Diastereoreactivity of a chiral oxathiane derived from 5-hydroxy-1-tetralone

Article abstract of DOI:10.1002/ejoc.200390039

The diastereoreactivity at the CH₂ bridge of a cis-oxathiane derived from 5-hydroxy-1-tetralone (unprotected and protected at the OH) was studied, and it appeared that all reactions at C-2 provided equatorial substitution. It was also found that: i) reductions of the equatorial benzoyl derivative with selectrides provided high diastereoselectivities at C-2' while LAH did not. Methyl Grignard addition was less selective and the selectivity of the propanoyl analogue was smaller; ii) condensation of aldehydes and/or ketones with the lithio derivative provided high equatorial diastereoselectivities at C-2 but low of nil diastereoselectivities at C-2′; iii) lithiation at C-2 was possible only with the oxathiane unsubstituted at C-2 (CH₂) and not possible with derivatives substituted at C-2 (CHR), perhaps due to the conformational rigidity of this oxathiane in the lithiation transition state and to the equatorial demand of all substituents at C-2, including lithium. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.

Full text of DOI:10.1002/ejoc.200390039

FULL PAPER
Diastereoreactivity of a Chiral Oxathiane Derived from 5-Hydroxy-1-tetralone
[a]
[a]
[b]
´
Arlette Solladie-Cavallo,* Milan Balaz, and Marta Salisova*
Keywords: Diastereoreactivity / Lithiation / 1,3-Oxathiane
The diastereoreactivity at the CH2 bridge of a cis-oxathiane
tivities at C-2 but low or nil diastereoselectivities at C-2Ј; iii)
derived from 5-hydroxy-1-tetralone (unprotected and pro- lithiation at C-2 was possible only with the oxathiane unsub-
tected at the OH) was studied, and it appeared that all reac- stituted at C-2 (CH2) and not possible with derivatives substi-
tions at C-2 provided equatorial substitution. It was also tuted at C-2 (CHR), perhaps due to the conformational rigid-
found that: i) reductions of the equatorial benzoyl derivative
with selectrides provided high diastereoselectivities at C-2Ј
ity of this oxathiane in the lithiation transition state and to
the equatorial demand of all substituents at C-2, including
while LAH did not. Methyl Grignard addition was less select- lithium.
ive and the selectivity of the propanoyl analogue was
smaller; ii) condensation of aldehydes and/or ketones with
( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
the lithio derivative provided high equatorial diastereoselec- Germany, 2003)
Introduction
ucts by chromatography. We thus decided to look for a
chiral oxathiane that would be available as both enanti-
omers and which could either be grafted onto a solid sup-
port (to be separated by filtration) or be derivatized with a
polyfluoro group (to be separated by extraction with a
fluorous phase). Oxathiane 5H-cis was therefore synthe-
sized and resolved, and its structure and absolute config-
uration were determined.[9]
Here we report the diastereoreactivity at the CH2 bridge
of unprotected and protected oxathiane 5H-cis, 5Bn-cis, and
5Si-cis.
The chiral 1,3-oxathianes 1,[1] 2,[2] 3,[3] and 4[4] have been
used since 1978 as CH2-bridge chiral auxiliaries for enantio-
selective syntheses of bioactive compounds, and in 1992 we
showed that oxathiane 4 could also be successfully used at
the sulfur atom as a chiral sulfide[5] for asymmetric syn-
thesis of monoaryl epoxides, trans-diaryl epoxides,[6] and
trans-cyclopropanes.[7]
Results and Discussion
Addition of Carbonyl Compounds to Lithio Derivative
5Bn-Li
Condensation of lithiated oxathiane 5Bn-Li with alde-
hydes and/or ketones exclusively afforded equatorial prod-
ucts 6Bn (Scheme 1), but with low diastereoselectivity at C-
2Ј, consistent with the results obtained with Eliel’s oxathi-
ane 1.[10] The results are collected in Table 1.
Oxathianes 2, 3, and 4, however, being derived from
natural products, are each available only as a single enan-
tiomer. Moreover, a drawback of these syntheses is the need
to separate the chiral auxiliaries 2Ϫ4 (used in stoichi-
ometric amounts) or some corresponding intermediate/pre-
cursor I[8] (formed during hydrolysis) from the desired prod-
The larger 70:30 and 80:20 diastereoselectivities observed
with benzaldehyde and with acetophenone, respectively
(Table 1, lines 3, 6) are interesting, but attempts to increase
these diastereoselectivities by changes in the solvent or ad-
dition of salts and/or HMPA to 5Bn-Li before addition of
benzaldehyde and/or acetophenone in fact resulted in more
complex mixtures in which at least three of the four possible
diastereomers could be detected.
[a]
´
´
Departement de Chimie Organique Fine, ECPM/Universite
Louis Pasteur,
67087 Strasbourg, France
After Eliel’s work[11] pointing out the important equator-
ial preference of lithium in lithiodithianes, Seebach and Du-
nitz[12] showed that 2-lithio-2-methyl-1,3-dithiane had a sul-
E-mail: cavallo@chimie.u-strasbg.fr
Department of Organic Chemistry, Comenius University,
84215 Bratislava, Slovakia
[b]
E-mail: salisova@fns.uniba.sk
Eur. J. Org. Chem. 2003, 337Ϫ345  2003 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim 1434Ϫ193X/03/0102Ϫ0337 $ 20.00ϩ.50/0
337

´
A. Solladie-Cavallo, M. Balaz, M. Salisova
FULL PAPER
Scheme 1
Table 1. Condensation of carbonyl compounds with the lithio derivative 5Bn-Li (*: from Table 2)
Electrophile
R1
R2
Compound
conversion
6Bn
I/II
Compound
Absol.
config. of I*
Acetaldehyde
Butyraldehyde
Benzaldehyde
Me
Pr
Ph
H
H
H
85%
83%
87%
50:50
57:43
70:30
6Bn-a
6Bn-b
6Bn-c
(R)
(R)
Benzyl methyl ketone
Butanone
Acetophenone
PhCH2
Et
Ph
Me
Me
Me
79%
89%
83%
53:47
58:42
80:20
6Bn-d
6Bn-e
6Bn-f
fur-bridged dimeric structure in the solid state (single-crys-
On the other hand, it is reasonable to suppose that the
tal X-ray diffraction). NMR studies[13] of 2-lithio-1,3-dithi- hybridization of C-2 should change from sp3-type to sp2-
ane and 2-lithio-2-methyl-1,3-dithiane then showed that type in the transition (upon addition of salts and/or of
these lithio derivatives were either monomeric or dimeric HMPA) from contact ions to separated ions (in which the
(sulfur-bridged) in THF solution at low temperature role of lithium should decrease), also making approach
(Ϫ100 °C), and cryoscopic measurements then indicated from the upper face of the oxathiane possible, and thus re-
that 2-lithio-2-methyl-1,3-dithiane was largely monomeric sulting in the potential formation of the two other diastere-
in THF.[14] Moreover, more recent NMR studies by omers, which would explain the more complex mixtures ob-
Reich[15] of 2-lithio-1,3-dithiane and of 2-tert-butyl-2-lithio- tained under these conditions.
1,3-dithiane and 2-lithio-2-phenyl-1,3-dithiane have shown
that all are monomeric contact ion pairs (CIPs) in THF/
Et2O mixtures (concentration of about 0.17 ), becoming
separated ion pairs (SIPs) in the presence of excess HMPA.
Therefore, speculating that 1,3-oxathianes might behave
similarly, we postulate that the lithium atom was equatorial
and that 5Bn-Li is monomeric at these reaction concentra-
tions (about 0.05  in THF), the coordination sphere of the
lithium atom being completed by solvent molecules. Con-
sequently, exclusive formation of the equatorial isomer (at
C-2) could be explained through approach A, and the poor
stereoselectivity at C-2Ј could then be explained by the fact
that the carbonyl group may approach from both faces
(Figure 1), with AI slightly preferred or identical to AII.
Oxo Derivatives 7Bn: Synthesis, Reductions, and Grignard
Additions
The oxo derivatives 7Bn-a and 7Bn-b were synthesized in
80% and 38% isolated yields by addition of benzonitrile and
propionitrile, respectively, to the lithio derivative 5Bn-Li,
followed by hydrolysis.[16] A better preparation of enolisable
oxo derivatives might be to treat the desired RϪCOϪCl
with the lithium cuprate 5Bn2-CuLi, but that method, al-
though attractive, is difficult to perform, as mentioned by
the authors themselves.[17]
It should be noted that the introduced COϪR groups
have equatorial orientations (Scheme 2).
Reduction of compounds 7Bn-a (Scheme 2) provided the
corresponding product 6Bn-c with high diastereoselectivity,
but only when selectrides were used (Table 2, lines 1, 2),
and it is worth noting that DIBAL provided a smaller and
reversed diastereoselectivity (as already observed by Eliel
with oxathiane 4[18,19]). In contrast to Eliel’s results[4] with
oxathiane 4, however, methyl Grignard addition to com-
pound 7Bn-a proceeded with low diastereoselectivity. Re-
duction of compound 7Bn-b with K-selectride gave a lower
diastereoselectivity than that from compound 7Bn-a (com-
pare lines 2 and 6, Table 2), and phenyl Grignard addition
Figure 1. Approach A
338
Eur. J. Org. Chem. 2003, 337Ϫ345

Diastereoreactivity of a Chiral Oxathiane Derived from 5-Hydroxy-1-tetralone
FULL PAPER
Scheme 2
Table 2. Reduction of and Grignard addition to oxo derivatives
7Bn [*: deduced from Cram’s model (see ref.[10,18])]
Reagent
R1 R2 Comp. (%)
6Bn
I/II
Absol.
config. of II*
L-selectride Ph
K-selectride Ph
H
H
H
H
6Bn-c (100) 3:97
(S)
6Bn-c (100) Ͻ 1:Ͼ 99 (S)
LiAlH4
DIBAL
MeMgI
Ph
Ph
6Bn-c (100) 12:88
6Bn-c (100) 77:23
(S)
(R)
(S)
(S)
(R)
Ph Me 6Bn-f (60)
20:80
K-selectride Et
PhMgBr
H
6Bn-g (100) 16:84
Et Ph 6Bn-h (59)
40:60
Scheme 3
Reactivity of 8 Towards Alkyllithium Bases
was still worse (with a 40:60 diastereomeric ratio). It is clear
that the selectivity in the ethyl ketone system 7Bn-b is less
than in the phenyl analogue 7Bn-a, as has often been ob-
served during reductions and Grignard additions.[4,18,19]
It is worth noting that while diastereomers I of products
6Bn-c and 6Bn-f were preferred on addition of benzal-
dehyde and acetophenone to 5Bn-Li, diastereomers II (6Bn-
cII and 6Bn-fII) were preferred by reduction of or methyl
Grignard addition to ketone 7Bn-a.
Any attempts to form the lithio derivatives of compounds
8 with an equatorial substituent present at C-2 failed
(Scheme 4 and Table 4), and no deuterium could be incorp-
orated at C-2 after quenching with D2O. The non-deuter-
ated starting substrates were quantitatively recovered in all
cases except for those of benzyl- or TMS-protected com-
pounds at 0 °C (Table 4, lines 4, 8).
By Eliel’s conclusions[10,18] concerning oxathianes 1 and
4, these additions follow Cram’s rule (open or rigid model)
and the (S) configuration should be expected at C-2Ј for
diastereomers II (6Bn-cII and 6Bn-fII). The (S) and (R)
configurations were consequently assigned to 6Bn-g and
6Bn-h, respectively (Table 2). Moreover, diastereomers I
(6Bn-cI and 6Bn-f) could then be assigned the (R) config-
uration at C-2Ј, consistently with approach AI (Figure 1).
Scheme 4
Alkylation and Quenching of Lithio Derivative 5Bn-Li
Addition of methyl iodide and quenching with TMSCl
or D2O exclusively afforded the equatorial diastereomers
8Bn-aI, 8Bn-bI, and 8Bn-cI, with high percentage conver-
sions (Table 3 and Scheme 3). Addition of isopropyl iodide,
however, resulted in an unidentified product, and 50% of
starting material was recovered.
It is worth noting that this treatment of 8Bn-bI, after
isolation, gave 15% of deprotected compound (8H-bI) and
57% of non-deuterated recovered 8Bn-bI (the remaining
28% being non-isolated and undetermined products), while
that of 8Bn-aI gave, in 71% isolated yield, a mixture corres-
ponding to 39% deuteration at the benzyl protecting group,
43% Wittig rearrangement, and 18% deprotection, but with
no starting material (deuterated or non-deuterated) being
recovered, the remaining 29% also being lost and unidenti-
fied (Scheme 5).
Table 3. Alkylation and quenching of lithio derivative 5Bn-Li to
give compounds 8Bna-c
Electrophile
R
Conversion Diastereomer. I (equatorial)
Methyl iodide Me
90%
TMS 97%
98%
8Bn-aI 100%
8Bn-bI 100%
8Bn-cI 100%
Direct Preparation of Type 8 Compounds
TMSCl
D2O
It is worth noting that compounds of type 8 with an
equatorial substituent at C-2, when not accessible through
D
Eur. J. Org. Chem. 2003, 337Ϫ345
339

´
A. Solladie-Cavallo, M. Balaz, M. Salisova
FULL PAPER
Table 4. Attempted deuteration of equatorially substituted compounds 8
R
Base
Solvent
Temp.
Deuterated
8
Non-deuterated
starting 8
8Bn-aI
Me
Me
Me
Me
tBuLi
nBuLi
nBuLi
nBuLi
THF
Et2O
THF
THF
Ϫ50 °C
Ϫ50 °C
Ϫ30 °C
0 °C
0%
0%
Ն 98%
Ն 98%
Ն 98%
0%
0%
0%[a]
8Bn-bI
TMS
TMS
TMS
TMS
tBuLi
nBuLi
nBuLi
nBuLi
THF
Et2O
THF
THF
Ϫ50 °C
Ϫ50 °C
Ϫ30 °C
0 °C
0%
0%
Ն 98%
Ն 98%
Ն 98%
57%
0%
0%[b]
8Si-aI
8Si-aI
8Si-gI
8Si-gI
Me
Me
Ph
sBuLi
tBuLi
sBuLi
tBuLi
THF
THF
THF
THF
0 °C
0 °C
0 °C
0 °C
0%
0%
0%
0%
97%
Ն 98%
97%
Ph
Ն 98%
8H-aI
Me
Me
Ph
PhLi[c]
tBuLi[c]
tBuLi[c]
THF
Ϫ50 °C
Ϫ50 °C
0 °C
0%
0%
0%
Ն 98%
Ն 98%
Ն 98%
THF/HMPA[d]
THF
8H-gI
[a]
[b]
No starting 8Bn-aI (deuterated or non-deuterated) was recovered (cf. Scheme 5). 57% of starting 8Bn-bI (non deuterated) and 14%
[c]
[d]
of deprotected 8H-bI were recovered. 2.3 equiv. used. 1 equiv. of HMPA.
Scheme 5
alkylation of the lithio derivatives (cf. above), can be dir-
ectly obtained in high yields (80Ϫ100%) by condensation
of the desired unprotected hydroxy thiol 9H-cis with the
corresponding aldehydes with a subsequent protection step
(allowing the introduction of various protecting groups as
desired, Scheme 6). Again, all type 8 compounds obtained
have the new substituent at C-2 in an equatorial position.
NMR Determination of the Configuration at C-2
The equatorial orientations of the ‘‘large’’ substituent in
compounds 6, 7, and 8 were determined by 2D NMR spec-
troscopy. The NOESY spectra showed correlations between
the proton at C-2, one of the methyl groups at C-4, and the
proton at C-6.
Conclusion
It was found that:
1. All reactions at C-2 of oxathiane 5Bn provide equator-
ial substitution at C-2.
2. Reductions of equatorial oxo derivative 7Bn-a with se-
lectrides provide high diastereoselectivities at C-2Ј, but
methyl Grignard addition is less selective.
3. Condensation of aldehydes and/or ketones with the li-
thio derivative 5Bn-Li provides high equatorial diastereose-
lectivities at C-2 but low or nil diastereoselectivities at C-2Ј.
4. The major configuration at C-2Ј is inverted on going
from condensation products (Table 1) to reduction/Grig-
nard addition products (Table 2).
Scheme 6
340
Eur. J. Org. Chem. 2003, 337Ϫ345

Diastereoreactivity of a Chiral Oxathiane Derived from 5-Hydroxy-1-tetralone
FULL PAPER
(Na2SO4), and, after filtration, concentrated under vacuum to af-
ford an oil that was analyzed by TLC and H NMR before being
purified by preparative layer chromatography PLC.
5. Lithiation at C-2 is possible only with the starting 5Bn
(CH2) and impossible with 8Bn derivatives substituted at C-
2 (CHR).
1
6. The selectivity with the ethyl ketone 7Bn-b is less than
with the phenyl analogue 7Bn-a, as has often been observed
during reductions and Grignard additions.[4,18,19]
Acetaldehyde
1
3
6Bn-aI: H NMR (CDCl3): δ ϭ 1.22 (d, J ϭ 6.5 Hz, 3 H, CH3),
1.35 (s, 3 H, Meeq), 1.45 (dt, 3J ϭ 12.5, 3J ϭ 3J ϭ 2.5 Hz, 1 H, 4a-
Concerning points 1Ϫ4, oxathiane 5Bn, although pos-
sessing a cis junction, has a reactivity at C-2 similar to that
of oxathianes 2, 3, and 4, which each possess a rigid trans
junction, and even to that of oxathiane 1, which is flexible.
However, differences in behavior arise where lithiation is
concerned (point 5). While lithiation of oxathianes 1,[1] 4,[4]
and 5Bn occurred readily with use of nBuli, lithiation of
oxathianes 2[2] and 3[3] was not possible with nBuLi, al-
though sBuLi allowed lithiation of oxathiane 2.
Attempted lithiation of oxathianes 5 substituted at C2
(8Bn, 8Si, 8 H) with nBuLi, sBuLi, and tBuLi all failed,
while lithiation of oxathianes 10Ϫ12, substituted at C-2,
worked readily (sBuLi/THF, Ϫ78 °C).[20Ϫ22]
H), 1.67 (s, 3 H, Meax), 1.90 (m, 1 H, 5-Heq), 2.14 (dq, J ϭ J ϭ
2
3
3
2
3
3J ϭ 12.5, J ϭ 6 Hz, 1 H, 5-Hax), 2.57 (ddd, J ϭ 18, J ϭ 12.5,
3J ϭ 6 Hz, 1 H, 6-Hax), 2.77 (d, J ϭ 2.5 Hz, 1 H, OH), 3.13 (ddd,
3
3
3
3
3
2J ϭ 18, J ϭ 6, J ϭ 1 Hz, 1 H, 6-Heq), 3.83 (dquint, J ϭ J ϭ
3
3
3J ϭ J ϭ 7, J ϭ 2.5 Hz, 1 H, 2Ј-H), 4.76 (s, 1 H, 10b-H), 4.88
(d, 3J ϭ 7 Hz, 1 H, 2-H), 5.08 (AB, JAB ϭ 12 Hz, 2 H, CH2O),
3
3
6.87 (d, J ϭ 8 Hz, 1 H, Har), 6.93 (d, J ϭ 8 Hz, 1 H, Har), 7.19
(t, 3J ϭ 8 Hz, 1 H, Har), 7.28Ϫ7.47 (m, 5 H, HPh) ppm. 13C NMR
(CDCl3): δ ϭ 17.9 (CH2), 18.2 (CH3), 23.8 (CH2), 29.2 (Me), 29.6
(Me), 43.0 (CH), 43.4 (C), 69.7 (C-2Ј), 69.8 (CH2O), 74.5 (C-10b),
84.4 (C-2), 110.9 (CH), 123.3 (CH), 126.6 (CH), 127.0 (C), 127.0
(CH), 127.8 (CH), 128.5 (CH), 136.7 (C), 137.2 (C), 156.2 (C) ppm.
IR: νOH ϭ 3436 cmϪ1
6Bn-aII: 1H NMR (CDCl3): δ ϭ 1.25 (d, 3J ϭ 5 Hz, 3 H, CH3),
.
1.36 (s, 3 H, Meeq), 1.44 (dt, J ϭ 12, J ϭ J ϭ 2.5 Hz, 1 H, 4a-
3
3
3
H), 1.67 (s, 3 H, Meax), 1.90 (m, 1 H, 5-Heq), 2.16 (dq, J ϭ J ϭ
2
3
3J ϭ 12, J ϭ 6 Hz, 1 H, 5-Hax), 2.25 (d, 3J ϭ 5 Hz, 1 H, OH), 2.55
2
3
3
2
(ddd, J ϭ 18.5, J ϭ 12, J ϭ 6 Hz, 1 H, 6-Hax), 3.12 (ddd, J ϭ
3
3
18.5, J ϭ 6, J ϭ 1 Hz, 1 H, 6-Heq), 3.99 (m, 1 H, 2Ј-H), 4.79 (s,
From the observation that the equatorial position is the
only one accepted at C-2 (even for Li) it is reasonable to
postulate that flexibility is necessary for lithiation of C-2-
substituted oxathianes.
3
1 H, 10b-H), 5.08 (s, 2 H, CH2O), 5.13 (d, J ϭ 3.5 Hz, 1 H, 2-H),
3
3
6.86 (d, J ϭ 8 Hz, 1 H, Har), 6.91 (d, J ϭ 8 Hz, 1 H, Har), 7.18
3
(t, J ϭ 8 Hz, 1 H, Har), 7.3Ϫ7.5 (m, 5 H, HPh) ppm. 13C NMR
(CDCl3): δ ϭ 17.9 (CH2), 18.3 (CH3), 23.8 (CH2), 29.4 (2 ϫ Me),
43.0 (C), 43.3 (CH), 69.5 (C-2Ј), 69.8 (CH2O), 74.8 (C-10b), 84.2
(C-2), 110.9 (CH), 123.3 (CH), 126.4 (CH), 127.1 (C), 127.0 (CH),
127.8 (CH), 128.5 (CH), 136.9 (C), 137.3 (C), 156.2 (C) ppm. IR:
Experimental Section
νOH ϭ 3421 cmϪ1
.
General: All reactions involving organolithium reagents were car-
ried out under argon in flame-dried glassware. THF was dried un-
der argon by distillation from sodium/benzophenone. nBuLi,
tBuLi, and sBuLi were purchased from Aldrich and Fluka. 1H and
13C NMR spectra were recorded with Bruker AC 200 (200 MHz)
or Bruker Avance (400 MHz) spectrometers with CDCl3 as solvent.
Chemical shifts (δ) are reported in ppm downfield from TMS.
TLCs were performed on Merck glass plates with 63 F254 silica gel,
and PLC (preparative layer chromatography) on Merck glass plates
with 60 F254 silica gel (2 mm). Si 60 silica gel (40Ϫ60 µm) from
Merck was used for chromatographic purifications. Usual IR spec-
tra were recorded with a PerkinϪElmer Spectrum one.
Butyraldehyde
6Bn-bI: 1H NMR (CDCl3): δ ϭ 0.92 (t, 3J ϭ 6 Hz, 3 H, CH3), 1.35
(s, 3 H, Meeq), 1.4Ϫ1.6 (m, 5 H, 4a-H ϩ CH2CH2), 1.67 (s, 3 H,
Meax), 1.9 (m, 1 H, 5-Heq), 2.12 (dq, 2J ϭ 3J ϭ 3J ϭ 12, 3J ϭ 6 Hz,
1 H, 5-Hax), 2.57 (ddd, 2J ϭ 18, 3J ϭ 12, 3J ϭ 6.5 Hz, 1 H, 6-Hax),
2
3
3
2.6 (1 H, OH, overlap), 3.12 (ddd, J ϭ 18, J ϭ 6, J ϭ 1 Hz, 1
H, 6-Heq), 3.68 (dt, J ϭ J ϭ 7, J ϭ 2.5 Hz, 1 H, 2Ј-H), 4.75 (s,
3
3
3
1 H, 10b-H), 4.95 (d, 3J ϭ 6.5 Hz, 1 H, 2-H), 5.08 (AB, JAB
ϭ
12 Hz, 2 H, CH2O), 6.86 (d, J ϭ 8 Hz, 1 H, Har), 6.92 (d, J ϭ
3
3
8 Hz, 1 H, Har), 7.18 (t, J ϭ 8 Hz, 1 H, Har), 7.26Ϫ7.45 (m, 5 H,
3
HPh) ppm. 13C NMR (CDCl3): δ ϭ 14.0 (CH3), 17.9 (CH2), 18.4
(CH2), 23.8 (CH2), 29.2 (Me), 29.5 (Me), 34.4 (CH2), 43.1 (C), 43.3
(CH), 69.8 (CH2), 73.0 (CH), 74.6 (C-10b), 83.3 (C-2), 110.9 (CH),
123.3 (CH), 126.6 (CH), 127.0 (C), 127.1 (CH), 127.8 (CH), 128.5
(CH), 136.7 (C), 137.3 (C), 156.2 (C) ppm. IR: νOH ϭ 3436 cmϪ1
.
1
3
6Bn-bII: H NMR (CDCl3): δ ϭ 0.92 (t, J ϭ 6.5 Hz, 3 H, CH3),
1.36 (s, 3 H, Meeq), 1.25Ϫ1.6 (m, 5 H, 4a-H ϩ CH2CH2), 1.43 (dt,
3
3
3J ϭ 12, J ϭ J ϭ 2 Hz, 1 H, 4a-H), 1.67 (s, 3 H, Meax), 1.9 (m,
2
3
3
General Procedures for the Treatment of Oxathiane 5Bn with Elec-
trophiles: nBuLi (1.6  solution in hexanes, 0.12 mL, 0.19 mmol,
1.3 equiv.) was added dropwise by syringe at Ϫ50 °C and under
argon to a solution of 5Bn (50 mg, 0.15 mmol, 1 equiv.) in anhyd-
rous THF (3.5 mL). After the mixture had been stirred for 40 min,
1 H, 5-Heq), 2.16 (dq, J ϭ J ϭ J ϭ 12, J ϭ 6 Hz, 1 H, 5-Hax),
2
3
3
2.16 (1 H, OH), 2.57 (ddd, J ϭ 18, J ϭ 12, J ϭ 6.5 Hz, 1 H, 6-
Hax), 3.12 (ddd, J ϭ 18, J ϭ 6, J ϭ 1 Hz, 1 H, 6-Heq), 3.83 (m,
2
3
3
1 H, 2Ј-H), 4.79 (s, 1 H, 10b-H), 5.08 (AB, JAB ϭ 12 Hz, 2 H,
3
3
CH2O), 5.15 (d, J ϭ 3.5 Hz, 1 H, 2-H), 6.86 (d, J ϭ 8 Hz, 1 H,
3
3
the desired electrophile (0.22 mmol, 1.5 equiv.) was added dropwise. Har), 6.91 (d, J ϭ 8 Hz, 1 H, Har), 7.18 (t, J ϭ 8 Hz, 1 H, Har),
After being stirred at Ϫ50 °C for 90 min, the reaction mixture was 7.26Ϫ7.45 (m, 5 H, HPh) ppm. 13C NMR (CDCl3): δ ϭ 14.0 (CH3),
quenched by addition of saturated aqueous NH4Cl (2 mL). The
18.0 (CH2), 18.9 (CH2), 23.8 (CH2), 29.4 (2 ϫ Me), 34.3 (CH2),
mixture was extracted with diethyl ether (4 ϫ 5 mL), dried
42.9 (C), 43.3 (CH), 69.8 (CH2O), 73.1 (CH), 74.8 (C-10b), 83.7
Eur. J. Org. Chem. 2003, 337Ϫ345
341

´
A. Solladie-Cavallo, M. Balaz, M. Salisova
FULL PAPER
(C-2), 110.8 (CH), 123.4 (CH), 126.4 (CH), 127.0 (CH), 127.1 (C), Butanone
127.8 (CH), 128.5 (CH), 136.9 (C), 137.3 (C), 156.2 (C) ppm. IR:
6Bn-eI: 1H NMR (CDCl3): δ ϭ 0.96 (t, 3J ϭ 7.5 Hz, 3 H,
CH3CH2), 1.20 (s, 3 H, CH3), 1.35 (s, 3 H, Meeq), 1.42 (d, 3J ϭ
12 Hz, 1 H, 4a-H), 1.61 (m, 2 H, CH2CH3), 1.62 (m, 2 H, CH2),
νOH ϭ 3431 cmϪ1
.
1
3
6Bn-cI: H NMR (CDCl3): δ ϭ 1.28 (s, 3 H, Meeq), 1.44 (dt, J ϭ
12.5, J ϭ J ϭ 2 Hz, 1 H, 4a-H), 1.56 (s, 3 H, Meax), 1.90 (m, 1
3
3
2
1.67 (s, 3 H, Meax), 1.90 (m, 1 H, 5-Heq), 2.13 (dq, J ϭ 3J ϭ 3J ϭ
H, 5-Heq), 2.19 (dq, J ϭ J ϭ J ϭ 12.5, J ϭ 6 Hz, 1 H, 5-Hax),
2
3
3
3
3
2
12, J ϭ 6 Hz, 1 H, 5-Hax), 2.50 (s, 1 H, OH), 2.59 (ddd, J ϭ 18,
2.58 (ddd, J ϭ 18.5, J ϭ 12.5, J ϭ 6 Hz, 1 H, 6-Hax), 3.15 (dd,
2
3
3
3J ϭ 12, 3J ϭ 6.5 Hz, 1 H, 6-Hax), 3.13 (dd, J ϭ 18, J ϭ 6 Hz, 1
H, 6-Heq), 4.76 (s, 1 H, 10b-H), 5.01 (s, 1 H, 2-H), 5.08 (s, 2 H,
CH2O), 6.89 (d, 3J ϭ 8 Hz, 1 H, Har), 6.93 (d, 3J ϭ 8 Hz, 1 H,
2
3
2J ϭ 18.5, 3J ϭ 6 Hz, 1 H, 6-Heq), 3.26 (s, 1 H, OH), 4.67 (d, J ϭ
3
8 Hz, 1 H, 2Ј-H), 4.81 (s, 1 H, 10b-H), 5.09 (s, 2 H, CH2O), 5.12
3
(d, J ϭ 8 Hz, 1 H, 2-H), 6.89 (d, 3J ϭ 8 Hz, 1 H, Har), 6.96 (d,
Har), 7.20 (t, J ϭ 8 Hz, 1 H, Har), 7.32Ϫ7.50 (m, 5 H, HPh) ppm.
3
3
3J ϭ 8 Hz, 1 H, Har), 7.18 (t, J ϭ 8 Hz, 1 H, Har), 7.28Ϫ7.48 (m,
13C NMR (CDCl3): δ ϭ 7.6 (CH3), 18.0 (CH2), 22.3 (CH3), 23.9
(CH2), 29.3 (Me), 29.4 (Me), 31.2 (CH2), 43.2 (CH ϩ C), 69.8
(CH2), 74.4 (C-2Ј), 75.0 (C-10b), 85.8 (C-2), 110.8 (CH), 123.3
(CH), 126.4 (CH), 127.1 (CH), 127.1 (C), 127.8 (CH), 128.5 (CH),
10 H, HPh) ppm. 13C NMR (CDCl3): δ ϭ 18.1 (CH2), 24.0 (CH2),
29.5 (Me), 43.2 (CH), 43.8 (CH), 70.1 (CH2O), 74.8 (C-10b), 76.7
(CH), 84.1 (C-2), 111.2 (CH), 123.6 (CH), 126.5 (CH), 126.8 (CH),
127.3 (CH), 127.5 (CH), 128.0 (CH), 128.5 (CH), 128.7 (CH), 136.8
137.0 (C), 137.3 (C), 156.2 (C) ppm. IR: νOH ϭ 3552 cmϪ1
.
(C), 137.5 (C), 138.7 (C), 139.0 (C), 156.5 (C) ppm. IR: νOH
ϭ
6Bn-eII: 1H NMR (CDCl3): δ ϭ 0.91 (t, 3J ϭ 7.5 Hz, 3 H,
CH3CH2), 1.22 (s, 3 H, CH3), 1.35 (s, 3 H, Meeq), 1.42 (d, 3J ϭ
12 Hz, 1 H, 4a-H), 1.60 (m, 2 H, CH2CH3), 1.63 (m, 2 H, CH2),
1.67 (s, 3 H, Meax), 1.90 (m, 1 H, 5-Heq), 2.09 (dq, 2J ϭ 3J ϭ 3J ϭ
3555 cmϪ1
.
6Bn-cII: 1H NMR (CDCl3): δ ϭ 1.30 (s, 3 H, Meeq), 1.42 (dt, 3J ϭ
12, J ϭ J ϭ 2 Hz, 1 H, 4a-H), 1.57 (s, 3 H, Meax), 1.91 (m, 1 H,
3
3
2
3
3
3
5-Heq), 2.16 (dq, J ϭ J ϭ J ϭ 12, J ϭ 6 Hz, 1 H, 5-Hax), 2.58
3
2
12, J ϭ 6 Hz, 1 H, 5-Hax), 2.33 (s, 1 H, OH), 2.59 (ddd, J ϭ 18,
(ddd, J ϭ 18, J ϭ 12, J ϭ 6 Hz, 1 H, 6-Hax), 2.82 (s, 1 H, OH),
2
3
3
3J ϭ 12, 3J ϭ 6.5 Hz, 1 H, 6-Hax), 3.13 (dd, J ϭ 18, J ϭ 6 Hz, 1
H, 6-Heq), 4.76 (s, 1 H, 10b-H), 5.01 (s, 1 H, 2-H), 5.08 (s, 2 H,
CH2O), 6.89 (d, 3J ϭ 8 Hz, 1 H, Har), 6.93 (d, 3J ϭ 8 Hz, 1 H,
2
3
3.13 (dd, 2J ϭ 18, 3J ϭ 6 Hz, 1 H, 6-Heq), 4.84 (s, 1 H, 10b-H),
3
3
5.06 (d, J ϭ 4 Hz, 1 H, 2Ј-H), 5.09 (s, 2 H, CH2O), 5.35 (d, J ϭ
4 Hz, 1 H, 2-H), 6.87 (d, J ϭ 8 Hz, 1 H, Har), 6.90 (d, J ϭ 8 Hz,
3
3
Har), 7.20 (t, J ϭ 8 Hz, 1 H, Har), 7.32Ϫ7.50 (m, 5 H, HPh) ppm.
3
1 H, Har), 7.21 (t, J ϭ 8 Hz, 1 H, Har), 7.26Ϫ7.48 (m, 10 H, HPh
)
3
13C NMR (CDCl3): δ ϭ 7.7 (CH3), 18.0 (CH2), 22.6 (CH3), 23.9
(CH2), 29.3 (Me), 29.4 (Me), 29.9 (CH2), 43.2 (CH ϩ C), 69.8
(CH2), 75.0 (C-10b), 76.6 (C-2Ј), 87.1 (C-2), 110.8 (CH), 123.3
(CH), 126.4 (CH), 127.1 (CH), 127.1 (C), 127.8 (CH), 128.5 (CH),
ppm. 13C NMR (CDCl3): δ ϭ 18.1 (CH2), 24.0 (CH2), 29.3 (Me),
43.2 (C), 43.3 (CH), 70.1 (CH2O), 75.1 (C-10b), 75.4 (CH), 84.9
(C-2), 111.1 (CH), 123.6 (CH), 126.6 (CH), 126.8 (CH), 127.2
(CH), 127.4 (CH), 128.0 (CH), 128.3 (CH), 128.7 (CH), 136.9 (C),
137.5 (C), 138.7 (C), 139.0 (C), 156.4 (C) ppm. IR: νOH ϭ 3431
137.0 (C), 137.3 (C), 156.2 (C) ppm. IR: νOH ϭ 3560 cmϪ1
.
cmϪ1
.
Acetophenone
1
3
6Bn-fI: H NMR (CDCl3): δ ϭ 1.35 (s, 3 H, Meeq), 1.44 (dt, J ϭ
Benzyl Methyl Ketone
3
3
12.5, J ϭ J ϭ 2 Hz, 1 H, 4a-H), 1.62 (s, 3 H, CH3), 1.67 (s, 3 H,
1
6Bn-dI: H NMR (CDCl3): δ ϭ 1.23 (s, 3 H, CH3), 1.36 (s, 3 H,
Meax), 1.93 (m, 1 H, 5-Heq), 2.16 (dq, J ϭ J ϭ J ϭ 12.5, J ϭ
2
3
3
3
3
3
3
Meeq), 1.40 (dt, J ϭ 12.5, J ϭ J ϭ 2.5 Hz, 1 H, 4a-H), 1.59 (s,
6 Hz, 1 H, 5-Hax), 2.61 (ddd, J ϭ 18, J ϭ 12.5, J ϭ 6.5 Hz, 1
2
3
3
3 H, Meax), 1.90 (m, 1 H, 5-Heq), 2.16 (dq, J ϭ J ϭ J ϭ 12.5,
2
3
3
H, 6-Hax), 3.16 (dd, J ϭ 18, 3J ϭ 6 Hz, 6-Heq), 3.21 (s, 1 H, OH),
2
3J ϭ 6 Hz, 1 H, 5-Hax), 2.57 (ddd, J ϭ 18, J ϭ 12.5, J ϭ 6 Hz,
2
3
3
4.79 (s, 1 H, 10b-H), 5.12 (s, 2 H, CH2O), 5.25 (s, 1 H, 2-H), 6.80
(d, 3J ϭ 8 Hz, 1 H, Har), 6.90 (d, 3J ϭ 8 Hz, 1 H, Har), 7.18 (t,
3J ϭ 8 Hz, 1 H, Har), 7.25Ϫ7.60 (m, 10 H, HPh) ppm. 13C NMR
(CDCl3): δ ϭ 18.1 (CH2), 23.9 (CH3), 24.0 (CH2), 29.4 (Me), 29.4
(Me), 43.2 (CH), 43.6 (C), 69.9 (CH2), 75.0 (C-10b), 76.1 (C-2Ј),
87.4 (C-2), 110.8 (CH), 123.5 (CH), 125.3 (CH), 126.0 (CH), 126.5
(CH), 127.2 (CH), 128.0 (CH), 128.0 (CH), 128.7 (CH), 136.9 (C),
1 H, 6-Hax), 2.63 (br. s, 1 H, OH), 2.89 (AB, JAB ϭ 14 Hz, 2 H,
2
3
3
CH2Ph), 3.12 (ddd, J ϭ 18, J ϭ 6, J ϭ 1 Hz, 1 H, 6-Heq), 4.71
(s, 1 H, 10b-H), 4.88 (s, 1 H, 2-H), 5.08 (s, 2 H, CH2O), 6.87 (d,
3J ϭ 8 Hz, 1 H, Har), 6.92 (d, J ϭ 8 Hz, 1 H, Har), 7.18 (t, J ϭ
8 Hz, 1 H, Har), 7.20Ϫ7.47 (m, 5 H, HPh) ppm. 13C NMR (CDCl3):
δ ϭ 18.0 (CH2), 23.4 (CH3), 23.8 (CH2), 29.2 (Me), 29.3 (Me), 43.2
(CH), 43.4 (C), 44.2 (CH2), 69.8 (CH2O), 74.4 (C-2Ј), 74.9 (C-10b),
85.1 (C-2), 110.8 (CH), 123.4 (CH), 126.4 (CH), 127.1 (CH), 127.2
(C), 127.8 (CH), 127.9 (CH), 128.5 (CH), 130.7 (CH), 136.9 (C),
3
3
137.4 (C), 143.9 (C), 156.2 (C) ppm. IR: νOH ϭ 3550 cmϪ1
.
6Bn-fII: 1H NMR (CDCl3): δ ϭ 1.31 (s, 3 H, Meeq), 1.44 (dt, 3J ϭ
137.1 (C), 137.3 (C), 156.2 (C) ppm. IR: νOH ϭ 3560 cmϪ1
.
3
3
12.5, J ϭ J ϭ 2 Hz, 1 H, 4a-H), 1.62 (s, 3 H, CH3), 1.71 (s, 3 H,
Meax), 1.88 (m, 1 H, 5-Heq), 2.16 (dq, J ϭ J ϭ J ϭ 12.5, J ϭ
2
3
3
3
1
6Bn-dII: H NMR (CDCl3): δ ϭ 1.17 (s, 3 H, CH3), 1.38 (s, 3 H,
6 Hz, 1 H, 5-Hax), 2.61 (ddd, J ϭ 18, J ϭ 12.5, J ϭ 6.5 Hz, 1
H, 6-Hax), 2.87 (s, 1 H, OH), 3.17 (dd, 2J ϭ 18, 3J ϭ 6 Hz, 6-Heq),
4.89 (s, 1 H, 10b-H), 5.14 (s, 2 H, CH2O), 5.33 (s, 1 H, 2-H), 6.93
(d, 3J ϭ 8 Hz, 1 H, Har), 6.95 (d, 3J ϭ 8 Hz, 1 H, Har), 7.23 (t,
3J ϭ 8 Hz, 1 H, Har), 7.25Ϫ7.60 (m, 10 H, HPh) ppm. 13C NMR
(CDCl3): δ ϭ 18.1 (CH2), 23.9 (CH3), 24.0 (CH2), 29.4 (Me), 29.4
(Me), 43.0 (CH), 43.4 (C), 69.9 (CH2), 75.2 (C-10b), 75.8 (C-2Ј),
87.2 (C-2), 110.6 (CH), 123.5 (CH), 125.4 (CH), 126.0 (CH), 126.5
(CH), 127.5 (CH), 128.1 (CH), 128.3 (CH), 128.7 (CH), 136.9 (C),
2
3
3
3
3
3
Meeq), 1.42 (dt, J ϭ 12.5, J ϭ J ϭ 2.5 Hz, 1 H, 4a-H), 1.65 (s,
3 H, Meax), 1.91 (m, 1 H, 5-Heq), 2.17 (dq, J ϭ J ϭ J ϭ 12.5,
2
3
3
3J ϭ 6 Hz, 1 H, 5-Hax), 2.32 (br. s, 1 H, OH), 2.58 (ddd, J ϭ 18,
2
3
3J ϭ 12.5, J ϭ 6.5 Hz, 1 H, 6-Hax), 2.92 (AB, JAB ϭ 14 Hz, 2 H,
2
3
CH2Ph), 3.12 (dd, J ϭ 18, J ϭ 6 Hz, 1 H, 6-Heq), 4.75 (s, 1 H,
10b-H), 5.00 (s, 1 H, 2-H), 5.09 (s, 2 H, CH2O), 6.88 (d, 3J ϭ 8 Hz,
3
3
1 H, Har), 6.92 (d, J ϭ 8 Hz, 1 H, Har), 7.19 (t, J ϭ 8 Hz, 1 H,
Har), 7.20Ϫ7.45 (m, 5 H, HPh) ppm. 13C NMR (CDCl3): δ ϭ 18.2
(CH2), 23.2 (CH3), 24.1 (CH2), 29.6 (Me), 29.6 (Me), 43.4 (CH),
43.6 (C), 43.7 (CH2), 70.1 (CH2O), 74.8 (C-2Ј), 75.2 (C-10b), 86.8
(C-2), 111.0 (CH), 123.6 (CH), 126.6 (CH), 126.6 (CH), 127.3
(CH), 127.4 (C), 128.0 (CH), 128.2 (CH), 128.7 (CH), 131 (CH),
137.2 (C), 137.4 (C), 137.5 (C), 156.4 (C) ppm. IR: νOH ϭ 3555
137.4 (C), 143.5 (C), 156.3 (C) ppm. IR: νOH ϭ 3556 cmϪ1
.
Methyl Iodide
1
3
8Bn-aI: H NMR (CDCl3): δ ϭ 1.34 (s, 3 H, Meeq), 1.44 (dt, J ϭ
cmϪ1
.
12.5, 3J ϭ 3J ϭ 2.5 Hz, 1 H, 4a-H), 1.52 (d, 3J ϭ 6 Hz, 3 H, CH3),
342
Eur. J. Org. Chem. 2003, 337Ϫ345

Diastereoreactivity of a Chiral Oxathiane Derived from 5-Hydroxy-1-tetralone
1.69 (s, 3 H, Meax), 1.93 (m, 1 H, 5-Heq), 2.23 (dq, 2J ϭ 3J ϭ 3J ϭ (CH), 43.3 (C), 74.9 (CH), 75.8 (CH), 117.6 (CH), 123.7 (CH),
FULL PAPER
3
2
3
3
12.5, J ϭ 6 Hz, 1 H, 5-Hax), 2.61 (ddd, J ϭ 18, J ϭ 12.5, J ϭ 126.4 (CH), 129.0 (C), 137.6 (C), 153.5 (C) ppm.
6 Hz, 1 H, 6-Hax), 3.15 (dd, J ϭ 18, J ϭ 6 Hz, 1 H, 6-Heq), 4.79
2
3
2-Methylpropionaldehyde
(s, 1 H, 10b-H), 5.10 (AB, JAB ϭ 12 Hz, 2 H, CH2OH), 5.25 (q,
3J ϭ 6 Hz, 1 H, 2-H), 6.86 (d, J ϭ 8 Hz, 1 H, Har), 6.96 (d, J ϭ
3
3
8Bn-dI: 1H NMR (CDCl3): δ ϭ 1.08 (d, 3J ϭ 7 Hz, 3 H, CH3),
8 Hz, 1 H, Har), 7.20 (t, J ϭ 8 Hz, 1 H, Har), 7.31Ϫ7.48 (m, 5 H,
3
3
3
1.12 (d, J ϭ 7 Hz, 3 H, CH3), 1.40 (s, 3 H, Meeq), 1.46 (dt, J ϭ
HPh) ppm. 13C NMR (CDCl3): δ ϭ 18.4 (CH2), 22.2 (CH3), 24.3
(CH2), 29.6 (Me), 30.0 (Me), 43.1 (C), 43.7 (CH), 70.3 (CH2O),
75.2 (CH), 76.2 (CH), 111.3 (CH), 123.8 (CH), 126.9 (CH), 127.5
(CH), 128.2 (C), 128.9 (CH), 137.6 (C), 137.8 (C), 156.7 (C) ppm.
12.5, 3J ϭ 3J ϭ 2.5 Hz, 1 H, 4a-H), 1.73 (s, 3 H, Meax), 1.95 (m, 1
3
2
H, 5-Heq), 2.03 (1 H, quint, J ϭ 6.5 Hz, CH), 2.23 (dq, J ϭ 3J ϭ
3J ϭ 12.5, 3J ϭ 5.5 Hz, 1 H, 5-Hax), 2.64 (ddd, 2J ϭ 18, 3J ϭ 12.5,
2
3
3J ϭ 6.5 Hz, 1 H, 6-Hax), 3.19 (dd, J ϭ 18, J ϭ 5.5 Hz, 1 H, 6-
Heq), 4.78 (s, 1 H, 10b-H), 4.93 (d, 3J ϭ 6 Hz, 1 H, 2-H), 5.13 (AB,
Chlorotrimethylsilane
JAB ϭ 11.5 Hz, 2 H, CH2OH), 6.90 (d, J ϭ 8 Hz, 1 H, Har), 6.98
3
(d, J ϭ 8 Hz, 1 H, Har), 7.23 (t, J ϭ 8 Hz, 1 H, Har), 7.35Ϫ7.55
(m, 5 H, HPh) ppm. 13C NMR (CDCl3): δ ϭ 18.5 (CH2), 19.2
(CH3), 19.4 (CH3), 24.4 (CH2), 29.9 (Me), 30.0 (Me), 34.0 (CH),
43.3 (C), 43.6 (CH), 70.2 (CH2O), 75.2 (CH), 86.5 (CH), 111.1
(CH), 123.9 (CH), 126.8 (CH), 127.5 (CH), 128.2 (CH), 128.9
(CH), 137.9 (C), 156.7 (C) ppm.
3
3
1
8bn-bI: H NMR (CDCl3): δ ϭ 0.14 [s, 9 H, Si(CH3)3], 1.36 (s, 3
H, Meeq), 1.43 (dt, J ϭ 12.5, J ϭ J ϭ 2 Hz, 1 H, 4a-H), 1.70 (s,
3
3
3
3 H, Meax), 1.91 (m, 1 H, 5-Heq), 2.24 (dq, J ϭ J ϭ J ϭ 12.5,
2
3
3
3J ϭ 6 Hz, 1 H, 5-Hax), 2.59 (ddd, 2J ϭ 18.5, 3J ϭ 12.5, 3J ϭ
6.5 Hz, 1 H, 6-Hax), 3.12 (dd, J ϭ 18.5, J ϭ 6 Hz, 1 H, 6-Heq),
2
3
4.63 (s, 1 H, 10b-H), 5.00 (s, 1 H, 2-H), 5.14 (AB, JAB ϭ 13 Hz, 2
H, CH2O), 6.87 (d, J ϭ 8 Hz, 1 H, Har), 6.91 (d, J ϭ 8 Hz, 1 H,
3
3
Hexanal
Har), 7.19 (t, J ϭ 8 Hz, 1 H, Har), 7.33Ϫ7.49 (m, 5 H, HPh) ppm.
3
13C NMR (CDCl3): δ ϭ Ϫ3.3 [(CH3)3Si], 18.5 (CH2), 24.6 (CH2),
28.9 (Me), 29.8 (Me), 42.0 (C), 44.5 (CH), 70.2 (CH2), 73.7 (CH),
76.0 (CH), 110.8 (CH), 124.0 (CH), 126.5 (CH), 127.5 (CH), 128.2
(CH), 128.9 (CH), 137.9 (C), 138.6 (C), 156.6 (C) ppm.
8Bn-eI: 1H NMR (CDCl3): δ ϭ 0.90 (t, 3J ϭ 7 Hz, 3 H, CH3CH2),
1.25Ϫ1.57 (m, 8 H), 1.34 (s, 3 H, Meeq), 1.44 (dt, J ϭ 12.5, J ϭ
3J ϭ 2.5 Hz, 1 H, 4a-H), 1.8 (m, 1 H), 1.69 (s, 3 H, Meax), 1.84
(m, 1 H), 1.92 (m, 1 H, 5-Heq), 2.20 (dq, 2J ϭ 3J ϭ 3J ϭ 12.5, 3J ϭ
3
3
6 Hz, 1 H, 5-Hax), 2.59 (ddd, J ϭ 18.5, J ϭ 12.5, J ϭ 6.5 Hz, 1
H, 6-Hax), 3.14 (dd, 2J ϭ 18.5, 3J ϭ 6 Hz, 1 H, 6-Heq), 4.75 (t,
3J ϭ 4J ϭ 1.5 Hz, 1 H, 10b-H), 5.09 (AB, JAB ϭ 12 Hz, 2 H,
2
3
3
Deuterated Water
8Bn-cI: H NMR (CDCl3): δ ϭ 1.37 (s, 3 H, Meeq), 1.49 (dt, J ϭ
1
3
3
3
3
CH2O), 5.10 (dd, J ϭ 7, J ϭ 5.5 Hz, 1 H, 2-H), 6.86 (dd, J ϭ
3
3
12.5, J ϭ J ϭ 2.5 Hz, 1 H, 4a-H), 1.72 (s, 3 H, Meax), 1.97 (m,
1 H, 5-Heq), 2.31 (dq, 2J ϭ 3J ϭ 3J ϭ 12.5, 3J ϭ 6 Hz, 1 H, 5-
Hax), 2.61 (ddd, 2J ϭ 18, 3J ϭ 12.5, 3J ϭ 6.5 Hz, 1 H, 6-Hax), 3.18
4
3
8, J ϭ 1 Hz, 1 H, Har), 6.93 (dd, J ϭ 8, 4J ϭ 1 Hz, 1 H, Har),
7.19 (t, J ϭ 8 Hz, 1 H, Har), 7.30Ϫ7.47 (m, 5 H, HPh) ppm. 13C
3
NMR (CDCl3): δ ϭ 14.5 (CH3), 18.4 (CH2), 23.0 (CH2), 24.3
(CH2), 26.0 (CH2), 29.4 (CH2), 29.6 (Me), 30.0 (Me), 32.1 (CH2),
36.2 (CH2), 43.5 (C), 43.5 (CH), 70.2 (CH2O), 75.1 (CH), 80.6
(CH), 111.1 (CH), 123.8 (CH), 126.8 (CH), 127.4 (CH), 128.1
(CH), 128.9 (CH), 137.7 (C), 137.8 (C), 156.7 (C) ppm.
(ddd, 2J ϭ 18, 3J ϭ 6, 3J ϭ 1.5 Hz, 1 H, 6-Heq), 4.74 (t, J ϭ 4J ϭ
3
2 Hz, 1 H, 10b-H), 5.11 (AB, JAB ϭ 12 Hz, 2 H, CH2OH), 5.24 (s,
1 H, H2ax), 6.88 (dd, J ϭ 8, J ϭ 1 Hz, 1 H, Har), 6.95 (dd, J ϭ
3
4
3
8, J ϭ 1 Hz, 1 H, Har), 7.20 (t, J ϭ 8 Hz, 1 H, Har), 7.33Ϫ7.49
(m, 5 H, HPh) ppm. 13C NMR (CDCl3): δ ϭ 18.2 (CH2), 23.9
(CH2), 28.5 (Me), 29.5 (Me), 42.2 (C), 43.9 (CH), 67.9 (t, C-2-HD),
69.9 (CH2O), 74.3 (C-10b), 111.0 (CH), 123.3 (CH), 126.7 (CH),
127.1 (CH), 127.9 (C), 128.7 (CH), 137.1 (C), 137.5 (C), 156.3
(C) ppm.
4
3
Cyclohexanecarbaldehyde
1
8Bn-fI: H NMR (CDCl3): δ ϭ 1.30Ϫ1.60 (m, 8 H), 1.36 (s, 3 H,
3
3
3
Meeq), 1.45 (dt, J ϭ 12.5, J ϭ J ϭ 2.5 Hz, 1 H, 4a-H), 1.70 (m,
1 H), 1.71 (s, 3 H, Meax), 1.83Ϫ1.98 (m, 2 H, 5-HeqϩH), 2.03 (m,
2
3
3
3
1 H), 2.22 (dq, J ϭ J ϭ J ϭ 12.5, J ϭ 6 Hz, 1 H, 5-Hax), 2.61
General Procedures for the Condensation of Hydroxy Thiol with Al-
dehydes. Direct Preparation of Type
(ddd, J ϭ 18, J ϭ 12.5, J ϭ 6.5 Hz, 1 H, 6-Hax), 2.95 (dd, J ϭ
18, 3J ϭ 6 Hz, 1 H, 6-Heq), 4.77 (br. s, 1 H, 10b-H), 5.11 (AB,
JAB ϭ 12 Hz, 2 H, CH2O), 5.12 (1 H, overlapped, 2-H), 6.87 (d,
2
3
3
2
8 Compounds: Boron
trifluorideϪdiethyl ether (0.21 mmol, 0.5 equiv.) was added under
argon to a cooled (ice bath), well-stirred solution of hydroxy thiol
(100 mg, 0.42 mmol, 1 equiv.) and aldehyde (1.26 mmol, 3 equiv.)
in dry dichloromethane (5 mL). After 15 min, the reaction mixture
was loaded directly onto a silica gel column and eluted with chloro-
form to give the oxathiane as a clear oil. The obtained oxathiane
was protected with benzyl bromide or TBDMSCl by standard pro-
cedures.[9,23]
3J ϭ 8 Hz, 1 H, Har), 6.96 (d, J ϭ 8 Hz, 1 H, Har), 7.21 (t, J ϭ
8 Hz, 1 H, Har), 7.30Ϫ7.50 (m, 5 H, HPh) ppm. 13C NMR (CDCl3):
δ ϭ 14.2 (CH), 18.4 (CH2), 22.7 (CH2), 24.1 (CH2), 25.8 (CH2),
29.2 (CH2), 29.4 (Me), 29.7 (Me), 31.8 (CH2),35.9 (CH2), 43.2
(CH), 43.3 (C), 69.9 (CH2), 74.8 (CH), 80.3 (CH), 110.8 (CH),
123.5 (CH), 126.6 (C), 127.1 (CH), 127.9 (CH), 128.6 (CH), 137.3
(C), 137.5 (C), 156.4 (C) ppm.
3
3
Acetaldehyde
Benzaldehyde
8Si-aI: 1H NMR (CDCl3): δ ϭ 0.26 (s, 6 H, 2 ϫ CH3Si), 1.04 [s, 9
1
H, (CH3)3], 1.34 (s, 3 H, Meeq), 1.40 (dt, 3J ϭ 12.5, 3J ϭ 3J ϭ 8Si-gI: H NMR (CDCl3): δ ϭ 0.27 (s, 3 H, CH3Si), 0.28 (s, 3 H,
2.5 Hz, 1 H, 4a-H), 1.52 (d, 3J ϭ 6 Hz, 3 H, CH3), 1.69 (s, 3 H, CH3Si), 1.06 [s, 9 H, (CH3)3], 1.37 (s, 3 H, Meeq), 1.50 (dt, 3J ϭ
Meax), 1.92 (m, 1 H, 5-Heq), 2.21 (dq, J ϭ J ϭ J ϭ 12.5, J ϭ 12.5, 3J ϭ 3J ϭ 2.5 Hz, 1 H, 4a-H), 1.81 (s, 3 H, Meax), 1.99 (m, 1
2
3
3
3
6 Hz, 1 H, 5-Hax), 2.53 (ddd, J ϭ 18, J ϭ 12.5, J ϭ 6 Hz, 1 H,
H, 5-Heq), 2.39 (dq, J ϭ J ϭ J ϭ 12.5, J ϭ 6 Hz, 1 H, 5-Hax),
2
3
3
2
3
3
3
6-Hax), 3.03 (ddd, J ϭ 18, J ϭ 6, J ϭ 1.5 Hz, 1 H, 6-Heq), 4.76 2.59 (ddd, 2J ϭ 18.5, 3J ϭ 12.5, 3J ϭ 6.5 Hz, 1 H, 6-Hax), 3.09
2
3
3
2
3
3
(t, 3J ϭ 4J ϭ 2 Hz, 1 H, 10b-H), 5.24 (q, 3J ϭ 6 Hz, 1 H, 2-H), (ddd, J ϭ 18.5, J ϭ 6, J ϭ 2 Hz, 1 H, 6-Heq), 4.94 (s, 1 H, 10b-
6.75 (dd, J ϭ 7.5, J ϭ 1 Hz, 1 H, Har), 6.93 (dd, J ϭ 7.5, J ϭ H), 6.16 (s, 1 H, 2-H), 6.76 (d, J ϭ 8 Hz, 1 H, Har), 6.93 (d, J ϭ
3
4
3
4
3
3
1 Hz, 1 H, Har), 7.11 (t, 3J ϭ 7.5 Hz, 1 H, Har) ppm. 13C NMR
8 Hz, 1 H, Har), 7.08 (t, J ϭ 8 Hz, 1 H, Har), 7.25Ϫ7.35 (m, 3 H,
3
(CDCl3): δ ϭ Ϫ4.1 (CH3Si), Ϫ4.0 (CH3Si), 18.2 (CH2), 18.4 (CSi), HPh), 7.50 (dd, 3J ϭ 8, 4J ϭ 1 Hz, 2 H, HPh) ppm. 13C NMR
21.9 (CH3), 24.7 (CH2), 25.9 (3 ϫ CH3), 29.2 (Me), 29.7 (Me), 42.8 (CDCl3): δ ϭ Ϫ3.7 (CH3Si), 18.7 (CH2), 25.1 (CH2), 26.2 (3 ϫ
Eur. J. Org. Chem. 2003, 337Ϫ345
343

´
A. Solladie-Cavallo, M. Balaz, M. Salisova
FULL PAPER
CH3), 29.4 (Me), 29.8 (Me), 43.3 (CH), 44.8 (C), 75.7 (CH), 81.6
(CH), 118.0 (CH), 124.3 (CH), 126.6 (CH), 127.0 (CH), 128.7 an oil that was analyzed by TLC and H NMR before being puri-
diethyl ether (4 ϫ 5 mL) and concentrated under vacuum to afford
1
(CH), 129.4 (C), 137.9 (C), 139.7 (C), 153.7 (C).
fied by PLC.
1
3
Typical Procedure for the Preparation of Oxo Derivatives 7Bn:
tBuLi (1.7  in pentane, 0.23 mL, 0.38 mmol, 1.3 equiv.) was added
6Bn-gII: H NMR (CDCl3): δ ϭ 1.00 (t, J ϭ 7.5 Hz, 2 H, CH3),
1.38 (s, 3 H, Meeq), 1.46 (dt, J ϭ 12.5, 3J ϭ 3J ϭ 2.5 Hz, 1 H, 4a-
3
dropwise by syringe under argon at Ϫ50 °C to oxathiane 5Bn H), 1.5Ϫ1.7 (m, 2 H, CH2), 1.70 (s, 3 H, Meax), 1.93 (m, 1 H, 5-
2
3
3
3
(100 mg, 0.29 mmol, 1 equiv.) in dry THF (6 mL). After the mix-
Heq), 2.18 (dq, J ϭ J ϭ J ϭ 12.5, J ϭ 6 Hz, 1 H, 5-Hax), 2.20
ture had been stirred for 15 min, PhCN (39 µL, 0.38 mmol, 1.3 (br. s, 1 H, OH), 2.60 (ddd, J ϭ 18, 3J ϭ 12.5, 3J ϭ 6 Hz, 1 H, 6-
2
2
3
3
equiv.) was added dropwise by syringe. Stirring at Ϫ50 °C was con-
tinued for 60 min, 2  HCl (1 mL) was added, and the mixture was
stirred briefly at room temperature until two clear phases appeared.
The organic layer was separated, and the aqueous layer was ex-
Hax), 3.15 (ddd, J ϭ 18, J ϭ 6, J ϭ 1 Hz, 1 H, 6-Heq), 3.76 (m,
3
4
1 H, 2Ј-H), 4.81 (t, J ϭ J ϭ 2 Hz, 1 H, 10b-H), 5.11 (AB, JAB
ϭ
3
3
12 Hz, 2 H, CH2O), 5.19 (d, J ϭ 4 Hz, 1 H, 2-H), 6.88 (d, J ϭ
8 Hz, 1 H, Har), 6.93 (d, J ϭ 8 Hz, 1 H, Har), 7.20 (t, J ϭ 8 Hz,
3
3
tracted four times with diethyl ether (15 mL each). The combined 1 H, Har), 7.32Ϫ7.48 (m, 5 H, HPh) ppm. 13C NMR (CDCl3): δ ϭ
organic solutions were washed with water, dried with Na2SO4, and
concentrated under vacuum to yield 150 mg of an oil. Purification
by PLC with 10% of acetone in hexane gave 106 mg (80%) of the
desired ketone 7Bn-a.
10.4 (CH3), 18.4 (CH2), 24.3 (CH2), 25.8 (CH2), 29.6 (Me), 29.9
(Me), 43.3 (C), 43.7 (CH), 70.3 (CH2O), 74.8 (CH), 75.2 (CH), 83.9
(C-2), 111.3 (CH), 123.8 (CH), 126.8 (CH), 127.4 (C), 128.2 (CH),
128.9 (CH), 137.3 (C), 137.7 (C), 156.7 (C) ppm. IR: νOH ϭ 3412
cmϪ1
.
7Bn-a: 1H NMR (CDCl3): δ ϭ 1.43 (s, 3 H, Me), 1.57 (dt, 3J ϭ
3
3
1
3
12.5, J ϭ J ϭ 2.5 Hz, 1 H, 4a-H), 1.84 (s, 3 H, Me), 2.00 (m, 1
6Bn-gI: H NMR (CDCl3): δ ϭ 1.02 (t, J ϭ 7.5 Hz, 2 H, CH3),
2
3
3
3
H, 5-Heq), 2.32 (dq, J ϭ J ϭ J ϭ 12.5, J ϭ 6 Hz, 1 H, 5-Hax), 1.37 (s, 3 H, Meeq), 1.47 (dt, 3J ϭ 12.5, 3J ϭ 3J ϭ 2.5 Hz, 1 H, 4a-
2
3
3
2.64 (ddd, J ϭ 18, J ϭ 12.5, J ϭ 6 Hz, 1 H, 6-Hax), 3.19 (ddd, H), 1.5Ϫ1.7 (m, 2 H, CH2), 1.70 (s, 3 H, Meax), 1.93 (m, 1 H, 5-
2J ϭ 18, J ϭ 6, J ϭ 1.5 Hz, 1 H, 6-Heq), 4.99 (d, J ϭ 1.5 Hz, 1 Heq), 2.17 (dq, J ϭ J ϭ J ϭ 12.5, J ϭ 6 Hz, 1 H, 5-Hax), 2.60
3
3
3
2
3
3
3
2
3
3
H, 10b-H), 5.1 (AB, JAB ϭ 12 Hz, 2 H, CH2O), 6.44 (s, 1 H, 2-H),
(ddd, J ϭ 18, J ϭ 12.5, J ϭ 6 Hz, 1 H, 6-Hax), 2.66 (br. s, 1 H,
3
3
2
3
3
6.86 (dd, J ϭ 8, 4J ϭ 1 Hz, 1 H, Har), 6.98 (d, J ϭ 8 Hz, 1 H,
OH), 3.14 (ddd, J ϭ 18, J ϭ 6, J ϭ 1 Hz, 1 H, 6-Heq), 3.64 (dt,
Har), 7.18 (t, 3J ϭ 8 Hz, 1 H, Har), 7.3Ϫ7.6 (m, 8 H, HPh), 8.14 3J ϭ 3J ϭ 7.5, 3J ϭ 4 Hz, 1 H, 2Ј-H), 4.78 (br. s, 1 H, 10b-H), 5.00
(dd, J ϭ 8, J ϭ 1 Hz, 2 H, HPh) ppm. 13C NMR (CDCl3): δ ϭ
18.3 (CH2), 24.0 (CH2), 29.1 (Me), 29.2 (Me), 43.2 (CH), 44.7 (C), 6.89 (d, J ϭ 8 Hz, 1 H, Har), 6.95 (d, J ϭ 8 Hz, 1 H, Har), 7.21
69.9 (CH2O), 75.8 (C-10b), 82.6 (C-2), 111.1 (CH), 123.7 (CH),
(t, 3J ϭ 8 Hz, 1 H, Har), 7.32Ϫ7.48 (m, 5 H, HPh) ppm. 13C NMR
(d, 3J ϭ 7 Hz, 1 H, 2-H), 5.11 (AB, JAB ϭ 12 Hz, 2 H, CH2O),
3
4
3
3
126.6 (CH), 127.2 (CH), 127.4 (C), 127.9 (CH), 128.5 (CH), 128.7 (CDCl3): δ ϭ 9.9 (CH3), 18.4 (CH2), 24.2 (CH2), 25.8 (CH2), 29.6
(CH), 129.8 (CH), 133.7 (CH), 134.2 (C), 136.3 (C), 137.4 (C), (Me), 29.9 (Me), 43.3 (C), 43.5 (CH), 70.3 (CH2O), 75.0 (CH), 75.3
156.3 (C), 192.8 (CϭO) ppm. IR: νCO ϭ 1694 cmϪ1
.
(CH), 83.4 (C-2), 111.3 (CH), 123.8 (CH), 127.0 (CH), 127.5 (C),
128.2 (CH), 128.9 (CH), 137.2 (C), 137.7 (C), 156.6 (C) ppm. IR:
3
7Bn-b: 1H NMR (CDCl3): δ ϭ 1.02 (t, J ϭ 7 Hz, 3 H, CH3), 1.36
νOH ϭ 3426 cmϪ1
.
(s, 3 H, Me), 1.46 (dt, 3J ϭ 12.5, 3J ϭ 3J ϭ 2.5 Hz, 1 H, 4a-H),
2
3
3
1.70 (s, 3 H, Me), 1.91 (m, 1 H, 5-Heq), 2.18 (dq, J ϭ J ϭ J ϭ Typical Procedure for the Grignard Addition to Oxo Derivatives
3
2
3
3
12.5, J ϭ 6 Hz, 1 H, 5-Hax), 2.59 (ddd, J ϭ 18, J ϭ 12.5, J ϭ 7Bn-a: A well-stirred solution of ketone (58 mg, 0.13 mmol) in dry
6 Hz, 1 H, 6-Hax), 2.70 (dq, 3J ϭ 7, J ϭ 3 Hz, 2 H, CH2), 3.14
THF (3 mL) was treated at Ϫ78 °C with MeMgI in dry Et2O (0.52
(ddd, 2J ϭ 18, 3J ϭ 6, 3J ϭ 1.5 Hz, 1 H, 6-Heq), 4.78 (t, 3J ϭ 2 Hz, , 1 mL, 0.52 mmol, 4 equiv.). After the mixture had been stirred
3
1 H, 10b-H), 5.09 (s, 2 H, CH2O), 5.63 (s, 1 H, 2-H), 6.90 (t, J ϭ for 5 h at the same temperature, it was quenched with 2 mL of
3
8 Hz, 2 H, Har), 7.18 (t, J ϭ 8 Hz, 1 H, Har), 7.3Ϫ7.55 (m, 5 H, saturated aqueous NH4Cl solution and allowed to warm to room
HPh) ppm. 13C NMR (CDCl3): δ ϭ 7.2 (CH3), 18.0 (CH2), 23.9
temperature. The mixture was extracted with diethyl ether (4 ϫ
(CH2), 29.2 (2 ϫ Me), 31.4 (CH2), 42.9 (CH), 44.1 (C), 69.9 5 mL) and concentrated under vacuum to afford an oil that was
1
(CH2O), 74.7 (C-10b), 83.6 (C-2), 111.0 (CH), 123.5 (CH), 126.6
(CH), 127.2 (CH), 127.9 (CH), 128.6 (CH), 136.6 (C), 137.4 (C),
analyzed by TLC and H NMR spectroscopy.
6Bn-hII: 1H NMR (CDCl3): δ ϭ 0.80 (t, 3J ϭ 7 Hz, 3 H, CH3),
1.35 (s, 3 H, Meeq), 1.42 (dt, 3J ϭ 12.5, 3J ϭ 3J ϭ 2.5 Hz, 1 H, 4a-
H), 1.63 (s, 3 H, Meax), 1.90 (m, 1 H, 5-Heq), 2.05 (m, 2 H, CH2),
156.3 (C), 206.8 (CϭO) ppm. IR: νCO ϭ 1720 cmϪ1
.
Typical Procedure for the Reduction of Oxo Derivatives 7Bn-a with
Selectrides: A well-stirred solution of ketone (22 mg, 0.05 mmol) in
dry toluene (1 mL) was treated at Ϫ78 °C with L-selectride (1.0
 solution in THF, 0.1 mL 0.1 mmol, 2 equiv.). After the mixture
had been stirred for 5 h at the same temperature, the excess redu-
2
3
3
3
2.12 (dq, J ϭ J ϭ J ϭ 12.5, J ϭ 6 Hz, 1 H, 5-Hax), 2.57 (ddd,
2J ϭ 18, 3J ϭ 12.5, 3J ϭ 6 Hz, 1 H, 6-Hax), 2.95 (s, 1 H, OH), 3.13
(ddd, J ϭ 18, J ϭ 6, J ϭ 1 Hz, 1 H, 6-Heq), 4.75 (t, J ϭ J ϭ
2
3
3
3
4
2 Hz, 1 H, 10b-H), 5.10 (s, 2 H, CH2O), 5.28 (s, 1 H, 2-H), 6.72
cing agent was quenched at Ϫ78 °C with NaOH in MeOH (1 , (d, 3J ϭ 8 Hz, 1 H, Har), 6.86 (d, 3J ϭ 8 Hz, 1 H, Har), 7.14 (t,
1 mL). The mixture was allowed to warm, and was extracted with 3J ϭ 8 Hz, 1 H, Har), 7.32Ϫ7.55 (m, 5 H, HPh) ppm. 13C NMR
diethyl ether (4 ϫ 5 mL) and concentrated under vacuum to afford
an oil that was analyzed by TLC and H NMR before being puri-
fied by PLC.
(CDCl3): δ ϭ 7.6 (CH3), 18.1 (CH2), 24.0 (CH2), 29.4 (2 ϫ Me),
30.4 (CH2), 43.3 (CH), 43.5 (C), 69.9 (CH2O), 75.2 (C-10b), 87.4
(C-2), 110.8 (CH), 123.4 (CH), 125.9 (CH), 126.5 (CH), 127.1
(CH), 127.8 (CH), 128.0 (CH), 128.7 (CH), 136.9 (C), 137.4 (C),
1
Typical Procedure for the Reduction of Oxo Derivatives 7Bn-a with
LiAlH4: A well-stirred solution of ketone (24 mg, 0.05 mmol) in
dry THF/Et2O (1:1, 2 mL) was treated at Ϫ78 °C with Li-
AlH4 (5 mg 0.1 mmol, 2 equiv.). After the mixture had been stirred
for 3 h at the same temperature, the excess reducing agent was
quenched at Ϫ78 °C with 1 mL of saturated aqueous NH4Cl solu-
tion. The mixture was allowed to warm, and was extracted with
142.4 (C), 156.2 (C) ppm. IR: νOH ϭ 3405 cmϪ1
.
6Bn-hI: 1H NMR (CDCl3): δ ϭ 0.66 (t, 3J ϭ 7 Hz, 3 H, CH3), 1.26
3
3
3
(s, 3 H, Meeq), 1.42 (dt, J ϭ 12.5, J ϭ J ϭ 2.5 Hz, 1 H, 4a-H),
1.62 (s, 3 H, Meax), 1.90 (m, 2 H, 5-Hax ϩ CH2), 2.20 (m, 2 H, 5-
2
3
3
Hax ϩ CH2), 2.57 (ddd, J ϭ 18, J ϭ 12.5, J ϭ 6.5 Hz, 1 H, 6-
Hax), 2.63 (s, 1 H, OH), 3.14 (dd, J ϭ 18, 3J ϭ 6 Hz, 1 H, 6-Heq),
2
344
Eur. J. Org. Chem. 2003, 337Ϫ345

Diastereoreactivity of a Chiral Oxathiane Derived from 5-Hydroxy-1-tetralone
FULL PAPER
[8]
3
4.89 (t, J ϭ 4J ϭ 2 Hz, 1 H, 10b-H), 5.15 (s, 2 H, CH2O), 5.37 (s,
As an example, compound I, isolated upon hydrolysis of oxa-
thiane derivatives 4, can be retransformed into the desired
starting oxathiane
3
3
1 H, 2-H), 6.89 (d, J ϭ 8 Hz, 1 H, Har), 6.94 (d, J ϭ 8 Hz, 1 H,
Har), 7.22 (t, J ϭ 8 Hz, 1 H, Har), 7.28Ϫ7.48 (m, 5 H, HPh) ppm.
3
13C NMR (CDCl3): δ ϭ 7.6 (CH3), 18.1 (CH2), 24.0 (CH2), 29.3
(Me), 29.5 (CH3), 32.3 (CH2), 43.1 (CH), 43.3 (C), 69.9 (CH2O),
75.1 (C-10b), 87.1 (C-2), 110.9 (CH), 123.5 (CH), 125.9 (CH), 126.5
(CH), 127.2 (CH), 127.4 (C), 127.9 (CH), 128.0 (CH), 128.7 (CH),
136.9 (C), 137.4 (C), 141.2 (C), 156.3 (C) ppm. IR: νOH ϭ 3410
cmϪ1
.
[9]
´
A. Solladie-Cavallo, M. Balaz, M. Salisova, C. Suteu, L. Nafie,
X. Cao, T. B. Freedman, Tetrahedron: Asymmetry 2001, 12,
2605.
Acknowledgments
We are grateful to the French Government (Sous-Direction des
Boursiers Etrangers et des Affaires Internationales) for a grant to
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`
M. B. (No. 19991885), the Ambassade de France a Bratislava Ϫ
´
Service de Cooperation et d’Action Culturelle (M. B. Paqueteau)
for encouragement and financial support to M. B. and M. S., and
to M. Schmitt for NMR spectral assistance.
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[O02429]
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345