Stereochemistry in palladium- and nickel-catalyzed addition of phenylmagnesium bromide to unsaturated carbohydrates

Article abstract of DOI:10.1016/S0022-328X(98)00679-2

Palladium complex PdCl₂(dppf) and nickel complex NiCl₂(dppe) catalyze cross-coupling of unsaturated aryloxy carbohydrates with phenylmagnesium bromide. The nickel catalyst leads to inversion of configuration at the anomeric center wh

Full text of DOI:10.1016/S0022-328X(98)00679-2

Journal of Organometallic Chemistry 567 (1998) 157–162
Stereochemistry in palladium- and nickel-catalyzed addition of
phenylmagnesium bromide to unsaturated carbohydrates
Christophe Moineau, Ve´ronique Bolitt, Denis Sinou *
Laboratoire de Synthe`se Asyme´trique, associe´ au CNRS, Uni6ersite´ Claude Bernard Lyon 1, CPE Lyon, 43, boule6ard du 11 no6embre 1918,
69622 Villeurbanne Ce´dex, France
Received 23 January 1998
Abstract
Palladium complex PdCl2(dppf) and nickel complex NiCl2(dppe) catalyze cross-coupling of unsaturated aryloxy carbohydrates
with phenylmagnesium bromide. The nickel catalyst leads to inversion of configuration at the anomeric center while only retention
occurs in the case of the palladium catalyst. This quite unusal retention is probably due to the influence of the ring oxygen atom
© 1998 Elsevier Science S.A. All rights reserved.
Keywords: Palladium; Nickel; Grignard reagents; Arylation; Stereochemistry; 2,3-Unsaturated glycosides
1. Introduction
We recently described a stereospecific palladium or
nickel-catalyzed new route to unsaturated h- and i-C-
aryl glycopyranosides [25]. If inversion of configuration
was observed in the presence of the nickel catalyst
NiCl2(dppe) [dppp: 1,2-bis(diphenylphosphino)ethane],
unexpected retention was obtained in the presence of
the palladium catalyst PdCl2(dppf) [dppf: 1,1%-bis(-
diphenylphosphino)ferrocene]. To the best of our
knowledge, this result constitutes the first example of a
coupling reaction between an allylic substrate and Grig-
nard reagents that proceeds with exclusive net retention
in the presence of a palladium catalyst. We describe in
this paper some experiments in order to try to have a
deeper insight on the scope of this reaction and to
propose some explanation for the observed
stereospecificity.
Transition-metal catalyzed substitution of allylic sub-
strates with organometallic reagents has emerged as an
important and well documented carbon–carbon bond-
forming reaction in organic synthesis [1–3]. These
organometallics reagents mainly based on magnesium,
zinc, tin, aluminium, zirconium and boron, are known
to couple under very mild conditions in the presence of
palladium or nickel catalysts. The stereochemistry as-
pect of these reactions has been studied by different
groups. So, it has been demonstrated that the coupling
of magnesium [4–7], zinc [8–11], tin [12–14], alu-
minium [15] or zirconium [16] reagents catalyzed by
palladium complexes as well as of magnesium [17–19]
or boron [20–23] derivatives in the presence of nickel
complexes proceeded with overall inversion of configu-
ration. Only quite recently Lautens et al. [24] observed
both inversion and retention of configuration in the
reaction of Grignard reagents with some unsaturated
bicyclic compounds under nickel catalysis.
2. Results and discussion
The reaction of 2,3-unsaturated carbohydrates 1h
and 3h with phenylmagnesium bromide in the presence
of PdCl2(dppf) catalyst gave the 2,3-unsaturated C-
phenylglycoside 2˜ and 4˜, respectively (Scheme 1),
* Corresponding author: Tel.:+33 472 446263; fax: +33 472
448160; e-mail sinou@univ-lyon1.fr
0022-328X/98/$19.00 © 1998 Elsevier Science S.A. All rights reserved.
PII S0022-328X(98)00679-2

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C. Moineau et al. / Journal of Organometallic Chemistry 567 (1998) 157–162
obtained in quite good yields (Table 1, entries 2 and 6).
The same stereoselectivity was observed when the
coupling reaction was realized on the i anomer 1™. The
palladium complex led exclusively to the unsaturated
C-glycoside 2™ with retention of configuration at the
anomeric center, in 87% yield (Table 1, entry 3), while
the nickel complex gave the anomer 2˜, with inversion
of configuration, in 50% yield, the reaction being how-
ever incomplete in this case (Table 1, entry 4).
We performed the same reactions on the h-unsatu-
rated carbohydrate 5, lacking the ether function at
position 6 [25]. The coupling reaction with C6H5MgBr
catalyzed by palladium and nickel complex gave respec-
tively the C-phenyl glycoside 6˜ with retention of
configuration and 6™ with inversion of configuration
(Scheme 1) (Table 1, entries 7 and 8).
To have a deeper insight on the possible role of the
oxygen atom at C-4 in the unsaturated carbohydrate
structure on the stereoselectivity of the reaction, we
performed the reactions on the erythro derivative 7. In
the coupling reaction of this compound with
C6H5MgBr in the presence of NiCl2(dppe), only degra-
dation products were observed, or no reaction at all.
However, in the presence of PdCl2(dppf) as the catalyst,
coupling reaction occured with retention of configura-
tion to give compound 8˜ in 44% yield (Table 1, entries
9 and 10).
Scheme 1.
These last results clearly showed that the oxygen
function at C-4 or at C-6 have no influence in the
unexpected retention of configuration observed with
PdCl2(dppf) as the catalyst.
having the h configuration only (Table 1, entries 1 and
5) [25]. When the same reaction was performed in the
presence of NiCl2(dppe), the 2,3-unsaturated C-phenyl
glycoside 2˜ and 4™, having the i configuration, were
Table 1
Stereoselectivity in the reaction of 2,3-unsaturated carbohydrates with phenylmagnesium bromide in the presence of palladium and nickel
complexes
Entry
Substrate
Catalyst
T (°C) (t/h)
25 (2)
Product (yield%)
Retention/inversiona (%)
1
2
1˜
PdCl2(dppf)
NiCl2(dppe)
PdCl2(dppf)
NiCl2(dppe)
PdCl2(dppf)
NiCl2(dppe)
PdCl2(dppf)
NiCl2(dppe)
PdCl2(dppf)
NiCl2(dppe)
2˜
(95)
2™
(70)
2
(87)
2˜
(50)
4˜
(80)
4™
(83)
6˜
(51)
6™
(68)
100/0
0/100
95/5
−40 (24)
25 (2)
3
1™
3
4
−40 (24)
25 (2)
0/100
100/0
0/100
100/0
0/100
100/0
5
6
−40 (2)
25 (24)
7
5
8
−40 (24)
25 (20)
9
7
8˜
(44)
10
−40 to 0
degradation or no reaction
a Isomeric purity determined by 1H-NMR and 13C-NMR.

C. Moineau et al. / Journal of Organometallic Chemistry 567 (1998) 157–162
159
and trans isomers, the former being however prepon-
derant. These results are in agreement with those al-
ready described by Hayashi et al. ([7]b).
3. Conclusion
Scheme 2.
The reaction of 2,3-unsaturated carbohydrates with
phenylmagnesium bromide gave the corresponding 2,3-
unsaturated C-phenylglycoside, with inversion of
configuration in the presence of NiCl2(dppe), but with
retention of configuration in the presence of
PdCl2(dppf). From these experiments concerning the
addition mechanism of phenylmagnesium bromide to
these unsaturated carbohydrates, it seems that the ring-
oxygen atom plays a crucial role on the retention of
configuration observed in the case of the palladium
catalyzed reaction.
Other substrates were also used in this coupling
reaction, and particularly the unsaturated carbohydrate
9 and the cyclohexenyl derivatives 12. The unsaturated
ethyl glycoside 9 was obtained by reaction of p-tert-
butylphenol on ethyl 6-O-(tert-butyldimethylsilyl)-4-O-
methoxycarbonyl-2,3-dideoxy-h-D-erythro-hex-2-enopyr
anoside [26] in the presence of Pd2(dba)3 and dppb
[1,4-bis(diphenylphosphino)butane] in THF. The cyclo-
hexenyl derivatives 12 and 13 were prepared from cis
5-(hydroxymethyl)cyclohex-2-en-1-ol [27]. Monosilyla-
tion of this diol with tert-butyldimethylsilyl chloride
gave the monosilylated derivative, which was treated
with trimethylsilyl chloride to afford compound 13. On
the other hand, transformation of the monosilylated
compound into the carbonate, followed by reaction
with p-tert-butylphenol in the presence of Pd2(dba)3
and dppb as the catalyst gave compound 12.
Reaction of phenylmagnesium bromide with com-
pound 9, having the leaving group at C-4 instead at the
anomeric center, in the presence of PdCl2(dppf), gave
the arylated product 10 in 46% yield, at 25°C (Scheme
2). In this case, we observed again a net retention of
configuration at the new created carbon center. When
the same reaction was performed in the presence of a
NiCl2(dppe) at −20°C, the formation of compound 11
was observed in 54% yield. In this case, due to some
steric effects, the alkylation occurs only at C-2, but with
complete inversion of configuration. So it seems that
the position of the leaving group at the anomeric center
is not crucial for the observed retention of configura-
tion with palladium complex.
4. Experimental
4.1. General methods and materials
NMR spectra were obtained in CDCl3, and chemical
shifts are given in ppm on the l scale from internal
tetramethylsilane. THF was distilled from sodium/ben-
zophenone, purged, and kept under a nitrogen atmo-
sphere. Reactions involving palladium or nickel
complexes were carried out in a Schlenk tube under a
nitrogen atmosphere.
PdCl2(dppf) [28], NiCl2(dppe) [29], compounds 1 [30],
3 [30], 5 [30], 7 [30], ethyl 6-O-(tert-butyldimethylsilyl)-
4-O-methoxycarbonyl-2,3-dideoxy-h-D-erythro-hex-2-
enopyranoside [26] and cis 5-(hydroxymethyl)cyclohex-
2-en-1-ol [27] were prepared according to known
procedures.
4.2. Synthesis of ethyl 6-O-(tert-butyldimethylsilyl)-
However, when the cyclohexenyl derivatives 12 cis
and 13 cis were reacted with C6H5MgBr in the presence
of PdCl2(dppf) or NiCl2(dppe) (Scheme 3), we mainly
observed inversion of the configuration (Table 2). The
NiCl2(dppe) mediated reaction was completely stereose-
lective, giving only the trans isomer 14 trans, although
the palladium catalyzed reaction gave a mixture of cis
4-O-(p-tert-butylphenyl)-2,3-dideoxy-h-
hex-2-enopyranoside (9)
D-erythro-
To a solution of ethyl 6-O-(tert-butyldimethylsilyl)-4-
O-methoxycarbonyl-2,3-dideoxy-h- -erythro-hex-2-
D
enopyranoside [26] (1.0 g, 2.9 mmol) and p-tert-
butylphenol (2.17 g, 14.4 mmol) in 10 ml of dry THF
was added the catalytic system obtained by reacting
Pd2(dba)3 (130 mg, 0.15 mmol) and dppb (250 mg, 0.58
mmol) in 2 ml of THF. The mixture was stirred at 25°C
for 24 h. Evaporation of the solvent under reduced
pressure, followed by column chromatography on silica
gel using petroleum ether/ethyl acetate (1/5) as the
eluent gave 1.1 g of compound 9 (90%). [h]2D0+125.5 (c
1
1.5, CH2Cl2). H-NMR (200 MHz) l 0.04 (s, 3H), 0.05
(s, 3H), 0.89 (s, 9H), 1.27 (t, 3H, J=7.1 Hz), 1.31 (s,
9H), 3.58 (dq, 1H, J=9.6, 7.1 Hz), 3.78–3.96 (m, 3H),
Scheme 3.

160
C. Moineau et al. / Journal of Organometallic Chemistry 567 (1998) 157–162
Table 2
Diastereoselectivity in the reaction of cyclohexenyl derivatives 12 and 13 with phenylmagnesium bromide in the presence of palladium and nickel
complexes
Entry
Substrate
12 cis
Catalyst
Yield (%)
Isomeric ratioa cis/trans (%)
Retention/inversion(%)
1
2
3
PdCl2(dppf)
NiCl2(dppe)
PdCl2(dppf)
72
70
60
30/70
0/100
37/63
30/70
0/100
37/63
13 cis
a
Isomeric purity determined by 1H-NMR and 13C-NMR.
4.04 (ddd, 1H, J=9.2, 5.1, 2.0 Hz), 4.79 (dd, 1H,
J=9.2, 1.2 Hz), 5.08 (brs, 1H), 5.83 (brd, 1H, J=9.2
Hz), 6.09 (brd, 1H, J=10.2 Hz), 6.85 (d, 2H, J=8.8
Hz), 7.30 (d, 2H, J=8.8 Hz). Anal. Calcd for
C24H40O4Si: C, 68.53; H, 9.58. Found: C, 68.67; H,
9.49.
and dppb (61 mg, 0.14 mmol) in 2 ml of THF. The
mixture was stirred at 25°C for 24 h. Evaporation of
the solvent under reduced pressure, followed by column
chromatography on silica gel using petroleum ether/
ethyl acetate (30/1) as the eluent gave 510 mg of
1
compound 12 (40%). H-NMR (200 MHz) l 0.00 (s,
6H), 0.85 (s, 9H), 1.26 (s, 9H), 1.57-2.25 (m, 5H), 3.48
(d, 2H, J=5.9 Hz), 4.85 (m, 1H), 5.65 (brd, 1H,
J=10.0 Hz), 5.85 (d, 1H, J=10.0 Hz), 6.83 (d, 2H,
J=8.0 Hz), 7.25 (d, 2H, J=8.0 Hz). 13C-NMR (50
MHz) l −5.3 (SiCH3), 18.4 (SiCMe3), 26.0 (SiCMe3),
28.5 (C-6), 31.6 (CMe3), 32.2 (C-4), 34.1 (CMe3), 35.9
(C-5), 67.5 (CH2O), 73.3 (C-1), 115.4, 126.3, 127.9,
129.6, 143.4 and 155.6 (C6H4, C-2 and C-3). Anal.
Calcd for C23H38O2Si: C, 73.74; H, 10.22. Found: C,
73.60; H, 10.24.
4.3. Synthesis of cis 5-[(tert-butyldimethylsilyoxy)
methyl]cyclohex-2-en-1-ol
Cis 5-(hydroxymethyl)cyclohex-2-en-1-ol [27] (1.1 g,
8.7 mmol) was treated with 1.25 equiv of TBDMSCl
(1.62 g, 10.8 mmol), 1.3 equiv of NEt3 (1.6 ml, 11.2
mmol), and 0.05 equiv of imidazole (30 mg, 0.43 mmol)
in CH2Cl2 (30 ml) at r.t. for 24 h. After addition of 25
ml of water and extraction with 3×30 ml of CH2Cl2,
the organic layer was dried. Evaporation of the solvent
under reduced pressure, and column chromatography
of the residue on silica gel using petroleum ether/ethyl
acetate (5/1) as the eluent gave 840 mg of cis 5-[(tert-
butyldimethylsilyoxy)methyl]cyclohex-2-en-1-ol as an
4.5. Synthesis of cis 5-[(tert-butyldimethylsilyloxy)
methyl]-1-(trimethylsilyloxy) cyclohex-2-ene (13)
To a solution of 100 mg (0.4 mmol) of cis 5-[(tert-
butyldimethylsilyloxy)methyl]-1-(p-tert-butylphenoxy)
cyclohex-2-ene in 25 ml of THF at r.t. was added 4
equiv of Et3N (0.06 mmol) and 3 equiv of Me3SiCl
(0.15 ml). After being stirred for 24 h, 50 ml of cold
water was added and the solution was extracted with
3×25 ml of CH2Cl2. Evaporation of the solvent and
column chromatography on silica gel neutralized with
1% Et3N using petroleum ether/ethyl acetate (5/1) as
1
oil (40%). H-NMR (200 MHz) l 0.06 (s, 6H), 0.90 (s,
9H), 1.58–2.19 (m, 6H), 3.55 (brd, 2H, J=5.9 Hz),
4.30 (m, 1H), 5.69 (d, 1H, J=10.0 Hz), 5.79 (d, 1H,
J=10.0 Hz). 13C-NMR (50 MHz) l -5.4 (SiCH3), 18.4
(SiCMe3), 26.0 (SiCMe3), 28.3 (C-6), 35.6 (C-4), 35.8
(C-5), 67.6 (C-1), 67.6 (CH2O), 128.4 and 131.2 (C-2
and C-3).
1
4.4. Synthesis of cis 5-[(tert-butyldimethylsilyoxy)
methyl]-1-(p-tert-butylphenoxy) cyclohex-2-ene (12)
the eluent gave 120 mg of compound 13 (96%). H-
NMR (200 MHz) l 0.05 (s, 6H), 0.15 (s, 9H), 0.90 (s,
9H), 1.14–2.06 (m, 5H), 3.49 (d, 2H, J=5.7 Hz), 4.35
(m, 1H), 5.58 (d, 1H, J=10.3 Hz), 6.02 (d, 1H, J=
10.3 Hz). 13C-NMR (50 MHz) l -5.2 (SiCH3), 0.4
(SiCH3), 18.4 (SiCMe3), 26.0 (SiCMe3), 28.4 (C-6), 36.1
(C-4), 36.3 (C-5), 67.8 (CH2O), 68.4 (C-1), 127.8 and
132.1 (C-2 and C-3).
To a solution of 850 mg (3.5 mmol) of cis 5-[(tert-
butyldimethylsilyoxy)methyl]-1-(p-tert-butylphenoxy)
cyclohex-2-en-1-ol in 30 ml of CH2Cl2 at r.t. was added
65 mg (0.7 mmol) of DMAP, 1.4 ml (17.5 mmol) of
pyridine, and 1.35 ml (17.5 mmol) of methyl chlorofor-
mate. The mixture was stirred at r.t. for 24 h. After
addition of 30 ml of a water of CuSO4 ·5H2O, the
solution was extracted with 4×25 ml of Et2O. Re-
moval of the solvent under reduced pressure gave the
crude carbonate which was immediatly mixed with
p-tert-butylphenol (530 mg, 3.5 mmol) in 5 ml of dry
THF. To this solution was added the catalytic system
obtained by reacting Pd2(dba)3 (31.6 mg, 0.036 mmol)
4.6. General procedure for palladium- and
nickel-catalyzed reaction
To a solution of the unsaturated substrate (0.44
mmol) and PdCl2(dppf) (31.9 mg, 0.044 mmol) or
NiCl2(dppe) (23 mg, 0.044 mmol) in 2 ml of THF was
added at the desired temperature a solution of the

C. Moineau et al. / Journal of Organometallic Chemistry 567 (1998) 157–162
161
Grignard reagent prepared from magnesium (64 mg,
4.7.1. [4,6-Di-O-(tert-butyldimethylsilyl)-2,3-dideoxy-
i- -erythro-hex-2-enopyranosyl] benzene (4™)
[h]2D0+189.1 (c 1.0, CH2Cl2). H-NMR (200 MHz) l
2.6 mmol) and phenyl bromide (2.18 mmol) in 5 ml
THF. After the time indicated in the Tables, di-
ethylether (50 ml) was added, the ethereal solution was
washed with water (2×10 ml) and dried. Concentra-
tion and column chromatography furnished the phenyl
derivative.
D
1
0.04 (s, 6H), 0.13 (s, 3H), 0.14 (s, 3H), 0.90 (s, 9H), 0.93
(s, 9H), 3.51 (ddd, 1H, J=8.5, 4.5, 2.1 Hz), 3.84 (dd,
1H, J=11.4, 4.5 Hz), 3.93 (dd, 1H, J=11.4, 2.1 Hz),
4.38 (dd, 1H, J=8.5, 2.9 Hz), 5.16 (d, 1H, J=2.9 Hz),
5.77 (s, 2H), 7.27-7.36 (m, 5H). 13C-NMR (50 MHz) l
−5.0 (SiMe3), −4.9 (SiMe3), −4.6 (SiMe3), −4.1
(SiMe3), 18.2 (SiCMe3), 18.6 (SiCMe3), 26.0 (SiCMe3),
26.1 (SiCMe3), 63.1 (C-6), 63.6 (C-4), 77.3 (C-1), 80.7
(C-5), 127.1, 127.8, 128.4, 129.9, 130.7 and 141.5 (C-2,
C-3 and C6H5). Anal. Calcd. for C24H42O3Si2: C, 66.30,
H, 9.74. Found: C, 66.00; H, 9.71.
4.6.1. (4,6-Di-O-benzyl-2,3-dideoxy-h-D-erythro-hex-
2-enopyranosyl)benzene (2˜)
1
[h]2D0+18.5 (c 0.9, CH2Cl2). H-NMR (300 MHz) l
3.50-3.70 (m, 3H), 4.19 (brd, 1H, J=7.3 Hz), 4.46 (d,
1H, J=11.5 Hz), 4.61 (d, 1H, J=11.5 Hz), 4.43 (d,
1H, J=12.1 Hz), 4.58 (d, 1H, J=12.1 Hz), 5.30 (brs,
1H), 6.06 (brd, 1H, J=10.9 Hz), 6.13 (brd, 1H, J=
10.9 Hz), 7.20–7.50 (m, 15H). 13C-NMR (50 MHz) l
69.1, 71.1 and 73.2 (C-6, 2xCH2), 70.1 and 70.7 (C-4
and C-5), 74.1 (C-1), 127.1, 127.5, 127.7, 127.8, 127.9,
128.0, 128.1, 128.3, 128.3, 128.3, 129.5, 138.2, 138.2 and
139.5 (C-2, C-3 and C6H5). Anal. Calcd for C26H26O3:
C, 80.80, H, 6.78. Found: C, 80.37; H, 6.69.
4.7.2. (4-O-Benzyl-2,3,6-trideoxy-h-D-erythro-hex-2-
enopyranosyl)benzene (6˜)
1
[h]2D0−20.6 (c 1.0, CH2Cl2). H-NMR (200 MHz) l
1.25 (d, 3H, J=6.0 Hz), 3.69-3.77 (m, 2H), 4.60 (d, 1H,
J=11.6 Hz), 4.70 (d, 1H, J=11.6 Hz), 5.21 (s, 1H),
6.07 (brd, 1H, J=11.3 Hz), 6.14 (brd, 1H, J=11.3
Hz), 7.25–7.45 (m, 10H). 13C-NMR (50 MHz) l 18.4
(CH3), 67.9 (C-5), 71.1 (CH2), 73.7 (C-4), 75.8 (C-1),
126.7, 127.9, 128.0, 128.1, 128.1, 128.5, 128.7, 130.3,
138.5 and 140.1 (C-2, C-3 and C6H5). Anal. Calcd for
C19H20O2: C, 81.40, H, 7.19. Found: C, 81.23; H, 7.15.
4.6.2. (4,6-Di-O-benzyl-2,3-dideoxy-i-D-erythro-hex-
2-enopyranosyl)benzene (2™)
1
[h]2D0+60.8 (c 0.7, CH2Cl2). H-NMR (300 MHz) l
3.60-3.90 (m, 3H), 4.16 (dm, 1H, J=8.6 Hz), 4.51 (d,
1H, J=11.5 Hz), 4.66 (d, 1H, J=11.5 Hz), 4.56 (d,
1H, J=12.1 Hz), 4.64 (d, 1H, J=12.1 Hz), 5.18 (brs,
1H), 5.86 (ddd, 1H, J=10.3, 1.6, 1.6 Hz), 6.01 (ddd,
1H, J=10.3, 2.0, 2.0 Hz), 7.20–7.40 (m, 15H). 13C-
NMR (50 MHz) l 69.9, 71.2 and 73.4 (C-6 and
2xCH2), 70.5 (C-4), 77.4 (C-5), 77.8 (C-1), 125.8, 126.0,
127.1, 127.5, 127.9, 128.2, 128.3, 128.4, 128.5, 131.7,
138.1, 138.4 and 140.8 (C-2, C-3 and C6H5). Anal.
Calcd. for C26H26O3: C, 80.80, H, 6.78. Found: C,
80.38; H, 6.82.
4.7.3. (4-O-Benzyl-2,3, 6-trideoxy-i-L-erythro-hex-2-
enopyranosyl)benzene (6™)
1
[h]2D0−219.2 (c 1.0, CH2Cl2). H-NMR (200 MHz) l
1.38 (d, 3H, J=5.9 Hz), 3.73 (dq, 1H, J=8.4, 5.9 Hz),
3.85 (dm, 1H, J=8.4 Hz), 4.60 (d, 1H, J=11.6 Hz),
4.73 (d, 1H, J=11.6 Hz), 5.14 (brs, 1H), 5.85 (brd, 1H,
J=10.3 Hz), 6.02 (brd, 1H, J=10.3 Hz), 7.24-7.39 (m,
10H). 13C-NMR (50 MHz) l 19.2 (CH3), 71.6 (CH2),
74.5 (C-4), 76.7 (C-5), 77.8 (C-1), 126.6, 127.6, 128.1,
128.3, 128.3, 128.8, 128.9, 131.9, 138.6 and 141.2 (C-2,
C-3 and C6H5). Anal. Calcd for C19H20O2: C, 81.40, H,
7.19. Found: C, 81.17; H, 7.10.
4.7. [4,6-Di-O-(tert-butyldimethylsilyl)-2,3-dideoxy-h-
D
-erythro-hex-2-enopyranosyl] benzene (4˜)
1
[h]2D0+3.9 (c 1.0, CH2Cl2). H-NMR (200 MHz) l
4.7.4. (6-O-Benzyl-4-O-methyl-2,3-dideoxy-h-D-threo-
0.02 (s, 3H), 0.04 (s, 3H), 0.07 (s, 3H), 0.08 (s, 3H), 0.87
(s, 9H), 0.89 (s, 9H), 3.41 (ddd, 1H, J=8.1, 6.2, 2.3
Hz), 3.70 (dd, 1H, J=11.1, 6.2 Hz), 3.85 (dd, 1H,
J=11.1, 2.3 Hz), 4.20 (dddd, 1H, J=8.1, 1.9, 1.9, 1.9
Hz), 5.28 (m, 1H), 5.88 (ddd, 1H, J=10.3, 1.9, 1.9 Hz),
6.07 (ddd, 1H, J=10.3, 3.1, 1.7 Hz), 7.25-7.49 (m, 5H).
13C-NMR (50 MHz) l −5.2 (SiMe3), −5.0 (SiMe3),
−4.6 (SiMe3), −4.0 (SiMe3), 18.1 (SiCMe3), 18.5
(SiCMe3), 25.9 (SiCMe3), 26.1 (SiCMe3), 63.4 (C-6),
64.3 (C-4), 73.7 (C-5), 74.6 (C-1), 127.5, 127.6, 128.4,
128.5, 130.9 and 140.4 (C-2, C-3 and C6H5). Anal.
Calcd for C24H42O3Si2: C, 66.30, H, 9.74. Found: C,
66.51; H, 9.84.
hex-2-enopyranosyl)benzene (8˜)
1
[h]2D0−173.6 (c 1.0, CH2Cl2). H-NMR (300 MHz) l
3.45 (s, 3H), 3.68 (dd, 1H, J=10.2, 7.0 Hz), 3.75 (dd,
1H, J=10.2, 5.4 Hz), 3.64-3.71 (m, 1H), 3.96 (ddd, 1H,
J=7.0, 5.4, 2.8 Hz), 4.49 (d, 1H, J=11.9 Hz), 4.56 (d,
1H, J=11.9 Hz), 5.35 (brs, 1H), 6.23 (ddd, 1H, J=
10.3, 2.8, 1.5 Hz), 6.32 (dd, 1H, J=10.3, 2.8 Hz),
7.22–7.44 (m, 10H). 13C-NMR (50 MHz) l 56.8
(CH3), 69.2 and 73.3 (CH2 and C-6), 70.2 and 71.2 (C-4
and C-5), 73.8 (C-1), 114.9, 124.6, 126.4, 127.6, 127.7,
127.8, 128.5, 138.5, 139.3 and 132.5 (C-2, C-3 and
C6H5). Anal. Calcd. for C20H22O3: C, 77.39, H, 7.14.
Found: C, 78.07; H, 7.16.

162
C. Moineau et al. / Journal of Organometallic Chemistry 567 (1998) 157–162
Acknowledgements
4.7.5. Ethyl 6-O-(tert-butyldimethylsilyl)-4-phenyl-
2,3,4-trideoxy-h- -erythro-hex-2-enopyran oside (10)
D
[h]2D0+91.6 (c 1.0, CH2Cl2). H-NMR (200 MHz) l
−0.04 (s, 6H), 0.85 (s, 9H), 1.25 (t, 3H, J=7.1 Hz),
3.45 (bd, 1H, J=11.2 Hz), 3.49–3.65 (m, 3H), 3.90
(dq, 1H, J=9.6, 7.1 Hz), 3.86 (m, 1H), 5.09 (bs, 1H),
5.86 (dd, 1H, J=10.1, 2.1 Hz), 5.93 (d, 1H, J=10.1
Hz), 7.19–7.30 (m, 5H). 13H-NMR (50 MHz) l −5.3
(SiCH3), −5.2 (SiCH3), 15.5 (CH3), 18.5 (SiCMe3),
26.0 (SiCMe3), 42.5 (C-4), 63.4 and 63.6 (C-6 and CH2),
73.8 (C-5), 94.2 (C-1), 125.6, 127.0, 128.6, 128.8, 133.6
and 140.9 (C-2, C-3 and C6H5). Anal. Calcd for
C20H32O3Si: C, 68.92; H, 9.25. Found: C, 68.81; H,
9.24.
1
Financial support from the CNRS and the MENESR
(grant to C.M.) is gratefully acknowledged
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[h]2D0+147.8 (c 1.0, CH2Cl2). H-NMR (300 MHz) l
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4.7.7. Trans 5-[(tert-butyldimethylsilyoxy)methyl]-1-
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1H-NMR (200 MHz) l −0.01 (s, 3H), 0.01 (s, 3H),
0.86 (s, 9H), 1.66–2.30 (m, 5H), 3.41–3.55 (m, 3H),
5.75 (dm, 1H, J=10.2 Hz), 6.02 (dm, 1H, J=10.2 Hz),
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phenylcyclohex-2-ene (14)
13C-NMR (50 MHz) in the mixture of cis and trans
isomers l −5.2 (SiCH3), 18.6 (SiCMe3), 26.2 (SiCMe3),
28.7 (C-6), 36.6 (C-4), 37.6 (C-5), 43.3 (C-1), 68.3
(CH2), 126.2, 127.4, 127.6, 128.6, 131.1 and 146.9 (C-2,
C-3 and C6H5).
.
.