27 (1H, dd, J¼6.7, 8.9 Hz), 3.64 (1H,
dt, J¼8.9, 12.5 Hz), 3.89–4.04 (1H, m), 4.65–4.89 (1H, m),
4.93 (1H, dd, J¼4.0, 5.8 Hz), 5.24–5.39 (2H, m), 5.70–5.85
(1H, m), 7.18–7.43 (5H, m). 13C NMR (67.5 MHz, CDCl3):
d 157.7, 141.2, 141.1, 134.3, 134.2, 128.2, 127.6, 126.0,
125.9, 118.7, 118.6, 76.5, 76.4, 74.5, 74.4, 55.1, 48.3, 48.1,
11.6, 11.4. EI MS m/z (%) 247 (2, Mþ), 190 (11), 118 (44),
105 (100), 91 (17), 77 (16), 56 (25). HRMS calcd for
C17H22O2N2 (Mþ) 247.2955; found 247.2941.
(10R, 5S)-2i: Rf¼0.43 (hexane/EtOAc¼2.5:1). [a]2D2¼þ37.3
(c 1.84, CHCl3).
4.2.7. 3-[(1R,2S)-2-Hydroxyindanyl]-5-vinyl-1,3-oxazoli-
din-2-one (2g). Yield: 41% (less polar 21%, more polar
20%). Rf¼0.17 and 0.29 (hexane/EtOAc¼2:1). Less polar:
colorless needles. Mp. 127–1288C. Rf¼0.29 (hexane/
EtOAc¼2:1). [a]2D2¼247.1 (c 1.2, CHCl3). IR (neat):
(10R,5R)-2i: Rf¼0.33 (hexane/EtOAc¼2.5:1). [a]2D2¼þ78.4
(c 1.84, CHCl3).
4.2.9. (10S, 5S)-5-Hydroxymethyl-3-(1-phenylethyl)oxa-
zolidin-2-one (19). To a solution of alkene (10S,5S)-2h
(50 mg, 0.23 mmol) in THF (4.2 mL) stirred under nitrogen
atmosphere was added 1% aqueous osmium tetraoxide
solution (1 mL). Then, sodium periodate (0.25 g,
1.15 mmol) in water (1.4 mL) was added to the solution
and the resulting mixture was stirred for 2 h.
1
3419, 2916, 1731, 1428, 1255, 757, 742 cm21. H NMR
(270 MHz, CDCl3): d 2.91 (1H, dd, J¼6.1, 16.5 Hz), 3.21–
3.42 (3H, m), 4.79–4.92 (2H, m), 5.43–5.23 (3H, m), 5.94
(1H, ddd, J¼7.0, 10.4, 17.1 Hz), 7.13–7.37 (4H, m). 13C
NMR (67.5 MHz, CDCl3): d 39.9, 48.6, 60.1, 73.0, 75.4,
119.2, 125.3, 125.7, 127.3, 129.0, 134.4, 137.1, 140.7,
158.6. EI MS m/z (%) 245 (2, Mþ), 188 (33), 176 (28), 144
(100), 115 (92), 103 (13), 91 (13), 77 (13), 56 (25). HRMS
calcd for C17H22O2N2 (Mþ) 245.2796; found 245.2818.
More polar: colorless liquid. Rf¼0.17 (hexane/EtOAc¼2:1).
[a]2D2¼þ36.6 (c 1.3, CHCl3). 1H NMR (270 MHz, CDCl3):
d 2.93 (1H, dd, J¼5.8, 16.8 Hz), 3.00 (1H, dd, J¼6.4,
8.9 Hz), 3.28 (1H, dd, J¼7.0, 16.8 Hz), 3.75 (1H, t,
J¼8.9 Hz), 4.83 (1H, dt, J¼5.8, 6.4 Hz), 4.99 (1H, dd,
J¼6.4, 15.3 Hz), 5.21–5.42 (3H, m), 5.84 (1H, ddd, J¼6.4,
10.4, 17.1 Hz), 7.13–7.38 (4H, m). 13C NMR (67.5 MHz,
CDCl3): d 39.8, 48.4, 60.2, 72.8, 74.5, 118.5, 125.3, 125.5,
127.2, 128.9, 134.4, 136.9, 140.7, 158.6.
The above mixture was diluted with ethanol (1 mL), sodium
borohydride (4.4 mg, 0.12 mmol) was added at 08C, and the
resulting mixture was stirred for 2.5 h at room temperature.
Water (5 mL) was added and the mixture was extracted with
ether. The combined organic phase was washed with water
and brine, dried over MgSO4, filtered, and evaporated in
vacuo to yield crude alcohol, which was purified by silica
gel chromatography (hexane/EtOAc¼1:2) to give pure
alcohol 19 (31 mg, 62%) as a white solid.
Yield: 62% (2 steps). Rf¼0.6 (EtOAc). IR (KBr): 3392,
1
2897, 1733, 1444, 1406, 1257, 1074, 760 cm21. H NMR
4.2.8. 3-(1-Phenyleth-1-yl)-5-vinyl-1,3-oxazolidin-2-one
(2h and 2i). A degassed solution of 2-butenylene dicarbo-
nate 1 (50 mg, 0.24 mmol), (S)-(2)-phenethylamine (0.046
mL, 0.36 mmol), Pd2(dba)3·CHCl3 (1.2 mg, 0.0012 mmol,
0.5 mol%), and DPPFOAc (2.0 mg, 0.0031 mmol,
1.3 mol%) in THF (1 ml) was stirred at 408C for 20 h. The
mixture was filtered through a pad of silica gel and the
solvent evaporated in vacuo. The residue was then subjected
to0 preparative TLC (50% EtOAc in hexane) to produce
(1 S,5R)-2h (29.2 mg, 55%) and (10S,5S)-2h (6 mg, 12%) as
an oil.
(270 MHz, CDCl3): d 1.5 (3H, d, J¼7.3 Hz, CH3), 3.15 (1H,
t, J¼8.5, 9.2 Hz, one of CH2N), 3.4 (1H, dd, J¼8.5, 9.2 Hz,
one of CH2N), 3.7 (2H, m, CH2OH), 3.8 (1H, br s, OH),
4.4–4.6 (1H, m, CH–O), 5.20 (1H, q, J¼7.0 Hz, NCH2Ph),
7.2–7.3 (5H, m, ArH). 13C NMR (67.5 MHz, CDCl3): d
16.2, 41.2, 51.5, 63.1, 73.4, 126.7, 127.8, 128.6, 139.3,
157.2. [a]2D9¼230.6 (c 0.5, CHCl3) (lit.7228.4 (c 5,
CHCl3)). Mp. 1018C (lit.7 1028C).
References
Yield: 67% (less polar 55%, more polar 12%). Less polar
isomer (10S,5R)-2h: colorless liquid. Rf¼0.43 (hexane/
EtOAc¼2.5:1). [a]2D2¼234.0 (c 0.75, CHCl3). IR (KBr):
2980, 1750, 1420, 1244, 1024, 703 cm21 1H NMR
.
1. Tanimori, S.; Kirihata, M. Tetrahedron Lett. 2000, 41,
6785–6788.
2. (a) Mai, A.; Artico, M.; Esposito, M.; Sbardella, G.; Massa, S.;
(270 MHz, CDCl3): d 1.56 (3H, d, J¼7.3 Hz, –CH3), 3.20
(1H, t, J¼8.6 Hz, one of CH2N), 3.30 (1H, t, J¼8.6 Hz, one
of CH2N), 4.82 (1H, dd, J¼7.3, 7.6 Hz, HC–O), 5.22 (1H,
q, J¼7.3 Hz, –CHMePh), 5.30 (1H, d, J¼10.6 Hz,
CHvCHH (cis)), 5.39 (1H, d, J¼17.2 Hz, CHvCHH
(trans)), 5.89 (1H, ddd, J¼7.6, 10.2, 17.2 Hz, CHvCH2),
7.20–7.43 (5H, m). 13C NMR (67.5 MHz, CDCl3): d 16.2,
`
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3. For recent examples, see: (a) Holden, K. G.; Mattson, M. N.;

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3751
Cha, K. H.; Rapoport, H. J. Org. Chem. 2002, 67, 5913–5918.
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1987, 43, 2505–2512.