Synthesis of enantiomerically pure divinyl- and diallylcarbinols

Article abstract of DOI:10.1039/b200976e

Acylated oxazolidinones and bornane sultams can be cleaved to divinyl- and diallylcarbinols by treatment with vinyl- or allylmetal compounds. For the preparation of divinylcarbinols, acylated bornane sultams are the starting materials of choice, while for the preparation of diallylcarbinols acylated oxazolidinones and bornane sultams work equally well.

Full text of DOI:10.1039/b200976e

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Synthesis of enantiomerically pure divinyl- and diallylcarbinols
Bernd Schmidt* and Holger Wildemann
Universität Dortmund, Fachbereich Chemie, Organische Chemie, Otto-Hahn-Strasse 6,
D-44227 Dortmund, Germany. E-mail: bschmidt@chemie.uni-dortmund.de
1
Received (in Cambridge, UK) 28th January 2002, Accepted 8th March 2002
First published as an Advance Article on the web 25th March 2002
Acylated oxazolidinones and bornane sultams can be cleaved to divinyl- and diallylcarbinols by treatment with
vinyl- or allylmetal compounds. For the preparation of divinylcarbinols, acylated bornane sultams are the starting
materials of choice, while for the preparation of diallylcarbinols acylated oxazolidinones and bornane sultams work
equally well.
Introduction
Carbinols with unsaturated side chains are interesting starting
materials for a variety of synthetic transformations. For
example, divinylcarbinols have been employed in hydroacyl-
ation reactions,1 formation of phosphorus heterocycles,2
enantioselective epoxidation,3–5 palladium-catalyzed malonate
addition,6 catalytic asymmetric intramolecular hydrosilation7
and radical cyclizations.8 Over the past few years several
examples have been reported where divinylcarbinols played a
key role in enantioselective9,10 and diastereoselective ring
closing metathesis reactions.11–15 Diallylcarbinols have been
Scheme 1 Reagents and conditions: i, NaHMDS (1.5 equiv.), THF,
used in silylformylation,16,17 Pauson–Khand reactions,18 Prins-
cyclizations,19 and various other reactions.20–23 Applications in
olefin metathesis have included the formation of cyclopent-
enols,24 spirocyclic cyclopentenes25 and oxacycles.26,27 Carbinols
are conveniently prepared from esters by treatment with excess
organometallic reagent. Thus, enantiomerically pure carbinols
with a stereogenic centre adjacent to the alcohol moiety become
available from esters with a centre of chirality in the α-position,
e.g. α-hydroxy carboxylic acid esters13 or α-amino acid esters.15,28
Well-established methods for the preparation of enantio-
merically pure carboxylic acids and derivatives use chiral amine
auxiliaries, such as oxazolidinones29,30 or camphor sultams.31
Standard methods for the cleavage of these auxiliaries are
reduction to the primary alcohols, or hydrolysis to the free
carboxylic acids. Surprisingly, the cleavage of oxazolidinones or
camphor sultams using organometallic reagents has hardly
been investigated. We are aware of only one example for each of
these cases: Kashima et al. reported several years ago the form-
ation of a diallylcarbinol by addition of an allylzinc reagent to
achiral benzoylated oxazolidinone in excellent yield,32 and the
cleavage of an acylated sultam with methylmagnesium iodide to
yield a dimethylcarbinol has been reported by Curran et al.33 In
this contribution we describe the scope and limitations of a
novel synthesis of α-chiral divinyl- and diallylcarbinols.
Ϫ78 ЊC, then ICH2CH᎐CH2 or BrCH2Ph; ii, [Cl2(Cy3P)2Ru᎐CHPh]
᎐
᎐
(3 mol%), DCM, 20 ЊC.
catalyst (Scheme 1).35 Alkylation of acylated bornane sultams
3a–d was achieved under the same conditions. From sultams
3a–d [derived from (S)-camphorsulfonic acid] alkylation pro-
ducts 4a–g result, which have, compared to products 2a–d, the
opposite configuration of the α-position. 4f was prepared by
ring closing olefin metathesis of 4e in the presence of Grubbs’
catalyst (Scheme 2).
Results and discussion
Alkylation of acylated oxazolidinones and bornane sultams
Scheme 2 Reagents and conditions: i, NaHMDS (1.5 equiv.), THF,
Acylated oxazolidinones and sultams were obtained from the
corresponding carboxylic acids via formation of the mixed
anhydrides using pivaloyl chloride.34 Alkylation of oxazolid-
inones 1a and 1b was achieved by treatment with NaHMDS,
followed by allyl iodide or benzyl bromide, respectively, to give
oxazolidinones 2a–c. Dihydropyran 2d was obtained from
2c by ring closing metathesis using 3 mol% of Grubbs’
Ϫ78 ЊC, then ICH2CH᎐CH2 or BrCH2Ph or BrCH2CO2Et; ii,
᎐
[Cl2(Cy3P)2Ru᎐CHPh] (3 mol%), DCM, 20 ЊC.
᎐
We also investigated the alkylation of oxazolidinones
acylated with allylated lactic acid and mandelic acid. 2-Allyloxy-
propionic acid (5a) was converted into the acylated oxazol-
idinone 6a. Allylation of 6a to the metathesis precursor 7 was
1050
J. Chem. Soc., Perkin Trans. 1, 2002, 1050–1060
This journal is © The Royal Society of Chemistry 2002
DOI: 10.1039/b200976e

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Table 1 Formation of diallylcarbinols from oxazolidinones 2 or born-
achieved in only moderate yield of 35% and a diastereomeric
ratio of 10 : 1, using NaHMDS and allyl iodide. Ring closing
metathesis of 7 gave the enantiomerically and diastereo-
merically pure dihydropyran 8. 2-Allyloxymandelic acid (5b)
was converted into the acylated valine-derived oxazolidinone
analogously. However, the allylation reaction failed. Instead,
allyl benzoate 9, which was unambiguously identified by com-
parison of its spectroscopic data, was the only isolable product.
The mechanism leading to the formation of allyl benzoate
remains unclear (Scheme 3).
ane sultams 4
Starting material
Product
R1
R2
Yield (%)
2a
2b
2c
2d
4a
4b
4c
4e
10a
10b
10c
10d
12a
12b
12c
12e
Me
Me
Allyl
Bn
Allyl
70
82
76
63
83
64
85
96
OAllyl
OCH2CH᎐CHCH2
Me
Allyl
OMe
OAllyl
᎐
Allyl
Bn
Allyl
Allyl
Scheme 3 Reagents and conditions: i, NEt3, PivCl, then lithiated
oxazolidinone [(S)-6a, 74%; 6b, 57% (dr = 1 : 1)]; ii, NaHMDS
(1.5 equiv.), THF, Ϫ78 ЊC, then ICH2CH᎐CH2 (7a, 35%; 9, 47%);
᎐
iii, [Cl2(Cy3P)2Ru᎐CHPh] (3 mol%), DCM, 20 ЊC (80% of 8).
Scheme 4 Reagents and conditions: i, AllylMgBr (1.0 M solution in
ether, 4 equiv.), ether, Ϫ78 ЊC, then aq. NH4Cl solution.
᎐
Formation of diallylcarbinols
resulting from 1,4- rather than 1,2-addition of the second
equivalent of vinylmagnesium chloride.27 In the case of 2a,b,
however, neither the expected divinylcarbinol 14a,b nor the
expected side product, butenone 15a,b, were observed. Instead,
the oxazolidinone is cleaved to yield acrylates 16a,b. The situ-
ation changes if an ether functionality is present in the α-posi-
tion. 2c is cleaved under the same conditions to yield all three
products 14c, 15c and 16c in a 1.5 : 1 : 1 ratio. It has been
described in the literature that the formation of 1,4-addition
products can be suppressed by transmetallation with ceric
chloride.36 When we repeated the cleavage of 2a–c under these
conditions, very similar results were obtained for 2a,b. In the
case of 2c only the divinylcarbinol 14c was isolated in moderate
yield (40%). Formation of the corresponding 1,4-addition
product 15c and of acrylate 16c was not observed under these
conditions. In the case of sterically congested oxazolidinone 8a,
the acrylate 17 was formed exclusively, despite the chelating
oxygen present in the molecule. It is interesting to note that
similarly substituted esters react with vinylmagnesium chloride
with exclusive formation of 1,4-addition products of type 15
(Scheme 5).
Upon treatment of an acylated oxazolidinone with excess
organometallic reagent, cleavage of the heterocycle by nucleo-
philic attack at the carbonyl carbon may occur. The report by
Kashima et al. demonstrates that this does not seem to be a
problem if the allylzinc reagent is used, the corresponding mag-
nesium compound, however, was not investigated previously.
Treatment of acylated oxazolidinones 2a–d with a fourfold
excess of allylmagnesium bromide leads to a clean cleavage of
the chiral auxiliary. Starting from (S)-phenylalanine-derived
oxazolidinones, the R-configured products 10a–d and the free
oxazolidinone 11 are formed. The products are easily separated
and no side products resulting from the cleavage of the hetero-
cycle were detected. Cleavage of the acylated sultams 4a–c and
4e under the same conditions gives S-configured diallylcarb-
inols 12a–c and 12e and the free bornane sultams 13 in good
yields. Examples 10a/12a and 10c/12e were obtained in both
enantiomeric forms (Scheme 4 and Table 1). The values of the
optical rotations are identical within the range of experimental
error.
Formation of divinylcarbinols
Formation of acrylates 16 is remarkable, because even in the
presence of a fourfold excess of vinyl metal compound only one
vinyl moiety is transferred to the oxazolidinone. A plausible
explanation is the intermediate formation of stable tetrahedral
intermediates A, which, analogously to the Weinreb-amides,37
are stabilized by chelation and decompose upon hydrolysis to
After we had observed that cleavage of acylated oxazolidinones
with allylmagnesium bromide is a very smooth process, we were
very surprised to see that cleavage with the vinylmagnesium
compound was not straightforward at all. The formation of
butenones 15 was an expected side reaction, these products
J. Chem. Soc., Perkin Trans. 1, 2002, 1050–1060
1051

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Table 2 Formation of divinylcarbinols from bornane sultams 4
Yield (%)
Starting material R1
R2
Conditionsa 18
19
b
b
b
b
4a
4a
4b
4b
4c
4d
4e
4e
4f
Me
Me
Allyl
Allyl
Bn
Bn
Allyl
Bn
Allyl
Allyl
᎐
i
ii
i
ii
ii
ii
i
ii
ii
i
Allyl
Allyl
OMe
OMe
OAllyl
OAllyl
70
73
59
79
62
43
—
—
20
—
—
17
–OCH2CH᎐CHCH2–
OAllyl
4g
–CH2CO2Et
a Conditions i and ii as given in Scheme 6 b No conversion.
Scheme 5 Reagents and conditions: i, H2C᎐CHMgCl (2.1 equiv.),
᎐
THF, Ϫ78 ЊC, then. aq. NH4Cl solution: 2a
(70%), 2c 14c (28%) ϩ 15c (19%) ϩ 16c (19%), 8a
ii, CeCl3 (4.0 equiv.), H2C᎐CHMgCl (3.6 equiv.), Ϫ78 ЊC, then aq. HCl
16a (60%), 2b
16b
17 (40%);
᎐
(1 M): 2a
16a (57%), 2b
16b (67%), 2c
15c (40%).
the acrylates 16. In the case of 2c an additional donor ligand
(the ether moiety in the α-position) is able to coordinate to the
metal and form a five-membered chelate complex (structure B).
This might explain why acrylate 16c is formed only in minor
amounts or not at all in this case (Fig. 1).
Scheme 6 Reagents and conditions: i, H2C᎐CHMgCl (2.1 equiv.),
᎐
THF, Ϫ78 ЊC, then. aq. NH4Cl solution; ii, CeCl3 (4.0 equiv.), H2C᎐
᎐
CHMgCl (3.6 equiv.), Ϫ78 ЊC, then aq. HCl (1 M).
Investigations directed towards the selective formation of
butenones
But-1-en-4-ones with a centre of chirality in the α-position are
normally prepared in a two-step procedure by transamidation
of acylated oxazolidinones or sultams with N,O-dimethyl-
hydroxylamine to the corresponding Weinreb-amides, and sub-
sequent addition of butenylmagnesium bromide.38–40 Direct
addition of butenylmagnesium bromide to the acylated oxazo-
lidinones and sultams would result in the formation of the
corresponding carbinols. A process leading directly from the
acylated chiral auxiliaries to the butenones might be an attract-
ive alternative. As outlined above, vinyl Grignard reagents
normally give this transformation only as a side reaction.41
A vinylcopper compound is the reagent of choice if selective
1,4-addition is the goal.42 Thus, we investigated the cleavage
of a bornane sultam auxiliary using a vinylcopper com-
pound (obtained by transmetallation of vinylmagnesium chlor-
ide with copper iodide) for one example. Conversion of 4e to
butenone 19e is highly regioselective, however, the reaction is
rather slow. The butenone 19e was isolated as the only product
in 45% yield, along with 50% of the starting material 4e
(Scheme 7).
Fig. 1 Rationalization of different product distributions in the
cleavage reactions of 2a–c.
We saw a good chance to avoid this undesired acrylate
formation by using the sultam- rather than the oxazolidinone-
auxiliary. Surprisingly, the initially investigated acylated bornane
sultams 4a,b were recovered unchanged in nearly quantitative
yield upon treatment with vinylmagnesium or vinylcerium
reagent. In contrast, treatment of 4c–g (which all have an oxy-
gen atom in the α-position) with the vinyl metal compounds
leads to a clean and rapid formation of the corresponding
divinylcarbinols 18c–g (when Grignard reagents are used, the
butenone by-products 19 are observed) and the free camphor
sultam 13. The inertness of 4a,b towards the vinyl metal com-
pounds suggests that a chelation effect similar to the one
described for the oxazolidinones is working here. Obviously,
intramolecular coordination of the metal by an ether oxygen
facilitates nucleophilic attack at the carbonyl carbon. The
formation of 18g is especially remarkable. This divinylcarbinol
results from the chemoselective cleavage of the amide in 4g. As
long as stoichiometric amounts of vinyl metal compound are
used, the ester group is not attacked. It might be speculated
that this unusual chemoselectivity also originates from the
intermediate formation of a chelate complex (Scheme 6 and
Table 2).
Scheme 7 Reagents and conditions: i, CuI (2.0 equiv.), H2C᎐CHMgCl
᎐
(5.0 equiv.), THF, Ϫ78 ЊC (45%).
1052
J. Chem. Soc., Perkin Trans. 1, 2002, 1050–1060

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Application of carbinols in ring closing metathesis reactions
mately 30 min). The reaction was quenched by addition of
water (100 ml). The aqueous layer was extracted with MTBE
and the combined organic extracts were dried with MgSO4,
filtered and evaporated. The residue was purified by flash
chromatography on silica using cyclohexane–MTBE mixtures
as the eluent.
Divinylcarbinols derived from α-hydroxy carboxylic acids
are precursors for diastereoselective ring closing metathesis
reactions, a field recently investigated by ourselves14,43 and
others.12,26,44 The sequence outlined in this contribution makes
starting materials conveniently accessible that are not directly
prepared from commercially available or easily prepared
enantiomerically pure α-hydroxy carboxylic acids. Ring closing
metathesis of the divinylcarbinol 18g in the presence of
Grubbs’ catalyst yields the dihydropyran 20 with an exo-vinyl
side chain. Ring closing metathesis of the diallylcarbinol 10b
requires elevated temperatures: in the presence of Grubbs’ cat-
alyst, no conversion was observed at ambient temperature,
while the reaction proceeded smoothly in refluxing toluene to
give the enantiomerically pure cyclopentenol 21 (Scheme 8).
(4S)-4-Benzyl-3-propionyloxazolidin-2-one (1a)
From (4S)-4-benzyloxazolidin-2-one (5.00 g, 28.2 mmol) and
propionic acid (2.10 ml, 28.2 mmol) 1a (4.10 g, 62%) was
1
obtained. H NMR (400 MHz, CDCl3): δ 7.28–7.23 (2H, Ph),
7.19 (m, 1H, Ph), 7.15–7.11 (2H, Ph), 4.59 (dddd, 1H, J = 9.5,
9.0, 3.3, 3.0, HCN), 4.12 (dd, 1H, J = 9.0, 9.0, H COC᎐O), 4.08
᎐
2
(dd, 1H, J = 9.0, 3.3, H COC᎐O), 3.22 (dd, 1H, J = 13.3, 3.0,
᎐
2
H2CCHN), 2.91 (dm, 1H, J = 7.3, H2CCH3), 2.84 (dm, 1H, J =
7.3, H2CCH3), 2.69 (dd, 1H, J = 13.3, 9.5, H2CCHN), 1.12 (t,
3H, J = 7.3, H3C). 13C NMR (100 MHz, CDCl3): δ 174.0 [(0),
CCH2], 153.4 [(0), CO], 135.2 [(0), Ph], 129.3, 128.8, 127.2 [(1),
Ph], 66.1 [(2), CH2O], 55.0 [(1), CHN], 37.8, 29.1 [(2), CH2], 8.2
[(3), CH3].
(4S)-3-(2-Allyloxyethanoyl)-4-benzyloxazolidin-2-one (1b)
From (4S)-4-benzyloxazolidin-2-one (4.50 g, 25.4 mmol) and
2-allyloxyacetic acid (2.95 g, 25.4 mmol), 1b (5.45 g, 78%) was
obtained. MS (EI) m/z (%) 275 (Mϩ, <5), 234 (100), 216 (60),
188 (40), 160 (80), 134 (99). IR (film): ν/cmϪ1 1782s, 1662s,
1394m, 1263m, 1215m, 984m, 702m. Found: C, 65.8%; H,
6.6%; N, 4.9%. C15H17O4N requires C, 65.4%; H, 6.2%; N, 5.1%.
1H NMR (400 MHz, CDCl3) δ 7.30–7.19 (3H, Ph), 7.17–7.10
(2H, Ph), 5.90 (dddd, 1H, J = 17.3, 10.5, 5.8, 5.8, HC᎐H ), 5.28
᎐
2
(dddd, 1H, J = 17.3, 1.5, 1.5, 1.5, H C᎐CH), 5.19 (dddd, 1H, J =
᎐
2
10.5, 1.5, 1.5, 1.5, H C᎐CH), 4.61 (d, 2H, J = 3.0, H CC᎐O),
᎐
᎐
2
2
4.22 (dd, 1H, J = 9.0, 8.0, H COC᎐O), 4.16 (dd, 1H, J = 9.0, 3.0,
᎐
2
Scheme 8 Reagents and conditions: i, [Cl2(Cy3P)2Ru᎐CHPh] (3 mol%),
᎐
H COC᎐O), 4.11 (m, 1H, H CO/HCN), 4.07 (m, 1H, H CO/
᎐
2
2
2
DCM, 20 ЊC (69%); ii, [Cl2(Cy3P)2Ru᎐CHPh] (5 mol%), toluene, 110 ЊC
᎐
HCN), 4.03 (m, 1H, H2CO/HCN), 3.26 (dd, 1H, J = 13.3, 3.0,
H2CCHN), 2.75 (dd, 1H, J = 13.3, 8.8, H2CCHN). 13C NMR
(100 MHz, CDCl3) δ 170.2 [(0), CCH2], 153.4 [(0), CO], 134.9
(79%).
In conclusion, we have developed a novel route to enantio-
merically pure carbinols with unsaturated side chains. Synthetic
concepts directed towards the differentiation of vinyl or allyl
side chains using olefin metathesis and other transformations
are currently under investigation in our laboratory.
[(0), Ph], 133.7 [(1), CH᎐CH ], 129.4, 129.0, 127.4, [(1), Ph],
᎐
2
118.2 [(2), CH ᎐CH], 72.5, 69.5, 67.2 [(2), CH O], 54.8 [(1),
᎐
2
2
CHN], 37.7 [(2), CH2CHN]. [α]2D0 ϩ 66.2 (c 1.50 in CH2Cl2).
(2R)-N-Propionylbornane-10,2-sultam (3a)
From (2S)-Bornane-10,2-sultam (10.00 g, 46.4 mmol) and
propionic acid (3.46 ml, 46.4 mmol) 3a (10.37 g, 83%) was
obtained. 1H NMR (400 MHz, CDCl3) δ 3.82 (dd, 1H, J = 7.8,
5.0, HCN), 3.46 (d, 1H, J = 14.0, H2CS), 3.39 (d, 1H, J = 14.0,
Experimental
Instrumentation, product identification and general experi-
mental methods have been described previously.45 J values are
given in Hz. The number of coupled protons was analyzed by
APT experiments and is denoted by a number in parentheses
following the δC value. Optical rotations are given in units of
H CS), 2.76–2.64 (2H, H CC᎐O), 2.10 (dm, 1H, J = 14.0, H C),
᎐
2
2
2
2.03 (dd, 1H, J = 14.0, 7.8, H2C), 1.91–1.81 (3H, H2C, HC), 1.37
(dm, 1H, J = 9.8, H2C), 1.31 (dm, 1H, J = 9.5, H2C), 1.12
(t, 3H, J = 7.3, H3CCH2), 1.11 (s, 3H, H3C), 0.97 (s, 3H, H3C).
13C NMR (100 MHz, CDCl ) δ 172.6 [(0), C᎐O], 65.2 [(1),
10Ϫ1 deg cm2 gϪ1
.
᎐
3
General procedure for the preparation of acylated oxazolidinones
and sultams
CHN], 52.8 [(2), CH2S], 48.4, 47.7 [(0), Cq], 44.6 [(1), CH],
38.4, 32.8, 28.8, 26.4 [(2), CH2], 20.5, 19.8, 8.3 [(3), CH3].
To a solution of the corresponding acid (74 mmol) and triethyl-
amine (12.2 ml, 87 mmol) in THF (100 ml) was slowly added
pivaloyl chloride (9.20 ml, 74 mmol) at Ϫ78 ЊC under an
atmosphere of dry argon. The mixture was stirred at this tem-
perature for 5 min and then for 1 h at 0 ЊC. In a second flask, a
solution of the corresponding (4S)-4-benzyloxazolidin-2-one
or (2S)-bornane-10,2-sultam (62 mmol) in THF (100 ml) was
cooled to Ϫ78 ЊC and n-BuLi (25.8 ml of a 2.4 M solution in
hexanes, 62 mmol) was added via syringe. The solution was
then stirred for 30 min at Ϫ78 ЊC. The first solution was re-
cooled to Ϫ78 ЊC and then the cold solution of the lithium salt
of the oxazolidinone or sultam was added rapidly. Stirring was
continued at this temperature for 15 min and then at 0 ЊC until
the starting material was fully consumed, as indicated by TLC
(cyclohexane–methyl tert-butyl ether (MTBE) 2 : 1, approxi-
(2R)-N-(Pent-4-enoyl)bornane-10,2-sultam (3b)
From (2S)-Bornane-10,2-sultam (12.00 g, 55.8 mmol) and
pentenoic acid (5.70 ml, 55.8 mmol) 3b (15.60 g, 94%) was
1
obtained. H NMR (400 MHz, CDCl3) δ 5.80 (dddd, 1H, J =
17.3, 10.3, 6.5, 6.5, HC᎐CH ), 5.05 (dddd, 1H, J = 17.3, 1.5, 1.5,
᎐
2
1.5, H C᎐CH), 4.97 (dddd, 1H, J = 10.3, 1.5, 1.5, 1.5, H C᎐
᎐
᎐
2
2
CH), 3.84 (dd, 1H, J = 7.3, 5.5, HCN), 3.48 (d, 1H, J = 13.8,
H2CS), 3.40 (d, 1H, J = 13.8, H2CS), 2.84 (ddm, 1H, J = 16.8,
9.0, H2C), 2.76 (ddm, 1H, J = 16.8, 9.3, H2C), 2.44–2.36 (2H,
H2C), 2.09 (dm, 1H, J = 14.1, H2C), 2.04 (ddm, 1H, J = 14.1,
7.8, H2C), 1.92–1.81 (3H, H2C, HC), 1.38 (dm, 1H, J = 8.5,
H2C), 1.35 (dm, 1H, J = 8.3, H2C), 1.13 (s, 3H, H3C), 0.94 (s,
3H, H3C). 13C NMR (100 MHz, CDCl ) δ 171.2 [(0), C᎐O],
᎐
3
136.4 [(1), CH᎐CH ], 115.7 [(2), CH ᎐CH], 65.2 [(1), CHN],
᎐
᎐
2
2
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52.9 [(2), CH2S], 48.4, 47.7 [(0), Cq], 44.6 [(1), CH], 38.5, 34.5,
32.8, 28.3, 26.4 [(2), CH2], 20.8, 19.9 [(3), CH3].
(4S)-3-[(2R/S)-2-Allyloxy-2-phenylethanoyl]-4-isopropyloxazo-
lidin-2-one (6b)
From (4S)-4-isopropyloxazolidin-2-one (5.20 g, 40.0 mmol)
and 2-allyloxymandelic acid (7.69 g, 40.0 mmol), 6b (6.92 g,
57%) was obtained as a 1 : 1 mixture of diastereoisomers. MS
(EI) m/z (%) 304 (Mϩ ϩ 1, <5), 147 (25), 105 (100), 91 (50), 77
(20). IR (film): ν/cmϪ1 1787s, 1709s, 1388s, 1205m, 1104m,
1025m, 723m. Found: C, 67.1%; H, 6.8%; N, 4.4%. C17H21O4N
(2R)-N-(2-Methoxyethanoyl)bornane-10,2-sultam (3c)
From (2S)-Bornane-10,2-sultam (10.17 g, 47.2 mmol) and
methoxyacetic acid (3.46 ml, 47.2 mmol) analytically pure 3c
(13.24 g, 98%) was obtained without further purification. Mp
118 ЊC. MS (EI) m/z (%) 288 (Mϩ ϩ 1, 100), 135 (90), 93 (40).
IR (disk, KBr): ν/cmϪ1 2956m, 1703s, 1330s, 1137s, 986m.
Found: C, 54.3%; H, 7.5%; N, 5.0%. C13H21O4SN requires C,
1
requires C, 67.3%; H, 7.0%; N, 4.6%. H NMR (400 MHz,
CDCl3) δ 7.52–7.46 (4H, Ph), 7.31–7.28 (6H, Ph), 6.29 (s, 1H,
1
HCO), 6.20 (s, 1H, HCO), 5.93 (ddm, 1H, J = 17.0, 10.5, HC᎐
᎐
54.3%; H, 7.4%; N, 4.9%. H NMR (500 MHz, CDCl3) δ 4.41
CH ), 5.88 (ddm, 1H, J = 17.0, 10.5, HC᎐CH ), 5.25 (dm, 2H,
᎐
(d, 1H, J = 16.5, H2CO), 4.34 (d, 1H, J = 16.5, H2CO), 3.87 (dd,
1H, J = 7.5, 5.0, HCN), 3.36 (d, 1H, J = 14.1, H2CS), 3.42 (s,
3H, H3CO), 3.40 (d, 1H, J = 14.1, H2CS), 2.15 (dm, 1H, J =
14.1, H2C), 2.07 (dd, 1H, J = 14.1, 7.5, H2C), 1.90–1.80 (3H,
H2C, HC), 1.40 (ddm, 1H, J = 18.8, 9.5, H2C), 1.30 (ddm,
1H, J = 18.8, 7.8, H2C), 1.10 (s, 3H, H3C), 0.93 (s, 3H, H3C).
13C NMR (125 MHz, CDCl ) δ 168.7 [(0), C᎐O], 70.9 [(2),
2
J =217.0, H C᎐CH), 5.17 (dm, 2H, J = 10.5, H C᎐CH), 4.49
᎐
᎐
2
2
(ddd, 1H, J = 8.5, 4.0, 3.5, HCN), 4.30 (ddd, 1H, J = 8.5, 4.0,
3.5, HCN), 4.24 (dm, 1H, J = 8.5, H2CO), 4.14 (dm, 1H, J = 8.5,
H2CO), 4.12 (dm, 1H, J = 9.0, H2CO), 4.08 (dm, 1H, J = 9.0,
H2CO), 4.00 (br s, 4H, H2CO), 2.48 [qqd, 1H, J = 7.0, 7.0, 3.5,
HC(CH3)2], 2.08 [qqd, 1H, J = 7.0, 7.0, 3.5, HC(CH3)2], 0.89
(d, 6H, J = 7.0, H3C), 0.73 (d, 3H, J = 7.0, H3C), 0.36 (d, 3H, J =
7.0, H3C). 13C NMR (100 MHz, CDCl3) δ 170.9, 170.7 [(0),
CCH], 153.4, 153.4 [(0), CO], 135.8, 135.6 [(0), Ph], 134.0, 133.9
᎐
3
CH2O], 64.9 [(1), CHN], 59.5 [(3), CH3O], 52.6 [(2), CH2S],
49.2, 47.8 [(0), Cq], 44.5 [(1), CH], 38.1, 32.7, 26.3 [(2), CH2],
20.7, 19.8 [(3), CH3]. [α]2D3 Ϫ107.8 (c 1.28 in CH2Cl2).
[(1), CH᎐CH ], 128.8, 128.6, 128.5, 128.5, 128.4, 128.4 [(1), Ph],
᎐
2
118.1, 118.1 [(2), CH ᎐CH], 78.0, 77.9 [(1), CHO], 70.5, 70.4
[(2), CH2OCH], 63.6, 63.4 [(2), CH2OC], 58.9, 57.8 [(1), CHN],
28.2, 28.0 [(1), CH(CH3)2], 17.9, 17.5, 14.5, 14.0 [(3), CH3].
᎐
2
(2R)-N-(2-Allyloxyethanoyl)bornane-10,2-sultam (3d)
From (2S)-Bornane-10,2-sultam (3.71 g, 17.2 mmol) and
allyloxyacetic acid (2.00 g, 17.2 mmol) 3d (4.32 g, 80%) was
obtained. Mp 52 ЊC. MS (EI) m/z (%) 314 (Mϩ ϩ 1, 60), 135
(100), 93 (40), 79 (30). IR (disk, KBr): ν/cmϪ1 2931s, 1719s,
1469s, 1332s, 1133s, 776m. Found: C, 57.5%, H, 7.3%; N, 4.5%.
C15H23O4SN requires C, 57.5%; H, 7.4%; N, 4.5%. H NMR
(400 MHz, CDCl3) δ 5.88 (dddd, 1H, J = 17.1, 10.3, 5.8, 5.8,
General procedure for the alkylation of acylated oxazolidinones
or sultams
1
A solution of NaHMDS (2.72 ml of a 2.0 M solution in THF,
5.5 mmol) was diluted with THF (25 ml) and a solution of the
corresponding N-acyl compound 1a,b or 3a–d (3.6 mmol) in
THF (25 ml) was added dropwise at Ϫ78 ЊC. The mixture was
stirred at this temperature for one hour. A solution of allyl
iodide, benzyl bromide or ethyl 2-bromoacetate (18.2 mmol)
in THF (5 ml) was added and the mixture was stirred until
the reaction was complete as indicated by TLC. The reaction
was quenched by addition of water and the aqueous layer was
extracted with MTBE. The combined organic extracts were
dried with MgSO4, filtered and evaporated. The residue was
purified by flash chromatography on silica.
HC᎐CH ), 5.27 (dddd, 1H, J = 17.1, 1.3, 1.3, 1.3, H C᎐CH),
᎐
᎐
2
2
5.18 (dddd, 1H, J = 10.3, 1.3, 1.3, 1.3, H C᎐CH), 4.46 (d, 1H,
᎐
2
J = 16.5, H CC᎐O), 4.38 (d, 1H, J = 16.5, H CC᎐O), 4.09
᎐
᎐
2
2
(dddd, 1H, J = 12.5, 5.8, 1.3, 1.3, H CCH᎐CH ), 4.03 (dddd,
᎐
2
2
1H, J = 12.5, 5.8, 1.3, 1.3, H CCH᎐CH ), 3.85 (dd, 1H, J = 7.8,
᎐
2
5.0, HCN), 3.44 (d, 1H, J = 213.8, H2CS), 3.38 (d, 1H, J = 13.8,
H2CS), 2.14 (ddm, 1H, J = 14.1, 5.0, H2C), 2.05 (dd, 1H, J =
14.1, 8.0, H2C), 1.92–1.80 (3H, H2C, HC), 1.39 (dm, 1H, J =
10.0, H2C), 1.31 (dm, 1H, J = 10.0, H2C), 1.09 (s, 3H, H3C), 0.93
(s, 3H, H3C). 13C NMR (100 MHz, CDCl ) δ 168.9 [(0), C᎐O],
᎐
3
133.6 [(1), CH᎐CH ], 118.2 [(2), CH ᎐CH], 72.5, 68.3 [(2),
᎐
᎐
2
2
CH2O], 64.9 [(1), CHN], 52.6 [(2), CH2S], 49.2, 47.4 [(0), Cq],
44.5 [(1), CH], 38.1, 32.7, 26.3 [(2), CH2], 20.6, 19.8 [(3), CH3].
[α]2D0 Ϫ115.0 (c 1.55 in CH2Cl2).
General procedure for ring closing metathesis: preparation of 2d,
4f and 8a
To a solution of the corresponding metathesis precursor 2c, 4e
or 7a (12.7 mmol) in DCM (50 ml) was added Grubbs’ catalyst
(216 mg, 3 mol%). The mixture was stirred until the starting
material was fully consumed, as indicated by TLC. The solvent
was evaporated off and the residue purified by flash chrom-
atography on silica.
(4S)-3-[(2S)-2-Allyloxypropanoyl]-4-benzyloxazolidin-2-one
(6a)
From (4S)-4-benzyloxazolidin-2-one (1.00 g, 5.6 mmol) and
2-allyloxypropionic acid (0.73 g, 5.6 mmol), 6a (1.20 g, 74%)
was obtained. MS (EI) m/z (%) 290 (Mϩ ϩ 1, <5), 248 (50), 178
(60), 117 (100), 91 (95). IR (film): ν/cmϪ1 1781s, 1709s, 1393m,
1261m, 1220m, 1108m. Found: C, 65.7%, H, 6.7%; N, 4.6%.
(4S)-4-Benzyl-3-[(2R)-2-methylpent-4-enoyl]oxazolidin-2-one
(2a)
1
C16H19O4N requires C, 66.4%; H, 6.6%; N, 4.8%. H NMR
(400 MHz, CDCl3) δ 7.30–7.24 (2H, Ph), 7.22 (m, 1H, Ph),
From 1a (3.00 g, 12.9 mmol) and allyl iodide (4.70 ml, 51.4
mmol) 2a (2.27 g, 65%) was obtained. H NMR (400 MHz,
1
7.17–7.14 (2H, Ph), 5.89 (dddd, 1H, J = 17.3, 10.5, 5.8, 5.8, HC᎐
᎐
CH ), 5.25 (dddd, 1H, J = 17.3, 1.5, 1.5, 1.5, H C᎐CH), 5.15
CDCl3) δ 7.23–7.07 (5H, Ph), 5.70 (dddd, 1H, J = 17.3, 10.3,
7.0, 7.0, CH᎐CH ), 4.98 (dddd, 1H, J = 17.3, 1.5, 1.5, 1.5, CH ᎐
᎐ ᎐
2 2
᎐
2
2
(dddd, 1H, J = 10.5, 1.5, 1.5, 1.5, H C᎐CH), 5.08 (q, 1H, J = 6.5,
᎐
2
HCCH3), 4.62 (dddd, 1H, J = 9.5, 7.5, 3.3, 3.3, HCN), 4.18 (dd,
CH), 4.94 (dm, 1H, J = 10.3, CH ᎐CH), 4.56 (dddd, 1H, J = 9.5,
᎐
2
9.0, 3.3, 3.3, HCN), 4.06 (dd, 1H, J = 9.0, 9.0, H COC᎐O), 4.02
᎐
2
1H, J = 9.0, 7.5, H COC᎐O), 4.14 (dd, 1H, J = 9.0, 3.0,
᎐
2
H COC᎐O), 4.04 (dddd, 1H, J = 12.3, 5.8, 1.5, 1.5, H COCH),
(dd, 1H, J = 9.0, 3.3, H COC᎐O), 3.74 (ddm, 1H, J = 7.0, 7.0,
᎐
2
᎐
2
2
3.94 (dddd, 1H, J = 12.3, 5.8, 1.5, 1.5, H2COCH), 3.28 (dd, 1H,
J = 13.5, 3.3, H2CCHN), 2.74 (dd, 1H, J = 13.5, 9.5, H2CCHN),
1.37 (d, 3H, J = 6.5, H3C). 13C NMR (100 MHz, CDCl3) δ 173.5
HCC᎐O), 3.16 (dd, 1H, J = 13.3, 3.3, H CCHN), 2.58 (dd, 1H,
᎐
2
J = 13.3, 9.5, H2CCHN), 2.40 (dddm, 1H, J = 14.0, 7.0, 7.0,
H CCH᎐CH ), 2.12 (dddm, 1H, J = 14.0, 7.0, 7.0, H CCH᎐
᎐
᎐
2
2
2
[(0), CCH], 153.0 [(0), CO], 135.0 [(0), Ph], 134.3 [(1), CH᎐
CH2), 1.06 (d, 3H, J = 7.0, H3C). 13C NMR (100 MHz, CDCl3) δ
176.4 [(0), CCH2], 153.0 [(0), CO], 135.2 [(0), Ph], 135.2 [(1),
᎐
CH ], 129.4, 129.0, 127.4 [(1), Ph], 117.9 [(2), CH ᎐CH], 73.4
᎐
2
2
[(1), CHO], 71.2 [(2), CH2OCH], 66.6 [(2), CH2OC], 55.4 [(1),
CHN], 37.7 [(2), CH2Ph], 18.5 [(3), CH3]. [α]2D0 ϩ2.8 (c 1.20 in
CH2Cl2).
CH᎐CH ], 129.3, 128.8, 127.2 [(1), Ph], 117.1 [(2), CH ᎐CH],
᎐ ᎐
2 2
65.9 [(2), CH2O], 55.3 [(1), CHN], 38.0, 37.9 [(2), CH2], 37.0
[(1), CHCH3], 16.3 [(3), CH3].
1054
J. Chem. Soc., Perkin Trans. 1, 2002, 1050–1060

View Article Online
(4S)-4-Benzyl-3-[(2R)-2-methyl-3-phenylpropanoyl]oxazolidin-
2-one (2b)
1.14 (s, 3H, J = 6.5, H3C), 1.13 (s, 3H, H3C), 0.94 (s, 3H, H3C).
13C NMR (100 MHz, CDCl ) δ 175.7 [(0), C᎐O], 135.0 [(1),
᎐
3
CH᎐CH ], 117.2 [(2), CH ᎐CH], 65.3 [(1), CHN], 53.2 [(2),
᎐
᎐
2
2
From 1a (0.50 g, 2.1 mmol) and benzyl bromide (1.30 ml, 10.7
mmol) 2b (0.38 g, 55%) was obtained. H NMR (400 MHz,
CDCl3) δ 7.23–7.11 (8H, Ph), 6.99–6.95 (2H, Ph), 4.58 (dddd,
1H, J = 9.5, 9.3, 3.3, 3.3, HCN), 4.11–4.04 (2H, HCCH3,
CH2S], 48.2, 47.7 [(0), Cq], 44.6 [(1), CH], 39.4 [(2), CH2], 39.3
[(1), CHCH3], 38.5, 32.9, 26.4 [(2), CH2], 20.8, 19.9, 16.1 [(3),
CH3].
1
H COC᎐O), 4.02 (dd, 1H, J = 9.0, 3.0, H COC᎐O), 3.07 (dd,
᎐
᎐
2
2
(2R)-N-[(2S)-2-Benzylpent-4-enoyl]bornane-10,2-sultam (4b)
1H, J = 13.3, 7.3, H2CPh), 2.99 (dd, 1H, J = 13.5, 3.3,
H2CCHN), 2.60 (dd, 1H, J = 13.3, 7.8, H2CPh), 2.48 (dd, 1H,
J = 13.5, 9.3, H2CCHN), 1.11 (d, 3H, J = 6.8, H3C). 13C NMR
(100 MHz, CDCl3) δ 176.5 [(0), CCH2], 153.0 [(0), CO], 139.1,
135.1 [(0), Ph], 129.3, 129.3, 128.8, 128.3, 127.2, 126.4 [(1), Ph],
65.8 [(2), CH2O], 55.0 [(1), CHN], 39.8 [(2), CH2], 39.5 [(1),
CHCH3], 37.6 [(2), CH2], 16.7 [(3), CH3].
From 3b (2.00 g, 6.7 mmol) and benzyl bromide (3.20 ml, 26.9
mmol) 4b (1.70 g, 65%) was obtained. Mp 118 ЊC. MS (EI)
m/z (%) 388 (Mϩ ϩ 1, 30), 135 (25), 105 (20), 91 (100), 67 (20).
IR (disk, KBr): ν/cmϪ1 1684s, 1331s, 1215s, 1135s, 1067m,
700m, 538s. Found: C, 67.9%; H, 7.5%; N, 3.5%. C22H29O3SN
1
requires C, 68.2%; H, 7.5%; N, 3.6%. H NMR (400 MHz,
CDCl3) δ 7.19–7.06 (5H, Ph), 5.74 (dddd, 1H, J = 17.1, 10.3,
(4S)-3-[(2R)-2-Allyloxypent-4-enoyl)-4-benzyloxazolidin-2-one
(2c)
7.0, 7.0, CH᎐CH ), 5.03 (dddd, 1H, J = 17.1, 1.5, 1.5, 1.5, CH ᎐
᎐
᎐
2
2
CH), 4.98 (dddd, 1H, J = 10.3, 1.5, 1.5, 1.5, CH ᎐CH), 3.73 (m,
᎐
2
1H, HCN), 3.38 (m, 1H, HCC᎐O), 3.34 (d, 1H, J = 13.8, H CS),
3.30 (d, 1H, J = 13.8, H2CS), 2.88 (dd, 1H, J = 13.8, 8.5,
H2CPh), 2.74 (dd, 1H, J = 13.8, 7.0, H2CPh), 2.58 (dddm, 1H,
᎐
2
From 1b (1.00 g, 3.6 mmol) and allyl iodide (1.66 ml, 18.2
mmol) 2c (0.71 g, 62%) was obtained. H NMR (400 MHz,
CDCl3) δ 7.28–7.23 (2H, Ph), 7.20 (m, 1H, Ph), 7.16–7.12 (2H,
1
J = 14.0, 7.0, 7.0, H CCH᎐CH ), 2.14 (dddm, 1H, J = 14.0, 7.0,
᎐
2
2
Ph), 5.91–5.80 (2H, HC᎐CH ), 5.23 (dddd, 1H, J = 17.3, 1.5,
᎐
2
7.0, H CCH᎐CH ), 1.89 (dd, 1H, J = 13.3, 5.5, H C), 1.81–1.64
᎐
2
2
2
1.5, 1.5, H C᎐CH), 5.11 (dddd, 1H, J = 10.3, 1.5, 1.5, 1.5, H C᎐
᎐
᎐
2
2
(4H, H2C, HC), 1.26 (dm, 1H, J = 10.0, H2C), 1.20 (dm, 1H,
CH), 5.08 (dddd, 1H, J = 17.3, 1.5, 1.5, 1.5, H C᎐CH), 5.05
᎐
2
J = 7.8, H2C), 0.80 (m, 3H, H2C), 0.61 (s, 3H, H3C). 13C NMR
(dddd, 1H, J = 17.3, 1.5, 1.5, 1.5, H C᎐CH), 5.04 (dd, 1H, J =
᎐
7.0, 4.8, HCO), 4.66 (dddd, 1H, J =210.0, 8.0, 3.5, 3.0, HCN),
(100 MHz, CDCl ) δ 174.1 [(0), C᎐O], 138.3 [(0), Ph], 135.2 [(1),
᎐
3
CH᎐CH ], 129.4, 128.2, 126.4 [(1), Ph], 117.3 [(2), CH ᎐CH],
᎐
᎐
2
2
4.19 (dd, 1H, J = 9.0, 8.0, H COC᎐O), 4.13 (dd, 1H, J = 9.0, 3.5,
᎐
2
65.0 [(1), CHN], 53.1 [(2), CH2S], 48.0, 47.5 [(0), Cq], 46.7, 44.6
[(1), CH], 38.9, 38.3, 35.3, 32.8, 26.3 [(2), CH2], 20.5, 19.8 [(3),
CH3]. [α]2D0 Ϫ27.9 (c 1.18 in CH2Cl2).
H COC᎐O), 4.04 (dddd, 1H, J = 12.3, 5.5, 1.5, 1.5, H COCH),
᎐
2
2
3.88 (dddd, 1H, J = 12.3, 5.8, 1.5, 1.5, H2COCH), 3.22 (dd, 1H,
J = 13.3, 3.0, H2CCHN), 2.63 (dd, 1H, J = 13.3, 10.0,
H2CCHN), 2.55 (ddm, 1H, J = 14.3, 4.8, H2CCHO), 2.46 (ddm,
1H, J = 14.3, 7.0, H2CCHO). 13C NMR (100 MHz, CDCl3) δ
172.2 [(0), CCH], 153.0 [(0), CO], 134.9 [(0), Ph], 134.1, 132.9
(2R)-N-[(2S)-2-Methoxypent-4-enoyl]bornane-10,2-sultam (4c)
From 3c (1.50 g, 5.2 mmol) and allyl iodide (1.91 ml, 20.9
mmol) 4c (1.07 g, 63%) was obtained. Mp 158 ЊC. MS (EI)
m/z (%) 328 (Mϩ ϩ 1, 20), 296 (5), 222 (5), 85 (100), 55 (20).
IR (disk, KBr): ν/cmϪ1 3002s, 2973s, 1697s, 1393m, 1326s,
1222s, 1135s, 915s, 648m, 537s. Found: C, 58.8%; H, 7.6%;
N, 4.2%. C16H25O4SN requires C, 58.7%; H, 7.7%; N, 4.3%.
1H NMR (400 MHz, CDCl3) δ 5.83 (dddd, 1H, J = 17.0, 10.3,
[(1), CH᎐CH ], 129.3, 128.9, 127.4 [(1), Ph], 118.1, 177.6 [(2),
᎐
2
CH ᎐CH], 76.7 [(1), CHO], 71.4, 66.8 [(2), CH O], 55.0 [(1),
᎐
2
2
CHN], 38.0, 37.2 [(2), CH2CHO, CH2CHN].
(4S)-3-[(R)-(3,6-Dihydro-2H-pyran-2-ylmethanoyl]-4-
benzyloxazolidin-2-one (2d)
7.5, 7.0, HC᎐CH ), 5.09 (dm, 1H, J = 17.0, H C᎐CH), 5.06 (dm,
᎐
᎐
2
From 2c (0.30 g, 1.0 mmol) and Grubbs’ catalyst (24 mg,
3 mol%) 2d (0.21 g, 77%) was obtained. MS (EI) m/z (%) 288
(Mϩ ϩ 1, 40), 270 (30), 83 (70), 55 (100). IR (film): ν/cmϪ1
3032w, 2929w, 2835w, 1790s, 1709s, 1398m, 1256m, 1103m,
705m. Found: C, 67.1%; H, 5.8%; N, 4.7%. C16H17O4N requires
C, 66.9%; H, 6.0%; N, 4.9%. 1H NMR (400 MHz, CDCl3)
δ 7.28–7.23 (2H, Ph), 7.20 (m, 1H, Ph), 7.14–7.11 (2H, Ph); 5.79
2
1H, J = 10.3, H C᎐CH), 4.49 (dd, 1H, J = 6.0, 5.5, HCO), 3.94
᎐
2
(dd, 1H, J = 7.5, 4.8, HCN), 3.48 (d, 1H, J = 13.8, H2CS), 3.43
(d, 1H, J = 13.8, H2CS), 3.35 (s, 3H, H3CO), 2.56 (dm, 1H, J =
14.3, H2CCHO), 2.48 (dd, 1H, J = 14.3, 7.0, H2CCHO), 2.07
(dd, 1H, J = 14.0, 7.5, H2C), 1.96 (dm, 1H, J = 14.0, H2C), 1.92–
1.83 (3H, H2C, HC), 1.41 (dm, 1H, J = 9.0, H2C), 1.34 (dm, 1H,
J = 9.0, H2C), 1.12 (s, 3H, H3C), 0.95 (s, 3H, H3C). 13C NMR
(dm, 1H, J = 10.3, CH᎐CH), 5.70 (dm, 1H, J = 10.3, CH᎐CH),
᎐
᎐
(100 MHz, CDCl ) δ 165.8 [(0), C᎐O], 132.7 [(1), CH᎐CH ],
᎐
᎐
5.06 (dd, 1H, J = 7.8, 5.5, CHO), 4.66 (dddd, 1H, J = 8.0, 8.0,
3.3, 3.3, HCN), 4.29 (dm, 1H, J = 16.5, HHCO), 4.22 (dm, 1H,
3
2
118.2 [(2), CH ᎐CH], 79.7 [(1), CHO], 65.0 [(1), CHN], 58.0
᎐
2
[(3), CH3O], 53.1 [(2), CH2S], 47.8, 47.3 [(0), Cq], 44.5 [(1),
CH], 38.2, 38.0, 32.8, 26.4 [(2), CH2], 20.7, 19.9 [(3), CH3]. [α]2D0
Ϫ10.2 (c 1.52 in CH2Cl2).
J = 16.5, HHCO), 4.21 (dd, 1H, J = 9.0, 8.0, H COC᎐O), 4.14
᎐
2
(dd, 1H, J = 9.0, 3.3, H COC᎐O), 3.17 (dd, 1H, J = 13.3, 3.3,
᎐
2
H2CCHN), 2.76 (dd, 1H, J = 13.3, 8.0, H2CCHN), 2.35–2.30
(2H, HHCCH᎐). 13C NMR (100 MHz, CDCl3) δ 171.0 [(0),
᎐
CCH], 152.7 [(0), CO], 134.8 [(0), Ph], 129.4, 128.8, 127.3 [(1),
(2R)-N-[(2S)-2-Methoxy-3-phenylpropanoyl]bornane-10,2-
Ph], 126.0, 122.7 [(1), CH᎐CH], 71.6 [(1), C2], 66.6, 66.0 [(2),
sultam (4d)
᎐
CH2O], 54.9 [(1), CHN], 37.6 [(2), CH2CHN], 26.9 [(2),
From 3c (4.00 g, 13.9 mmol) and benzyl bromide (8.30 ml, 69.6
mmol) 4d (2.33 g, 44%) was obtained. Mp 160 ЊC. MS (EI)
m/z (%) 378 (Mϩ ϩ 1, 40), 346 (20), 216 (40), 135 (100), 91 (30).
IR (disk, KBr): ν/cmϪ1 3002m, 2966m, 1694s, 1330s, 1284s,
1218s, 1137s, 700m, 534s. Found: C, 63.6%; H, 7.1%; N, 3.7%.
HHCCH᎐]. [α]2D0 ϩ132.4 (c 1.22 in CH Cl ).
᎐
2
2
(2R)-N-[(2S)-2-Methylpent-4-enoyl]bornane-10,2-sultam (4a)
From 3a (2.00 g, 7.4 mmol) and allyl iodide (2.71 ml, 29.6
1
1
mmol) 4a (1.22 g, 53%) was obtained. H NMR (400 MHz,
C20H27O4SN requires C, 63.6%; H, 7.2%; N, 3.7%. H NMR
CDCl ) δ 5.74 (dddd, 1H, J = 17.0, 10.0, 7.5, 6.3, HC᎐CH ),
(400 MHz, CDCl3) δ 7.31–7.23 (4H, Ph), 7.18 (m, 1H, Ph), 4.61
(dd, 1H, J = 9.5, 3.5, HCO), 3.94 (dd, 1H, J = 7.5, 4.8, HCN),
3.49 (d, 1H, J = 13.8, H2CS), 3.44 (d, 1H, J = 13.8, H2CS), 3.27
(s, 3H, H3CO), 3.06 (dd, 1H, J = 13.8, 3.5, H2CPh), 2.87 (dd,
1H, J = 13.8, 9.5, H2CPh), 2.08 (dd, 1H, J = 13.8, 7.5, H2C),
1.95 (dm, 1H, J = 13.8, H2C), 1.91–1.83 (3H, H2C, HC), 1.41
(dm, 1H, J = 9.5, H2C), 1.33 (dm, 1H, J = 9.5, H2C), 1.01 (s, 3H,
H3C), 0.94 (s, 3H, H3C). 13C NMR (100 MHz, CDCl3) δ 172.2
᎐
3
2
5.04 (dddd, 1H, J = 17.0, 1.5, 1.5, 1.5, H C᎐CH), 4.96 (dddd,
᎐
2
1H, J = 10.0, 1.5, 1.5, 1.5, H C᎐CH), 3.85 (dd, 1H, J = 7.3, 5.3,
᎐
2
HCN), 3.47 (d, 1H, J = 13.8, H2CS), 3.40 (d, 1H, J = 13.8,
H2CS), 3.19 (dqm, 1H, J = 7.5, 6.5, HCCH3), 2.41 (dddm, 1H,
J = 13.8, 7.5, 6.3, H2CCHCH3), 2.21 (dddm, 1H, J = 13.8, 7.5,
6.3, H2CCHCH3), 2.04–1.98 (2H, H2C), 1.92–1.79 (3H, H2C,
HC), 1.38 (dm, 1H, J = 9.0, H2C), 1.30 (dm, 1H, J = 9.0, H2C),
J. Chem. Soc., Perkin Trans. 1, 2002, 1050–1060
1055

View Article Online
[(0), C᎐O], 136.9 [(0), Ph], 129.6, 128.2, 126.7 [(1), Ph], 81.4 [(1),
CH2O], 65.0 [(1), CHN], 60.8 [(2), CH2O], 53.0 [(2), CH2SO2],
᎐
CHO], 65.0 [(1), CHN], 58.2 [(3), CH3O], 53.1 [(2), CH2S],
48.7, 47.6 [(0), Cq], 44.5 [(1), CH], 39.8, 38.1, 32.8, 26.4 [(2),
CH2], 20.7, 19.8 [(3), CH3]. [α]2D5 Ϫ76.4 (c 1.00 in CH2Cl2).
48.9 [(0), Sul], 47.8 [(0), Sul], 44.4 [(1), Sul], 38.4 [(2), Sul], 34.1
[(2), CH C᎐O], 32.7 [(2), Sul], 26.4 [(2), Sul], 20.5 [(3), Sul], 19.8
᎐
2
[(3), Sul], 14.1 [(3), CH3CH2]. [α]2D0 Ϫ62.6 (c 1.40 in CH2Cl2).
(4S)-3-[(2R)-2-Allyloxy-2-methylpent-4-enoyl]-4-
benzyloxazolidin-2-one (7)
(2R)-N-[(2S)-2-Allyloxypent-4-enoyl]bornane-10,2-sultam (4e)
From 3d (6.00 g, 19.1 mmol) and allyl iodide (8.75 ml, 95.7
mmol) 4e (4.25 g, 63%) was obtained. Mp 93 ЊC. MS (EI)
m/z (%) 354 (Mϩ ϩ 1, 35), 135 (30), 111 (100), 93 (40), 67 (50),
55 (55). IR (disk, KBr): ν/cmϪ1 2941m, 1695s, 1330s, 1273m,
1138s, 1062m, 914m, 545s. Found: C, 61.1%; H, 7.7%; N, 3.9%.
From 6a (1.18 g, 4.1 mmol) and allyl iodide (1.87 ml, 20.5
mmol), 7 (0.45 g, 35%) was obtained. MS (EI) m/z (%) 329 (Mϩ,
<5), 270 (100), 218 (90), 157 (50), 129 (30), 91 (50). IR (film)
ν/cmϪ1 3079w, 2964w, 2914w, 1790s, 1692s, 1348m, 1256m,
1182m, 1105m, 1004m, 917m, 734m. Found: C, 69.0%; H,
7.3%; N, 4.1%. C19H23O4N requires C, 69.3%; H, 7.0%; N, 4.3%.
1H NMR (400 MHz, CDCl3) δ 7.27–7.15 (5H, Ph), 5.85 (dddd,
1
C18H27O4SN requires C, 61.2%; H, 7.7%; N, 4.0%. H NMR
(400 MHz, CDCl ) δ 5.91–5.79 (2H, HC᎐CH ), 5.27 (dddd, 1H,
᎐
3
2
J = 17.1, 1.5, 1.5, 1.5, H C᎐CH), 5.15 (dm, 1H, J = 10.3, H C᎐
᎐
᎐
2
2
1H, J = 17.3, 10.3, 5.5, 5.5, HC᎐CH ), 5.72 (dddd, 1H, J = 17.3,
᎐
CH), 5.08 (dm, 1H, J = 17.3, H C᎐CH), 5.04 (dm, 1H, J = 10.1,
2
᎐
2
10.0, 7.5, 7.5, HC᎐CH ), 5.22 (dddd, 1H, J = 17.3, 1.5, 1.5, 1.5,
᎐
H C᎐CH), 4.61 (dd, 1H, J = 7.0, 5.0, HCO), 4.07 (dddd, 1H, J =
2
᎐
2
H C᎐CH), 5.09 (dddd, 1H, J = 17.3, 1.5, 1.5, 1.5, H C᎐CH),
᎐
᎐
2
12.8, 5.5, 1.5, 1.5, H2CO), 3.91 (dd, 1H, J = 7.8, 5.0, HCN), 3.87
(dddd, 1H, J = 12.8, 6.0, 1.5, 1.5, H2CO), 3.47 (d, 1H, J = 13.8,
H2CS), 3.41 (d, 1H, J = 13.8, H2CS), 2.57 (ddm, 1H, J = 13.8,
5.0, H2C), 2.50 (ddm, 1H, J = 13.8, 7.0, H2C), 2.05 (dd, 1H, J =
14.1, 7.8, H2C), 1.95 (dm, 1H, J = 14.1, H2C), 1.90–1.81 (3H,
H2C, HC), 1.40 (m, 1H, H2C), 1.33 (m, 1H, H2C), 1.11 (s, 3H,
H3C), 0.94 (s, 3H, H3C). 13C NMR (100 MHz, CDCl3) δ 172.1
2
5.08 (dddd, 1H, J = 10.5, 1.5, 1.5, 1.5, H C᎐CH), 5.04 (dddd,
᎐
2
1H, J = 10.0, 1.5, 1.5, 1.5, H C᎐CH), 4.57 (dddd, 1H, J = 10.0,
᎐
2
7.0, 3.5, 3.5, HCN), 4.07 (dd, 1H, J = 9.0, 7.0, H COC᎐O), 4.03
᎐
2
(dd, 1H, J = 9.0, 3.3, H COC᎐O), 3.98 (dddd, 1H, J = 12.3, 5.5,
᎐
2
1.5, 1.5, H2COC), 3.84 (dddd, 1H, J = 12.3, 5.5, 1.5, 1.5,
H2COC), 3.23 (dd, 1H, J = 13.0, 3.5, H2CCHN), 3.03 (dd, 1H,
J = 14.0, 7.5, H2CCO), 2.71 (dd, 1H, J = 14.0, 7.0, H2CCO),
2.66 (dd, 1H, J = 13.0, 10.0, H2CCHN), 1.52 (s, 3H, H3CC).
13C NMR (100 MHz, CDCl3) δ 174.5 [(0), CCCH3], 151.4 [(0),
[(0), C᎐O], 133.9, 132.9 [(1), CH᎐CH ], 118.0, 117.7 [(2), CH ᎐
᎐
2
᎐
᎐
2
CH], 77.6 [(1), CHO], 71.1 [(2), CH2O], 65.0 [(1), CHN], 53.1
[(2), CH2S], 48.6, 47.8 [(0), Cq], 44.5 [(1), CH], 38.2, 38.1, 32.8,
26.4 [(2), CH2], 20.7, 19.8 [(3), CH3]. [α]2D0 Ϫ96.6 (c 1.55 in
CH2Cl2).
CO], 135.4 [(0), Ph], 134.6, 132.7 [(1), CH᎐CH ], 129.3, 128.8,
᎐
2
127.2 [(1), Ph], 118.7, 116.5 [(2), CH ᎐CH], 82.7 [(0), CCH ],
᎐
2
3
66.1, 65.4 [(2), CH2O], 57.5 [(1), CHN], 40.5, 37.8 [(2), CH2C],
20.8 [(3), CH3]. [α]2D0 ϩ38.4 (c 1.13 in CH2Cl2).
(2R)-N-[(1S)-3,6-Dihydro-2H-pyran-2-ylmethanoyl]bornane-
10,2-sultam (4f )
(4S)-3-[(2R)-2-Methyl-3,6-diyhdro-2H-pyran-2-ylmethanoyl]-4-
From 4e (4.48 g, 12.7 mmol) and Grubbs’ catalyst (216 mg,
3 mol%) 4f (3.44 g, 83%) was obtained. Mp 168 ЊC. MS (EI)
m/z (%) 326 (Mϩ ϩ 1, 80), 216 (15), 135 (10), 83 (85), 55 (100).
Found: C, 59.2%; H, 7.1%; N, 4.2%. C16H23O4SN requires C,
benzyloxazolidin-2-one (8)
From 7 (0.94 g, 2.8 mmol) and Grubbs’ catalyst (70 mg,
3 mol%) 8 (0.68 g, 80%) was obtained. MS (EI) m/z (%) 302
(Mϩ ϩ 1, 60), 97 (100). IR (film) ν/cmϪ1 2926m, 1789s, 1349m,
1
59.1%; H, 7.1%; N, 4.3%. H NMR (400 MHz, CDCl3) δ 5.80
1
1190s, 1093s, 703m. H NMR (400 MHz, CDCl3) δ 7.28–7.24
(ddm, 1H, J = 10.3, 2.0, CH᎐CH ), 5.72 (dm, 1H, J = 10.3, CH᎐
᎐
᎐
(2H, Ph), 7.21 (m, 1H, Ph), 7.17–7.13 (2H, Ph); 5.79 (dm, 1H,
CH ), 4.68 (dd, 1H, J = 10.3, 3.8, HCO), 4.33 (dm, 1H, J = 16.5,
HHCO), 4.25 (dm, 1H, J = 16.5, HHCO), 3.92 (dd, 1H, J = 7.8,
4.8, HCN), 3.47 (d, 1H, J = 13.8, H2CS), 3.42 (d, 1H, J = 13.8,
J = 10.5, HC᎐CH ), 5.66 (dm, 1H, J = 10.5, HC᎐CH ), 4.60
᎐
᎐
(dddd, 1H, J = 10.0, 9.0, 3.0, 3.0, HCN), 4.39 (dm, 1H, J = 17.0,
HHCO), 4.22 (dm, 1H, J = 17.0, HHCO), 4.13 (dd, 1H, J = 9.0,
H CS), 2.41 (dm, 1H, J = 16.8, HHCCH᎐), 2.28 (dm, 1H, J =
᎐
2
9.0, H COC᎐O), 4.08 (dd, 1H, J = 9.0, 3.0, H COC᎐O), 3.26
᎐
᎐
2
2
16.8, HHCCH᎐), 2.09 (dd, 1H, J = 14.0, 7.8, H C), 1.97 (dm,
᎐
2
(dd, 1H, J = 13.3, 3.0, H2CCHN), 2.88 (dm, 1H, J = 17.5,
1H, J = 14.0, H2C), 1.91–1.83 (3H, H2C, HC), 1.45–1.30 (2H,
H2C), 1.09 (s, 3H, H3C), 0.94 (s, 3H, H3C). 13C NMR (100
HHCCH᎐), 2.68 (dd, 1H, J = 13.3, 10.0, H CCHN), 2.19 (dm,
᎐
2
1H, J = 17.5, HHCCH᎐), 1.61 (3H, H C). 13C NMR (100 MHz,
᎐
3
MHz, CDCl ) δ 170.6 [(0), C᎐O], 126.0, 122.7 [(1), CH᎐CH],
᎐
᎐
3
CDCl3) δ 174.5 [(0), CCCH3], 151.8 [(0), CO], 135.3 [(0), Ph],
129.3, 128.9, 127.3 [(1), Ph], 125.0, 122.0 [(1), HC᎐CH], 76.8
72.8 [(1), HCO], 65.7 [(2), HHCO], 64.9 [(1), CHN], 53.0 [(2),
CH2S], 48.7, 47.8 [(0), Cq], 44.4 [(1), CH], 38.0, 32.6, 28.6, 26.4
[(2), CH2, C3], 20.7, 19.8 [(3), CH3]. [α]2D0 Ϫ179.0 (c 1.75 in
CH2Cl2).
᎐
[(0), C(CH3)O], 66.4, 62.4 [(2), CH2O], 57.4 [(1), CHN], 37.8
[(2), CH CHN)], 31.9 [(2), HHCCH᎐], 22.2 [(3), CH ]. [α]2D0
᎐
2
3
ϩ42.7 (c 1.45 in CH2Cl2).
(2R)-N-[(2S)-2-Allyloxy-3-ethoxycarbonylpropanoyl]bornane-
10,2-sultam (4g)
Attempted allylation of acylated oxazolidinone 6b
From 6b (1.80 g, 5.9 mmol) and allyl iodide (2.71 ml, 29.7
mmol) only allyl benzoate 9 (0.50 g, 47%) was obtained. H
NMR (400 MHz, CDCl3) δ 8.07–8.03 (2H, Ph), 7.55 (m, 1H,
Ph), 7.45–7.40 (2H, Ph), 6.03 (dddd, 1H, J = 17.1, 10.5, 5.8, 5.5,
From 3d (3.00 g, 9.6 mmol) and ethyl 2-bromoacetate (5.31 ml,
47.9 mmol) 4g (2.45 g, 64%) was obtained. MS (EI) m/z (%) 401
(Mϩ ϩ 1, 80), 399 (100), 390 (100), 354 (85), 296 (100). IR (disk,
KBr): ν/cmϪ1 2961m, 1744s, 1708s, 1337m, 1135m, 538m.
Found: C, 57.2%; H, 7.4%; N, 3.7%. C19H29NO6S requires C,
1
HC᎐CH ), 5.40 (dddd, 1H, J = 17.1, 1.5, 1.5, 1.5, H C᎐CH),
᎐
᎐
2
2
5.27 (dddd, 1H, J = 10.5, 1.5, 1.5, 1.5, H2C᎐CH), 4.84 (dddd,
1
᎐
57.1%; H, 7.3%; N, 3.5%. H NMR (500 MHz, CDCl3) δ 5.86
1H, J = 19.8, 5.8, 1.5, 1.5, H2CO), 4.79 (dddd, 1H, J = 19.8, 5.5,
(dddd, 1H, J = 17.1, 10.7, 6.0, 6.0, CH᎐CH ), 5.25 (dd, 1H, J =
᎐
1.5, 1.5, H2CO). 13C NMR (100 MHz, CDCl3) δ 166.2 [(0),
2
17.1, 1.5, CH ᎐CH), 5.15 (dd, 1H, J = 10.6, 1.5, CH ᎐CH), 4.88
᎐
᎐
2
(1H, dd, J =28.2, 4.0, CHC᎐O), 4.07–4.17 (4H, OCH ), 3.92
C᎐O], 133.0, 132.2 [(1), Ph/CH᎐CH ], 130.1 [(0), Ph], 129.6,
᎐
᎐
2
᎐
2
128.3 [(1), Ph/CH᎐CH ], 118.2 [(2), CH ᎐CH], 65.2 [(2),
᎐
᎐
2
2
(1H, dd, J = 6.2, 6.0, CHN), 3.47 (d, 1H, J = 14.0, CH2SO2),
3.42 (d, 1H, J = 13.7, CH2SO2), 2.79 (1H, dd, J = 15.7, 4.0,
CH2CHO), 2.72 (1H, dd, J = 15.7, 8.1, CH2CHO), 2.00–2.11
(2H, CH2CHN), 1.80–1.93 (3H, Sul), 1.20–1.27 (2H, Sul & 3H,
CH3CH2), 1.09 (s, 3H, Sul), 0.93 (s, 3H, Sul); 13C NMR (125
CH2O].
General procedure for the preparation of diallylcarbinols
A solution of allylmagnesium bromide (1.0 M solution in ether,
7.6 ml, 7.6 mmol) was added to a solution of the corresponding
oxazolidinone 2 or bornane sultam 4 (1.90 mmol) in ether
MHz, CDCl ) δ 170.8 [(0), C᎐O], 169.3 [(0), C᎐O], 133.6 [(1),
᎐
᎐
3
CH᎐CH ], 118.1 [(2), CH ᎐CH], 74.9 [(1), CHO], 71.7 [(2),
᎐
᎐
2
2
1056
J. Chem. Soc., Perkin Trans. 1, 2002, 1050–1060

View Article Online
(5 ml) at Ϫ78 ЊC. When the reaction was complete as indicated
by TLC, the mixture was poured into aqueous NH4Cl solution
and extracted. After evaporation, the residue was purified by
flash chromatography on silica to give the corresponding S-
or R-configured diallylcarbinols, along with the free oxazolid-
inone or bornane sultam, respectively.
[(2), CH ᎐CH], 76.8 [(1), CHO], 74.6 [(0), COH], 66.4 [(2),
᎐
2
CH2O], 40.4, 39.0, 24.5 [(2), CH2]. [α]2D2 ϩ14.5 (c 1.00 in
CH2Cl2).
(S)-4-Allyl-5-methylocta-1,7-dien-4-ol (12a)
From 4a (1.50 g, 4.8 mmol) 12a (0.73 g, 83%) was obtained.
Spectroscopic data are identical to those observed for the
enantiomer (10a). [α]2D2 Ϫ3.2 (c 1.00 in CH2Cl2).
(R)-4-Allyl-5-methylocta-1,7-dien-4-ol (10a)
From 2a (4.21 g, 15.4 mmol) 10a (1.94 g, 70%) was obtained.
MS (EI) m/z (%) 179 (Mϩ Ϫ 1, <5), 139 (100), 69 (40). IR (film):
ν/cmϪ1 3485br m, 3076s, 2977s, 2937s, 1640s, 1383m, 996s, 911s.
(S)-4-Allyl-5-benzylocta-1,7-dien-4-ol (12b)
From 4b (0.50 g, 1.3 mmol) 12b (0.22 g, 64%) was obtained. MS
(EI) m/z (%) 256 (Mϩ, 40), 244 (90), 216 (90), 135 (100), 93 (50),
57 (50). IR (film): ν/cmϪ1 3480br m, 3079m, 2934s, 1643s, 925s.
1H NMR (400 MHz, CDCl3) δ 7.27–7.22 (2H, Ph), 7.19–7.14
1H NMR (400 MHz, CDCl ) δ 5.92–5.81 (2H, HC᎐CH ), 5.70
᎐
3
2
(ddm, 1H, J = 17.3, 10.3, HC᎐CH ), 5.13 (dm, 1H, J = 10.3,
᎐
2
H C᎐CH), 5.13 (dm, 1H, J = 10.3, H C᎐CH), 5.09 (dm, 1H, J =
᎐
᎐
2
2
17.8, H C᎐CH), 5.09 (dm, 1H, J = 17.8, H C᎐CH), 5.00 (dm,
᎐
᎐
2
1H, J =217.3, H C᎐CH), 4.97 (dm, 1H, J = 10.8, H C᎐CH), 2.43
(3H, Ph), 5.96–5.84 (2H, HC᎐CH ), 5.71 (dddd, 1H, J = 17.1,
᎐
2
᎐
᎐
2
2
10.0, 7.0, 7.0, HC᎐CH ), 5.17 (dm, 1H, J = 17.1, H C᎐CH), 5.12
᎐
᎐
2
2
(m, 1H, H2C), 2.32–2.25 (2H, H2C), 2.23–2.17 (2H, H2C), 1.76
(dm, 1H, J = 13.3, H2C), 1.64 (dqm, 1H, J = 7.0, 2.8, HCCH3),
1.57 (br s, 1H, HO), 0.89 (d, 3H, J = 7.0, H3C). 13C NMR (100
(dm, 1H, J = 10.0, H C᎐CH), 5.12 (dm, 1H, J = 17.1, H C᎐CH),
᎐
᎐
2
2
5.10 (dm, 1H, J = 10.0, H C᎐CH), 4.94 (ddm, 1H, J = 17.1, 1.5,
᎐
2
H C᎐CH), 4.90 (dm, 1H, J = 10.0, H C᎐CH), 2.98 (dd, 1H, J =
᎐
᎐
2
13.8, 3.8, H2CPh), 2.44 (dd, 1H, J =214.1, 9.8, H2C), 2.39 (dd,
2H, J = 14.1, 7.3, H2C), 2.34–2.23 (3H, HCCOH, H2C), 2.08
(dm, 1H, J = 14.3, H2C), 1.98 (dm, 1H, J = 14.3, H2C), 1.73 (br
s, 1H, HO). 13C NMR (100 MHz, CDCl3) δ 141.6 [(0), Ph],
MHz, CDCl ) δ 138.2, 133.9, 133.8 [(1), CH᎐CH ], 118.6,
᎐
3
2
118.6, 115.7 [(2), CH ᎐CH], 75.4 [(0), COH], 41.4, 40.6 [(2),
᎐
2
CH2], 40.1 [(1), CHCH3], 35.5 [(2), CH2], 13.6 [(3), CH3]. ϩ4.3
(c 1.20 in CH2Cl2).
138.4, 133.9, 133.8 [(1), CH᎐CH ], 129.2, 128.3, 125.8 [(1), Ph],
᎐
2
(R)-4-Allyl-2-benzylhex-5-en-3-ol (10b)
118.7, 118.6, 115.8 [(2), CH ᎐CH], 76.2 [(0), COH], 47.3 [(1),
᎐
2
CHCOH], 41.8, 41.5, 35.4, 33.7 [(2), CH2]. [α]2D1 Ϫ7.1 (c 1.30 in
From 2b (0.53 g, 1.6 mmol) 10b (0.31 g, 82%) was obtained. MS
(EI) m/z (%) 231 (Mϩ ϩ 1, <5), 189 (100), 171 (70), 119 (80), 91
(25). IR (film): ν/cmϪ1 3476br m, 2976s, 2937s, 1639m, 999s,
CH2Cl2).
1
(S)-4-Allyl-5-methoxyocta-1,7-dien-4-ol (12c)
914s, 711s. H NMR (400 MHz, CDCl3) δ 7.31–7.26 (2H, Ph),
7.21–7.16 (3H, Ph), 6.02–5.89 (2H, HC᎐CH ), 5.22 (dm, 1H,
᎐
2
From 4c (0.59 g, 1.8 mmol) 12c (0.30 g, 85%) was obtained. MS
(EI) m/z (%) 195 (Mϩ Ϫ 1, <5), 179 (20), 147 (40), 137 (50), 85
(100). IR (film) ν/cmϪ1 3480br m, 2978m, 2935m, 1639m,
J = 10.0, H C᎐CH), 5.20 (dm, 1H, J = 17.1, H C᎐CH), 5.18
᎐
᎐
2
2
(dm, 1H, J = 10.0, H C᎐CH), 5.17 (dm, 1H, J = 17.0, H C᎐CH),
᎐
᎐
2
2
1
3.12 (dd, 1H, J = 13.0, 2.5, H2CPh), 2.41 (dm, 2H, J = 14.0,
H2C), 2.33 (dd, 2H, J = 14.0, 7.5, H2C), 2.19 (dd, 1H, J = 13.0,
11.3, H2CPh), 1.89 (dqd, 1H, J = 11.3, 7.0, 2.5, HCCH3), 1.67
(br s, 1H, HO), 0.84 (d, 1H, J = 7.0, H3C). 13C NMR (100 MHz,
1437m, 1098s, 914s. H NMR (400 MHz, CDCl3) δ 5.95–5.80
(3H, HC᎐CH ), 5.13–5.07 (4H, H C᎐CH), 5.06 (dm, 1H, J =
᎐
᎐
᎐
2
17.8, H C᎐CH), 5.03 (dm, 1H, J = 217.0, H C᎐CH), 3.42 (s, 3H,
᎐
2
2
H3C), 3.12 (dd, 1H, J = 8.3, 3.5, HCO), 2.41–2.32 (3H, H2C),
2.27 (dm, 1H, J = 9.0, H2C), 2.23 (br s, 1H, HO), 2.21 (dm, 1H,
J = 8.3, H2C), 2.10 (dd, 1H, J = 14.1, 8.3, H2C). 13C NMR
CDCl ) δ 141.8 [(0), Ph], 133.9, 133.7 [(1), CH᎐CH ], 129.1,
᎐
3
2
128.2, 125.7 [(1), Ph], 118.8, 118.7 [(2), CH ᎐CH], 75.3 [(0),
᎐
2
COH], 42.8 [(1), CHCH3], 41.3, 40.8, 37.2 [(2), CH2], 13.2 [(3),
(100 MHz, CDCl ) 136.1, 133.9, 133.6 [(1), CH᎐CH ], 118.3,
᎐
3
2
CH3]. [α]2D2 Ϫ2.5 (c 1.70 in CH2Cl2).
118.0, 116.6 [(2), CH ᎐CH], 85.1 [(1), CHO], 75.8 [(0), COH],
᎐
2
60.0 [(2), CH3O], 40.7, 39.9, 34.6 [(2), CH2]. [α]2D2 ϩ23.3 (c 1.25
(R)-4-Allyl-5-allyloxyocta-1,7-dien-4-ol (10c)
in CH2Cl2).
From 2c (0.60 g, 1.9 mmol) 10c (0.32 g, 76%) was obtained. MS
(EI) m/z (%) 221 (Mϩ Ϫ 1, <5), 205 (100), 177 (40), 149 (20), 91
(20). IR (film) ν/cmϪ1 3483br w, 3078m, 2926m, 1640m, 1261m,
1087m, 998m, 925s, 804m. 1H NMR (400 MHz, CDCl3) δ 5.95–
(S)-4-Allyl-5-allyloxyocta-1,7-dien-4-ol (12e)
From 4e (0.50 g, 1.3 mmol) 12e (0.29 g, 96%) was obtained.
Spectroscopic data are identical to those observed for the
enantiomer (10c). [α]2D0 ϩ30.3 (c 1.45 in CH2Cl2).
5.81 (4H, HC᎐CH ), 5.23 (dddd, 1H, J = 17.3, 1.8, 1.8, 1.8,
᎐
2
H C᎐CH), 5.14–5.03 (6H, H C᎐CH), 5.02 (dm, 1H, J = 10.3,
᎐
᎐
2
2
H C᎐CH), 4.18 (dddd, 1H, J = 12.5, 5.3, 1.5, 1.5, H CO), 3.97
Preparation of divinylcarbinols
᎐
2
2
(dddd, 1H, J = 12.5, 5.8, 1.5, 1.5, H2CO), 3.29 (dd, 1H, J = 8.0,
3.5, HCO), 2.43–2.29 (3H, H2C), 2.31 (ddm, 1H, J = 13.5, 7.0,
H2C), 2.27 (br s, 1H, HO), 2.24 (ddm, 1H, J = 14.3, 7.5, H2C),
2.12 (dd, 1H, J = 14.3, 8.0, H2C). 13C NMR (100 MHz, CDCl3)
Procedure A. A solution of vinylmagnesium chloride (1.7 M
solution in THF, 1.85 ml, 3.2 mmol) was added to a solution
of the corresponding oxazolidinone 2 or bornane sultam 4
(1.50 mmol) in ether (15 ml) at Ϫ78 ЊC. When the reaction was
complete as indicated by TLC, the mixture was poured into
aqueous NH4Cl solution and extracted. After evaporation, the
residue was purified by flash chromatography on silica to give
the corresponding S- or R-configured divinylcarbinols, along
with a butenone by-product. When oxazolidinones 2a,b and 8a
were used, acrylates 16a,b and 17 were formed exclusively.
δ 136.1, 134.8, 133.9, 133.7 [(1), CH᎐CH ], 118.3, 118.0, 116.7,
᎐
2
116.4 [(2), CH ᎐CH], 83.4 [(1), CHO], 75.7 [(0), COH], 73.0
᎐
2
[(2), CH2O], 40.8, 40.0, 34.9 [(2), CH2]. [α]2D2 Ϫ28.3 (c 1.25 in
CH2Cl2).
(R)-4-(3,6-Dihydro-2H-pyran-2-yl)hepta-1,6-dien-4-ol (10d)
From 2d (0.96 g, 3.3 mmol) 10d (0.38 g, 63%) was obtained. MS
(EI) m/z (%) 195 (Mϩ ϩ 1, <5), 177 (90), 55 (100). IR (film):
ν/cmϪ1 3440s, 2937s, 1648m, 915m. 1H NMR (400 MHz,
Procedure B. The vinylcerium reagent was prepared from
CeCl3ؒ7H2O (2.73 g, 7.3 mmol) and vinylmagnesium chloride
(1.7 M solution in THF, 3.77 ml, 6.4 mmol) as described by
Lautens et al.36 Acylated oxazolidinones 2 or bornane sultams 4
(1.8 mmol) were added in dry, degassed THF (22 ml) at Ϫ78 ЊC.
The reaction mixture was stirred until the starting material was
fully consumed, as indicated by TLC. Water (30 ml) was added
dropwise and the minimum amount of hydrochloric acid (1M)
CDCl ) δ 5.92–5.78 (3H, HC᎐CH ), 5.68 (dm, 1H, J = 10.0,
᎐
3
2
HC᎐), 5.15–5.03 (4H, H C᎐CH), 4.22 (d, 1H, J = 16.2,
᎐
᎐
2
OCHH ), 4.15 (d, 1H, J = 16.2, OCHH ), 3.40 (dd, 1H, J = 10.7,
3.0, HCO), 2.40–2.18 (5H, CH2, OH ), 2.09 (dd, 1H, J = 14.2,
8.2, CH2), 1.91 (dm, 1H, J = 17.0, CH2). 13C NMR (100 MHz,
CDCl ) δ 133.6, 133.5, 125.9, 124.4 [(1), CH᎐CH ], 118.3, 118.0
᎐
3
2
J. Chem. Soc., Perkin Trans. 1, 2002, 1050–1060
1057

View Article Online
was added to ensure solution of inorganic precipitates. The
aqueous layer was extracted and the combined organic extracts
were dried with MgSO4, filtered and evaporated. The resulting
divinylcarbinols were easily separated from the oxazolidinone
11 or bornane sultam 13, respectively, by flash chromatography
on silica. When oxazolidinones 2a,b were used, acrylates 16a,b
were formed exclusively.
40%) was obtained. Mp 79 ЊC. MS (EI) m/z (%) 329 (Mϩ, <5),
301 (20), 238 (40), 166 (70), 97 (100). IR (disk, KBr): ν/cmϪ1
3353m, 2844w, 1720s, 1648s, 1408m, 1300m, 1079s, 811m,
703m. 1H NMR (400 MHz, CDCl3) δ 7.30–7.26 (2H, Ph), 7.23–
7.18 (3H, Ph), 6.78 (d, 1H, J = 8.8, HN), 6.43 (dd, 1H, J = 17.5,
1.5, H C᎐CH), 6.16 (dd, 1H, J = 17.5, 10.5, HC᎐CH ), 5.87 (dd,
᎐
᎐
2
2
1H, J = 10.5, 1.5, H C᎐CH), 5.76 (dm, 1H, J = 10.5, CH᎐CH),
᎐
᎐
2
5.63 (dm, 1H, J = 10.5, CH᎐CH), 4.58 (m, 1H, HCN), 4.20–
4.13 (3H, H2CO, HHCO), 4.09 (dm, 1H, J = 16.5, H6), 2.88 (d,
᎐
(S)-2-[(R)-2-Methylpent-4-enamido]-3-phenylpropyl acrylate
(16a)
2H, J = 7.3, H CPh), 2.32 (dm, 1H, J = 17.5, HHCCH᎐), 2.08
᎐
2
(dm, 1H, J = 17.5, HHCCH᎐), 1.36 (s, 3H, H C). 13C NMR
᎐
3
Following procedure A, from 2a (0.80 g, 2.9 mmol) 16a (0.53 g,
60%) was obtained. Following procedure B, from 2a (0.80 g,
2.9 mmol) 16a (0.50 g, 57%) was obtained. Mp 107 ЊC. MS (EI,
70 eV): m/z (%) = 302 (Mϩ ϩ 1, 100), 230 (20), 138 (40), 114
(30), 91 (30), 69 (65), 55 (70). IR (disk, KBr): ν/cmϪ1 3287s,
2965w, 1725s, 1648s, 1552m, 1299m, 1211m, 700m. Found: C,
71.7%; H, 7.6%; N, 4.6%. C18H23O3N requires C, 71.7%; H,
(100 MHz, CDCl ) δ 174.6, 165.9 [(0), C᎐O], 137.0 [(0), Ph],
᎐
3
131.4 [(2), CH ᎐CH], 129.2, 128.6, 128.0, 126.7, 124.3, 122,7
᎐
2
[(1), Ph, CH᎐CH, CH᎐CH2], 74.6 [(0), C(CH3)O], 64.9, 61.7
᎐
᎐
[(2), CH2O], 48.8 [(1), CHN], 37.6, 31.8 [(2), CH2Ph,
HHCCH᎐], 21.7 [(3), CH ]. [α[2D2 Ϫ51.2 (c 0.86 in CH Cl ).
᎐
3
2
2
1
(4S)-4-Methoxy-3-vinylhepta-1,6-dien-3-ol (18c)
7.7%; N, 4.7%. H NMR (400 MHz, CDCl3) δ 7.25–7.12 (5H,
Ph), 6.37 (dd, 1H, J = 17.3, 1.5, H C᎐CH), 6.08 (dd, 1H, J =
᎐
2
Following procedure B, from 4c (0.66 g, 2.0 mmol) 0.24 g (70%)
of 18c were obtained. MS (EI) m/z (%) 167 (Mϩ Ϫ 1, <5), 151
(40), 119 (95), 85 (100), 55 (45). IR (film) ν/cmϪ1 3479br m,
2933m, 1413w, 1102s, 922s, 799w. 1H NMR (400 MHz, CDCl3)
17.3, 10.3, HC᎐CH ), 5.82 (dd, 1H, J = 10.3, 1.5, H C᎐CH),
᎐
᎐
2
2
5.60–5.52 (m, 2H, HN, HC᎐CH ), 4.94 (dddd, 1H, J = 17.3, 1.8,
᎐
2
1.8, 1.8, H C᎐CH), 4.90 (dddd, 1H, J = 10.3, 1.8, 1.8, 1.8, H C᎐
᎐
᎐
2
2
CH), 4.42 (m, 1H, HCN), 4.13 (dd, 1H, J = 11.5, 5.8, H2CO),
4.05 (dd, 1H, J = 11.5, 4.5, H2CO), 2.83 (dd, 1H, J = 13.8, 6.5,
H2CPh), 2.75 (dd, 1H, J = 13.8, 7.8, H2CPh), 2.23 (ddm, 1H, J =
13.8, 7.3, H2CCHCH3), 2.12 (dm, 1H, J = 6.8, HCCH3), 2.00
(ddm, 1H, J = 13.8, 6.3, H2CCHCH3), 1.02 (d, 3H, J = 6.8,
H3C). 13C NMR (100 MHz, CDCl ) δ 175.3, 166.2 [(0), C᎐O],
δ 5.98 (dd, 1H, J = 17.3, 10.8, HC᎐CH ), 5.95 (dd, 1H, J = 17.3,
᎐
2
10.8, HC᎐CH ), 5.86 (dddd, 1H, J = 17.3, 10.3, 7.0, 7.0, HC᎐
᎐
᎐
2
CH ), 5.34 (dm, 1H, J = 17.3, H C᎐CH), 5.34 (dm, 1H, J = 17.3,
᎐
2
2
H C᎐CH), 5.17 (dm, 1H, J = 17.3, H C᎐CH), 5.17 (dm, 1H, J =
᎐
᎐
2
2
10.8, H C᎐CH), 5.07 (dddd, 1H, J = 17.3, 1.5, 1.5, 1.5, H C᎐
᎐
᎐
2
2
᎐
3
CH), 5.01 (dddd, 1H, J = 10.3, 1.5, 1.5, 1.5, H C᎐CH), 3.41
᎐
2
136.9 [(0), Ph], 135.7 [(1), CH᎐CH ], 131.6 [(2), CH ᎐CH],
᎐
᎐
2
2
(s, 3H, H3CO), 3.14 (dd, 1H, J = 7.5, 3.8, HCO), 2.40–2.32
129.2, 128.6, 127.9, 126.8, [(1), Ph, CH᎐CH ], 116.8 [(2), CH ᎐
᎐
᎐
2
2
(2H, HO, H CCH᎐CH ), 2.21 (dm, 1H, J = 14.8, H CCH᎐
᎐ ᎐
2 2 2
CH2). 13C NMR (100 MHz, CDCl3) δ 140.0, 139.0, 135.9 [(1),
CH᎐CH ], 116.7, 114.5, 114.5 [(2), CH ᎐CH], 86.7 [(1), CHO],
CH], 64.9 [(2), CH2O], 49.4 [(1), CHN], 41.3 [(1), CHCH3],
38.2, 37.6 [(2), CH2], 17.3 [(3), CH3]. [α]2D2 Ϫ28.9 (c 1.40 in
CH2Cl2).
᎐
᎐
2
2
78.1 [(0), COH], 60.3 [(3), CH O], 35.0 [(2), CH CH᎐CH ].
᎐
3
2
2
[α]2D3 Ϫ10.7 (c 1.52 in CH2Cl2).
(S)-2-[(R)-2-Methyl-3-phenylpropanamido]-3-phenylpropyl
acrylate (16b)
(4S)-4-Methoxy-5-phenyl-3-vinylpent-1-en-3-ol (18d)
Following procedure A, from 2b (0.56 g, 1.5 mmol) 16b (0.43 g,
70%) was obtained. Following procedure B, from 2b (0.56 g,
1.5 mmol) 16b (0.41 g, 67%) was obtained. Mp 89 ЊC. MS (EI)
m/z (%) 352 (Mϩ ϩ 1, 40), 280 (30), 188 (60), 119 (30), 91 (100),
55 (50). IR (disk, KBr) ν/cmϪ1 3298s, 2964w, 1726s, 1648s,
1545m, 1409m, 1300m, 1216m, 703s. Found: C, 74.5%; H,
7.2%; N, 3.9%. C22H25O3N requires C, 75.1 %; H, 7.2%; N,
4.0%. 1H NMR (400 MHz, CDCl3) δ 7.24–7.08 (8H, Ph), 6.94–
Following procedure B, from 4d (0.67 g, 2.0 mmol) 18d (0.28 g,
73%) was obtained. MS (EI) m/z (%) 217 (Mϩ Ϫ 1, <5), 169
(100). IR (film): ν/cmϪ1 3470br m, 2931s, 1496m, 1454m, 1105s,
924m, 700s. 1H NMR (400 MHz, CDCl3) δ 7.30–7.19 (5H, Ph),
6.08 (dd, 1H, J = 17.3, 10.8, HC᎐CH ), 6.05 (dd, 1H, J = 17.3,
᎐
2
10.8, HC᎐CH ), 5.43 (dd, 1H, J = 17.3, 1.5, H C᎐CH), 5.42 (dd,
᎐
᎐
2
2
1H, J = 17.3, 1.5, H C᎐CH), 5.26 (dd, 1H, J = 10.8, 1.5, H C᎐
᎐
᎐
2
2
CH), 5.24 (dd, 1H, J = 10.8, 1.5, H C᎐CH), 3.32 (dd, 1H, J =
᎐
2
6.90 (2H, Ph), 6.31 (dd, 1H, J = 17.3, 1.3, H C᎐CH), 6.02 (dd,
᎐
2
9.8, 2.8, HCO), 3.10 (s, 3H, H3CO), 2.94 (dd, 1H, J = 14.3, 2.8,
1H, J = 17.3, 10.3, HC᎐CH ), 5.79 (dd, 1H, J = 10.3, 1.3, H C᎐
᎐
᎐
2
2
H2CPh), 2.67 (dd, 1H, J = 14.3, 9.8, H2CPh), 2.46 (br s, 1H,
HO). 13C NMR (100 MHz, CDCl ) δ 140.1 [(1), CH᎐CH ],
CH), 5.34 (d, 1H, J = 8.3, HN), 4.33 (m, 1H, HCN), 3.99 (dd,
1H, J = 11.5, 6.0, H2CO), 4.96 (dd, 1H, J = 11.5, 4.3, H2CO),
2.83 (dd, 1H, J = 13.8, 8.8, H2CPh), 2.68 (dd, 1H, J = 13.8, 5.3,
H2CPh), 2.57 (dd, 1H, J = 13.8, 6.3, H2CPh), 2.45 (dd, 1H, J =
13.8, 8.0, H2CPh), 2.31 (dm, 1H, J = 7.0, HCCH3), 1.07 (d, 3H,
J = 7.0, H3C). 13C NMR (100 MHz, CDCl3) δ 175.1, 166.1 [(0),
᎐
3
2
139.7 [(0), Ph], 139.1 [(1), CH᎐CH ], 129.4, 128.3, 126.0 [(1),
᎐
2
Ph], 114.6, 114.6 [(2), CH ᎐CH], 88.8 [(1), CHO], 78.2 [(0),
᎐
2
COH], 61.1 [(3), CH3O], 37.1 [(2), CH2Ph].
(4S)-4-Allyloxy-3-vinylhepta-1,6-dien-3-ol (18e) and (S)-4-
Allyloxynona-1,8-dien-5-one (19e)
C᎐O], 139.8, 136.7 [(0), Ph], 131.5 [(2), CH ᎐CH], 129.2, 129.0,
᎐
᎐
2
128.6, 128.4, 127.8, 126.7, 126.3, [(1), Ph, CH᎐CH ], 64.4 [(2),
᎐
2
CH2O], 49.6 [(1), CHN], 44.0 [(1), CHCH3], 40.4, 37.2 [(2),
Following procedure A, from 4e (0.72 g, 2.0 mmol) a mixture of
18e (59%) and 19e (20%) was obtained. The compounds were
separated by column chromatography on silica. Following pro-
cedure B, from 4e (0.72 g, 2.0 mmol) 18e (0.31 g, 79%) was
obtained as a single isomer. Spectroscopic data for 18e: MS (EI)
m/z (%) 195 (Mϩ ϩ 1, <5), 137 (60), 93 (40), 81 (50), 67 (50), 55
(100). IR (film) ν/cmϪ1 3465br w, 3079w, 2923m, 1088m, 995m,
921s, 805w. Found: C, 73.6%; H, 9.2%. C12H18O2 requires C,
CH2], 17.7 [(3), CH3]. [α]2D2 Ϫ39.5 (c 1.06 in CH2Cl2).
Attempted cleavage of oxazolidinone 2c
Following procedure A, from 2c (0.47 g, 1.5 mmol) an insepar-
able 1.5 : 1 : 1 mixture of 14c, 15c and 16c was obtained, along
with the oxazolidinone 11. Following procedure B, from 2c
(0.80 g, 2.5 mmol) only the R-configured divinylcarbinol 14c
(0.19 g, 40%) was obtained. Spectroscopic data were identical
to those observed for 12e. [α]2D2 ϩ13.3 (c 1.10 in CH2Cl2).
1
74.2%; H, 9.3%. H NMR (400 MHz, CDCl3) δ 6.00 (dd, 1H,
J = 17.3, 10.8, HC᎐CH ), 5.96 (dd, 1H, J = 17.3, 10.8, HC᎐
᎐
᎐
2
CH ), 5.90–5.80 (2H, HC᎐CH ), 5.34 (dd, 1H, J = 17.3, 1.5,
᎐
2
2
H C᎐CH), 5.33 (dd, 1H, J = 17.3, 1.5, H C᎐CH), 5.21 (dddd,
᎐
᎐
2
2
(S)-2-{1-[(S)-2-Methyl-3,6-dihydro-2H-pyran-2-yl]methanoyl-
amino}-3-phenylpropyl acrylate (17)
1H, J = 17.3, 1.5, 1.5, 1.5, H C᎐CH), 5.17 (dd, 1H, J = 10.8, 1.5,
᎐
2
H C᎐CH), 5.17 (dd, 1H, J = 10.8, 1.5, H C᎐CH), 5.12 (dddd,
᎐
᎐
2
2
Following procedure A, from 8a (0.39 g, 1.3 mmol) 17 (0.17 g,
1H, J = 10.3, 1.5, 1.5, 1.5, H C᎐CH), 5.06 (dddd, 1H, J = 17.3,
᎐
2
1058
J. Chem. Soc., Perkin Trans. 1, 2002, 1050–1060

View Article Online
1.5, 1.5, 1.5, H C᎐CH), 5.00 (dddd, 1H, J = 10.0, 1.5, 1.5, 1.5,
Spectroscopic data for 19g: MS (EI) m/z (%) 241 (Mϩ ϩ 1,
᎐
2
H C᎐CH), 4.11 (dddd, 1H, J = 12.5, 5.5, 1.5, 1.5, H CO), 4.02
<5), 157 (20), 138 (40), 115 (100), 71 (30), 55 (80). IR (film)
ν/cmϪ1 2981m, 2931m, 1729s, 1373m, 1184m, 995m, 921m.
Found: C, 64.4%; H, 8.4%. C13H20O4 requires C, 64.5%; H,
8.4%. 1H NMR (400 MHz, CDCl3) δ 5.84 (dddd, 1H, J = 17.1,
᎐
2
2
(dddd, 1H, J = 12.5, 5.5, 1.5, 1.5, H2CO), 3.30 (dd, 1H, J = 8.5,
3.5, HCO), 2.45 (br s, 1H, HO), 2.36 (dm, 1H, J = 14.5,
H2CCHO), 2.24 (dm, 1H, J = 14.5, H2CCHO). 13C NMR (100
MHz, CDCl ) δ 140.1, 139.1, 135.9, 134.7 [(1), CH᎐CH ],
10.5, 5.8, 5.8, HC᎐CH ), 5.76 (dddd, 1H, J = 17.1, 10.3, 6.5, 6.5,
᎐
2
᎐
3
2
116.8, 116.7, 114.4, 114.4 [(2), CH ᎐CH], 84.6 [(1), CHO], 78.1
HC᎐CH ), 5.24 (dm, 1H, J = 17.1, H C᎐CH), 5.16 (dm, 1H, J =
᎐ ᎐
2 2
᎐
2
[(0), COH], 73.3 [(2), CH2O], 35.3 [(2), CH2CHO]. [α]2D2 Ϫ12.8
(c 1.90 in CH2Cl2). Spectroscopic data for 19e are reported
below.
10.5, H C᎐CH), 4.99 (dm, 1H, J = 17.1, H C᎐CH), 4.92 (dm,
᎐ ᎐
2
1H, J =210.3, H C᎐CH), 4.11 (dd, 1H, J = 6.5, 5.3, HCO), 4.10
᎐
2
(q, 2H, J = 7.0, H2CCH3), 4.03 (dm, 2H, J = 6.5, H2CCHO),
2.80–2.55 (4H, H2C), 2.28 (ddm, 2H, J = 14.8, 7.0, H2C), 1.20 (t,
3H, J = 7.0, H3CCH2). 13C NMR (100 MHz, CDCl3) δ 210.2,
3-[(2S)-3,6-Dihydro-2H-pyran-2-yl)penta-1,4-dien-3-ol (18f )
and 1-[(2S)-3,6-Dihydro-2H-pyran-2-yl)pent-4-en-1-one (19f )
170.3 [(0), C᎐O], 137.0, 133.7 [(1), CH᎐CH ], 117.9, 115.2 [(2),
᎐
᎐
2
CH ᎐CH], 80.5 [(1), CHO], 71.8, 60.8 [(2), CH O], 37.6, 36.8,
᎐
2
2
Following procedure A, from 4f (0.55 g, 1.7 mmol) a mixture of
18f (0.12 g, 43%) and 19f (0.05 g, 19%) was obtained. The com-
pounds were separated by column chromatography on silica.
Following procedure B, from 4f (0.60 g, 1.8 mmol) 18f (0.19 g,
62%) was obtained as a single isomer. Spectroscopic data for
18f: MS (EI) m/z (%) 167 (Mϩ ϩ 1, <5), 83 (70), 55 (100). IR
(film) ν/cmϪ1 3477br m, 2938m, 1727m, 1092s, 924m, 800w,
27.0 [(2), CH2], 14.0 [(3), CH3]. [α]2D5 Ϫ19.4 (c 1.10 in CH2Cl2).
Procedure for the selective preparation of 19e by vinylcuprate
addition to 4e
To a suspension of CuI (0.53 g, 2.8 mmol) in THF (40 ml) was
added a solution of vinylmagnesium chloride (4.1 ml of a 1.7 M
solution in THF, 6.9 mmol) at Ϫ78 ЊC. After 30 min at this
temperature, 4e (0.49 g, 1.4 mmol) in THF (5 ml) was added.
After 24 h at Ϫ10 ЊC the reaction was quenched at 50% conver-
sion by addition of water. After usual aqueous work-up the
product 19e (0.12 g, 45%) was isolated by column chrom-
atography on silica, along with recovered starting material 4e
(0.22 g, 45%) and bornane sultam 13 (0.12 g, 40%). MS (EI)
m/z (%) 195 (Mϩ ϩ 1, 5%), 137 (55), 55 (100). IR (film) ν/cmϪ1
1
656m. H NMR (400 MHz, CDCl3) δ 5.97 (dd, 1H, J = 17.3,
10.8, HC᎐CH ), 5.92 (dd, 1H, J = 17.3, 10.8, HC᎐CH ), 5.78
᎐
᎐
2
2
(dm, 1H, J = 10.0, HC᎐CH ), 5.65 (dm, 1H, J = 10.0, HC᎐CH ),
᎐
᎐
5.36 (dd, 1H, J = 17.3, 1.5, H C᎐CH), 5.35 (dd, 1H, J = 17.3,
᎐
2
1.5, H C᎐CH), 5.19 (dd, 1H, J = 10.8, 1.5, H C᎐CH), 5.18 (dd,
᎐
᎐
2
2
1H, J = 10.8, 1.5, H C᎐CH), 4.21 (dm, 1H, J = 16.3, HHCO),
᎐
2
4.16 (dm, 1H, J = 16.3, HHCO), 3.48 (dd, 1H, J = 10.8, 3.3,
HCO), 2.61 (br s, 1H, HO), 2.22 (m, 1H, HCOCHH), 1.91 (dm,
1H, J = 17.5, HCOCHH). 13C NMR (100 MHz, CDCl3)
1
2962s, 1719s, 1261s, 803s. H NMR (400 MHz, CDCl3) δ 5.86
(dddd, 1H, J = 17.5, 10.5, 5.7, 5.3, ᎐CHCH O), 5.81–5.70 (2H,
᎐
2
δ 139.8, 138.2 [(1), CH᎐CH ], 125.6, 124.2 [(1), HC᎐CH],
᎐
᎐
2
HC᎐CH ), 5.26 (dm, 1H, J = 17.2, ᎐CH ), 5.17 (dm, 1H, J =
᎐
᎐
2
2
115.0, 114.6 [(2), CH ᎐CH], 78.2 [(1), HCO], 76.8 [(0), COH],
᎐
2
10.5, ᎐CH ), 5.08 (dm, 1H, J = 17.0, ᎐CH ), 5.04 (dm, 1H,
66.5 [(2), HHCO], 25.0 [(2), HHCCH᎐]. [α]2D4 Ϫ103.6 (c 1.12 in
᎐
᎐
2
2
᎐
J = 10.2, ᎐CH ), 5.01 (dm, 1H, J = 17.2, ᎐CH ), 4.94 (dm, 1H,
᎐
᎐
2
2
CH2Cl2).
J = 10.2, ᎐CH2), 4.01 (ddm, 1H, J = 12.7, 5.5, OCH2), 3.93
1
᎐
Spectroscopic data for 19f: H NMR (400 MHz, CDCl3) δ
(ddm, 1H, J = 12.7, 5.7, OCH2), 3.79 (dd, 1H, J = 6.2, 6.2,
5.82 (dm, 1H, J = 10.0, CH᎐CH ), 5.78 (dddd, 1H, J = 17.0,
᎐
CHO), 2.62–2.25 (6H, H2C). 13C NMR (100 MHz, CDCl3) δ
10.5, 6.5, 6.5, HC᎐CH ), 5.71 (dm, 1H, J = 10.0, CH᎐CH ),
᎐
᎐
2
211.4 [(0), C᎐O], 137.1, 133.9, 133.0 [(1), CH᎐CH ], 117.9,
᎐
᎐
2
5.00 (dm, 1H, J = 17.3, H C᎐CH), 4.94 (dm, 1H, J = 10.5,
᎐
2
117.6, 115.2 [(2), CH ᎐CH], 84.2 [(1), CHO], 71.3 [(2), CH O],
᎐
2
2
H C᎐CH), 4.30 – 4.17 (2H, HHCO), 3.97 (dd, 1H, J = 10.3, 4.5,
37.3, 36.4, 27.0 [(2), CH2]. [α]2D2 Ϫ27.4 (c 1.35 in CH2Cl2).
᎐
2
HCO), 2.68 (dd, 1H, J = 7.3, 7.3, H CC᎐O), 2.32 (dm, 1H, J =
᎐
2
7.3, H2C), 2.29 (dm, 1H, J = 7.3, H2C), 2.22–2.12 (3H, 3 ×
[(2S,3S)-3-Hydroxy-3-vinyl-3,6-dihydro-2H-pyran-2-yl)acetic
acid ethyl ester (20)
CHH ). 13C NMR (100 MHz, CDCl ) δ 209.7 [(0), C᎐O], 137.1
᎐
3
[(1), CH᎐CH ], 126.1, 123.3 [(1), CH᎐CH], 115.1 [(2), CH ᎐
᎐
2
᎐
᎐
2
CH], 78.4 [(1), HCO], 65.9 [(2), HHCO], 37.1, 27.0, 26.9 [(2),
CH2].
Following the general procedure for ring closing metathesis
reactions, from 18g (0.13 g, 0.54 mmol) and Grubbs’ catalyst
(13 mg, 3 mol%) a mixture of diastereoisomers of 20
[(2S,3S):(2S,3R) = 3 : 1) (77 mg, 67%) was isolated. MS (EI)
m/z (%) 211 (Mϩ Ϫ 1, <5), 107 (20), 95 (100), 77 (50), 67 (70).
IR (film) ν/cmϪ1 3469br m, 2983w, 1744s, 1300m, 1182m, 929m.
Found: C, 61.8%; H, 7.2%. C11H16O4 requires C, 62.2%; H,
(3S)-3-Allyloxy-4-hydroxy-4-vinylhex-5-enoic acid ethyl ester
(18g) and (3S)-3-Allyloxy-4-oxooct-7-enoic acid ethyl ester (19g)
Following procedure A, from 4g (1.51 g, 3.8 mmol) a mixture of
18g (0.39 g, 43%) and 19g (0.15 g, 17%) was obtained. The
compounds were separated by column chromatography on
silica. Spectroscopic data for 18g: MS (EI) m/z (%) 241 (Mϩ ϩ
1, <5), 115 (80), 83 (40), 55 (100). IR (film): ν/cmϪ1 3503br w,
2983w, 1732s, 1307m, 1182m, 926m. Found: C, 64.4%; H, 8.1%.
1
7.6%. H NMR (400 MHz, CDCl3) δ 5.88 (dm, 1H, J = 10.0,
CHCH ), 5.71 (ddd, 1H, J = 10.0, 2.0, 2.0, CHCH ), 5.71 (dd,
1H, J = 17.3, 10.8, HC᎐CH ), 5.37 (dd, 1H, J = 17.3, 1.5, H C᎐
᎐
᎐
2
2
CH), 5.18 (dd, 1H, J = 10.8, 1.5, H C᎐CH), 4.16–4.08 (4H,
᎐
2
H2CO, HHCO), 3.85 (dd, 1H, J = 7.3, 5.0, HCO), 2.53 (dm, 1H,
1
C13H20O4 requires C, 64.5%; H, 8.4%. H NMR (400 MHz,
J = 7.3, H CC᎐O), 2.52 (dm, 1H, J = 5.0, H CC᎐O), 2.30 (br s,
᎐ ᎐
2 2
CDCl ) δ 5.98 (dd, 1H, J = 17.3, 10.8, HC᎐CH ), 5.89 (dd, 1H,
1H, HO), 1.20 (t, 3H, J = 7.3, H3CCH2). 13C NMR (100 MHz,
CDCl ) δ 171.9 [(0), C᎐O], 138.4 [(1), CH᎐CH ], 130.1, 128.6
᎐
3
2
J = 17.3, 10.8, HC᎐CH ), 5.79 (dddd, 1H, J = 17.3, 10.3, 5.8,
᎐
᎐
᎐
2
3
2
5.8, HC᎐CH ), 5.33 (dd, 1H, J = 17.3, 1.3, H C᎐CH), 5.32 (dd,
[(1), HC᎐CH], 116.0 [(2), CH ᎐CH], 78.2 [(1), HCO], 69.7 [(0),
᎐ ᎐
2
–CHHCH᎐], 66.0, 60.5 [(2), CH O], 34.6 [(2), CH C᎐O], 14.1
᎐ ᎐
2 2
᎐
᎐
2
2
1H, J = 17.3, 1.3, H C᎐CH), 5.18 (dddd, 1H, J = 17.3, 1.5, 1.5,
᎐
2
1.5, H C᎐CH), 5.16 (dd, 1H, J = 10.8, 1.3, H C᎐CH), 5.13 (dd,
[(3), CH3].
᎐
᎐
2
2
1H, J = 10.8, 1.3, H C᎐CH), 5.08 (dddd, 1H, J = 10.3, 1.5, 1.5,
NMR spectroscopic data for the minor diastereomer
᎐
2
1.5, H C᎐CH), 4.14–4.02 (4H, H CO), 3.81 (dd, 1H, J = 8.0,
(obtained from the mixture): 1H NMR (400 MHz, CDCl3)
᎐
2
2
4.0, HCO), 2.62 (dd, 1H, J = 16.1, 4.0, H CC᎐O), 2.46 (br s, 1H,
δ 5.89 (dd, 1H, J = 17.5, 10.5, HC᎐CH ), 5.76 (dm, 1H, J = 10.0,
᎐
2
᎐
2
HO), 2.42 (dd, 1H, J = 16.1, 8.0, H CC᎐O), 1.20 (t, 3H, J = 7.3,
CH᎐CH), 5.56 (ddd, 1H, J = 10.0, 2.3, 2.3, CH᎐CH), 5.28
᎐
᎐ ᎐
2
H3CCH2). 13C NMR (100 MHz, CDCl ) δ 172.3 [(0), C᎐O],
(dd, 1H, J = 17.5, 1.5, H C᎐CH), 5.17 (dd, 1H, J = 10.5, 1.5,
᎐
2
᎐
3
139.8, 138.8, 134.5 [(1), CH᎐CH ], 116.9, 114.7, 114.6 [(2),
H C᎐CH), 4.14–4.04 (4H, H CO), 3.84 (dd, 1H, J = 7.0, 4.3,
᎐
2 2
᎐
2
CH ᎐CH], 81.1 [(1), CHO], 77.7 [(0), COH], 73.2, 60.6 [(2),
HCO), 2.69 (br s, 1H, HO), 2.61 (dd, 1H, J = 16.1, 4.3, H CC᎐
᎐
᎐
2
2
CH O], 36.1 [(2), CH C᎐O], 14.1 [(3), CH ]. [α]2D5 Ϫ22.1 (c 1.10
O), 2.35 (dm, 1H, J = 16.1, H CC᎐O), 1.20 (t, 3H, J = 7.3,
᎐
᎐
2
2
3
2
in CH2Cl2).
H3CCH2). 13C NMR (100 MHz, CDCl ) δ 172.2 [(0), C᎐O],
᎐
3
J. Chem. Soc., Perkin Trans. 1, 2002, 1050–1060
1059

View Article Online
11 M. J. Bassindale, P. Hamley, A. Leitner and J. P. A. Harrity,
Tetrahedron Lett., 1999, 40, 3247.
137.8 [(1), CH᎐CH ], 130.9, 126.1 [(1), C4, C5], 114.9 [(2),
᎐
2
CH ᎐CH], 77.6 [(1), C2], 71.2 [(0), C3], 65.8, 60.7 [(2), CH O,
᎐
2
2
12 M. Lautens and G. Hughes, Angew. Chem., 1999, 111, 160;
M. Lautens and G. Hughes, Angew. Chem., Int. Ed., 1999, 38, 129.
13 B. Schmidt and H. Wildemann, Synlett, 1999, 1591.
14 B. Schmidt and H. Wildemann, J. Org. Chem., 2000, 65, 5817.
15 D. J. Wallace, C. J. Cowden, D. J. Kennedy, M. S. Ashwood, I. F.
Cottrell and U.-H. Dolling, Tetrahedron Lett., 2000, 41, 2027.
16 J. L. Leighton and E. Chapman, J Am. Chem. Soc., 1997, 119,
12416.
C6], 35.634.6 [(2), CH C᎐O], 14.0 [(3), CH ].
᎐
2
3
1-[(R)-1-Methyl-2-phenylethyl]cyclopent-3-enol (21)
No conversion of diallylcarbinol 10b to cyclopentenol 21 was
observed at ambient temperature. In refluxing toluene (20 ml)
in the presence of Grubbs’ catalyst (253 mg, 5 mol%) 10b (1.42
g, 6.2 mmol) reacted smoothly to give 21 (0.99 g, 79%). MS (EI)
m/z (%) 202 (Mϩ, <5), 186 (100), 91 (20). IR (film) ν/cmϪ1 3454
bm, 3060m, 3026m, 2967m, 2933m, 1464m, 885m, 702s. Found:
17 M. J. Zacuto and J. L. Leighton, J. Am. Chem. Soc., 2000, 122, 8587.
18 H. Cao, S. G. Van Ornum and J. M. Cook, Tetrahedron Lett., 2000,
41, 5313.
19 S. A. Kozmin, Org. Lett., 2001, 3, 755.
1
C, 82.4%; H, 8.4%. C14H18O requires C, 83.1%; H, 9.0%. H
20 P. Müller and Z. S. Miao, Helv. Chim. Acta, 1994, 77, 1826.
21 Y. N. Bubnov, M. A. Misharin and A. V. Ignatenko, Tetrahedron
Lett., 1997, 38, 6259.
NMR (400 MHz, CDCl3) δ 7.30–7.25 (2H, Ph), 7.21–7.15 (3H,
Ph), 5.74 (s, 2H, HC᎐CH), 2.99 (dd, 1H, J = 13.3, 3.0, H CPh),
᎐
2
22 G. A. Molander, P. J. Nichols and B. C. Noll, J. Org. Chem., 1998,
63, 2292.
23 S. Okamoto and T. Livinghouse, J. Am. Chem. Soc., 2000, 122, 1223.
24 D. L. J. Clive and H. Cheng, Chem. Commun., 2001, 605.
25 M. Michaut, M. Santelli and J.-L. Parrain, J. Organomet. Chem.,
2000, 606, 93.
26 D. J. Wallace, P. G. Bulger, D. J. Kennedy, M. S. Ashwood, I. F.
Cottrell and U.-H. Dolling, Synlett, 2001, 357.
27 B. Schmidt and H. Wildemann, J. Chem. Soc., Perkin Trans. 1, 2000,
2916.
2.61 (d, 1H, J = 16.5, H2C), 2.56 (d, 2H, J = 16.5, H2C), 2.43
(d, 1H, J = 16.8, H2C), 2.36 (dd, 1H, J = 13.3, 10.8, H2CPh),
2.33 (d, 1H, J = 16.8, H2C), 1.89 (dqd, 1H, J = 10.8, 6.5, 3.0,
HCCH3), 1.75 (br s, 1H, HO), 0.86 (d, 1H, J = 6.5, H3C).
13C NMR (100 MHz, CDCl3) δ 141.5 [(0), Ph], 129.6, 128.7,
128.6, 128.1, 125.6 [(1), Ph, CH᎐CH ], 84.0 [(0), COH], 46.3,
᎐
2
46.0 [(2), CH2], 44.4 [(1), CHCH3], 38.3 [(2), CH2], 14.1 [(3),
CH3]. [α]2D4 ϩ4.5 (c 1.55 in CH2Cl2).
28 D. J. Wallace, J. M. Goodman, D. J. Kennedy, A. J. Davies,
C. J. Cowden, M. S. Ashwood, I. F. Cottrell, U.-H. Dolling and
P. J. Reider, Org. Lett., 2001, 3, 671.
Acknowledgements
29 D. A. Evans, Aldrichimica Acta, 1982, 15, 23.
Generous financial support from the DFG and the Fonds der
Chemischen Industrie is gratefully acknowledged. We thank
Prof. P. Eilbracht for encouragement and support.
30 D. A. Evans, in Stereoselective Alkylation Reactions of Chiral Metal
Enolates, ed. J. D. Morrison, Academic Press, New York, 1984.
31 W. Oppolzer, Tetrahedron, 1987, 43, 1969.
32 C. Kashima, X. C. Huang, Y. Harada and A. Hosomi, J. Org.
Chem., 1993, 58, 793.
33 D. P. Curran and T. A. Heffner, J. Org. Chem., 1990, 55, 4585.
34 D. A. Evans, J. R. Gage and J. L. Leighton, J. Am. Chem. Soc., 1992,
114, 9434.
35 P. Schwab, R. H. Grubbs and J. W. Ziller, J. Am. Chem. Soc., 1996,
118, 100.
36 M. Lautens, G. Hughes and V. Zunic, Can. J. Chem., 2000, 78, 868.
37 S. Nahm and S. M. Weinreb, Tetrahedron Lett., 1981, 22, 3815.
38 C. Agami, F. Couty and H. Mathieu, Tetrahedron Lett., 1998, 39,
3505.
39 M. J. Batchelor, R. J. Gillespie, J. M. C. Golec, C. J. R. Hedgecock,
S. D. Jones and R. Murdoch, Tetrahedron, 1994, 50, 809.
40 P. A. Wender, K. D. Rice and M. E. Schnute, J. Am. Chem. Soc.,
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