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Stereoselective synthesis of erythro - and threo -1,2-diols from diketo sulfides via cis -3,4-dihydroxythiolanes
Tetrahedron
STEREOSELECTIVE SYNTHESIS OF erythro- AND threo-1,2-DIOLS FROM DIKETO SULFIDES VIA cis-3,&DIHYDROXYTHIOLANES -
Juzo Nakayama,* Shoji Yamaoka, and Masamatsu Hoshino Department of Chemistry, Faculty of Science, Saitama University, Urawa, Saitama 338, Japan
Summary: Intramolecular reductive coupling reaction of a series of diketo sulfides
(1) by a low-valent
titanium
leads to &-3,4_dihydroxythiolanes Desulfurization
of 2 by Raney nickel
or threo-1,2-diols
reagent
at 0 "C in tetrahydrofuran
(2) exclusively in ethanol
in 67-89% yields.
affords
either erythro-
or
(3) in 51-82% yields.
Diketo sulfides (1) are readily accessible compounds.
Symmetrically
substituted 1 are obtained by reaction of a-haloketones with sodium sulfide and unsymmetrically substituted ones are by reaction of a-haloketones with a-mercaptoketones. l-4 We previously reported that treatment of 1 at 0 "C or so by a low-valent titanium reagent (prepared from titanium(IV) chloride and zinc powder in tetrahydrofuran) 5 leads to 3,4-dihydroxythiolanes now found that two hydroxy groups of 2 are in d-configuration
(2).3
We
each other
in any case and hence desulfurization of 2 by Raney nickel gives rise to either erythro- or threo-1,2-diols (3) depending on the substituents on the thiolane ring. Thus, intramolecular reductive coupling reaction of diketo sulfides la-c _- I by the foregoing low-valent titanium reagent at 0 "C in tetrahydrofuran 6 afforded cc&-3,4-diaryl-3,4-dihydroxythiolanes __ 2a-c _ exclusively in good yields. Desulfurization of __ 2a-c _ by Raney nickel in refluxing ethanol gave the 7. corresponding erythro(meso)-1,2-diols 3a-c ~__ _ in good yields. HO R
OH
TiC14-Zn
Raney-nickel ,P+ EtOH, refl.
THF, 0 'C la
: R = C6H5
b : R = 4-MeC6H4 c : R = 4-MeOC6H4
2a b c
: 82% : 78% : 67%
1799
HO
OH
3a : 75% b c
: 82% : 82%
1800
The exclusive explained
as
titanium(I1) zinc,
to
produced
2a-c _.” .
a cyclic after
a-3,4-dihydroxythiolanes
Reduction
a titanium(II1)
rise
c&-diols
of
below.
chloride,
affords
4 gives
formation
depicted
of
one
by reduction species
of
of
(4).
titanium(IV)
Intramolecular
titanium(IV)
derivative 8 hydrolysis.
alkaline
2a-c may best be _P. I groups of ;a-c by S chloride with
carbonyl
(S), I
cycloaddition
which
should
of
lead
to
TiC12 Tic12
la-c
)
R<:yR
)
R._'$R
"2'
~
2a_c
S
4
Diketo reaction.
sulfide
also
afforded
Desulfurization
accompanied thus
Id
5
by
providing
the
c&-diol
2d on reductive
2d by Raney nickel __ reductive desulfurization
in
of
concomitant
refluxing of
ethanol
the
erythro-5,6-dihydroxy-5,6_dimethyldecane
coupling was
thiophene
(3d)7 __
in
9
rings,
71% yield.
EtOH, refl. Id
Diketo isomers.
2d
89%
sulfides
If are obtained as a mixture .le.._ and -.., of a mixture of meso- and &l-isomers
Reduction
affords
2e and 2f which are a mixture of __ __ that there exist three isomers in 2e and __ 10 cis each other). However, desulfurization only
erythro-isomers
ethanol
2f _-
of
m-
and d_,l_-
of
le and If __ __ isomers (note
geometrical
even
if
two hydroxy
groups
of
these
isomeric
mixtures
it
required
Raney
prolonged
nickel
HO
probably
OH
TiC14-Zn
because
THF, 0 "C
Me le
EtOH, refl.
: R = Ph
f:
only
erythro-isomers of
substituted
3g7 was __
satisfactorily
diketo
Et
Et 3e
: 51%
71%
f
: 81%
were
t-o-isomers
OH
: 82%
f:
preparation
unsymmetrically
threo-1,2-diol
2e
R = Me
Although instances,
HO
Raney-Ni
synthesized is
also
sulfide synthesized.
in
the
foregoing
possible.
Thus,
lg, -I
substituted
highly
are gave
refluxing
reason. R
from
three
3e and 3f,7 although __ _-. of a large excess of
and the use 11
steric
3d
71%
starting
in of
1801
HO
OH
TiC14-Zn e-
e -w
THF, 0 "C
HO
Raney-Ni
OH
EtOH, refl. 79%
72%
19
39
29
Finally effort was made to elaborate both erythro- and threo-isomers -~ Thus, starting from sulfides __ lh and
starting from different diketo sulfides.
11, erythro-1,2-diols ~IJ (=zf) and 3j7 __ were satisfactorily synthesized, while the corresponding threo-isomers 3i 3k7 were cleanly prepared from __ and ..W sulfides W_ li and a?. lk, respectively. E
HO Et._._
TiC14-Zn THF, 0 'C *
H 67%
lh
Me
S
OH mm..Et Raney-Ni EtOH, refl. 76%
2h
as above
-
as above
HO
69%
lj
X _-Me
HO
---Et -
as above
tf S 2j HO
Me
Et
-
H
Ph ---F-4 Me 77% 3j
OH as above
3:
HO
2k
Me
Ph--Et
Me 77%
--.-Et
OH
HO
Me lk
OH
Et----
OH
Ph--
as above *
YYY S
3h(=3f)
75%
li
Et
OH
Me
Me
Ph
HO
80%
3k
One of general methods for the preparation of 1,2-aiols involves pinacolic reduction of carbonyl compounds.12
This method, however, leads to
a mixture of erythro- and threo-isomers, when applied to aldehydes and unsymmetrically substituted ketones, and usually cannot be applied to the preparation of constitutionally unsymmetrical 1,2-dials (cross-coupling reaction between different carbonyl compounds). Diketo sulfides 1 are prepared from ketones as starting material. The net result of the present conversion, therefore, implies that stereospecific pinacolic reduction, not only between same carbonyl compounds but also between different carbonyl compounds, could be attained. In summary, the method developed here provides a novel selective synthesis of both erythro- and threo-1,2-diols, whose 12 preparation hitherto required pure E- or Z-olefins.
1802
References
and Notes
1.
Y. Miyahara,
J. HeterocycZ.
2.
J. Nakayama,
H. Motoyama,
&em., 16, 1147 (1979). IH. Machida, M. Shimomura, and M. Hoshino,
HeteroeycZes,
22, 1527 (1984). 3.
?a") J. Nakayama,
H. Machida,
R. Saito, and M. Hoshino,
H. Machida,
and M. Hoshino,
Tetrahedron
26, 1983 _-.
Lett.,
(1985). (b) J. Nakayama, 4.
E. Vedejs, Schwartz,
T. H. Everlein,
D. J. Mazur,
D. L. Varie,
J. S. Stults,
Tetrahedron
C. K. McClure,
R. G. Wilde,
Lett.,
2'6, 1981 (1985).
D. A. Perry, R. Ruggeri,
and S. Wittenberger,
E.
J. Org. them.,
51, 1556 (1986). 5.
7: Mukaiyama,
6.
CA-Configuration
T. Sato, and J. Hanna, &em. of 2a is also established
HO
OH __
7.
mp and 'H-NMR
'
m-CPBA
Ph---
---Ph
data (CDC13 as solvent)
3b: mp 136-137
S
of 1,2-diols
3a-k are as follows.
"C (lit., mp 134-135
2.24 (2H, s, OH),
"C); 'H-NMR 6 1.51 (6H, s, Me),
(BH, m, benzene
rings).
3c: mp 169-171
(8H, m, benzene
139 "C (lit., mp 138 "C);
rings).
3_d: viscous
oil; 'H-NMR 6 0.92
(6H, t, Me),
(12H, m, methylene), 2.0 (2H, broad s, OH). 3e: mp 138NW ’ H-NMR 6 0.60 (6H, t, Me), 1.2-2.6 (4H, double quartet,
2.12 (2H, s, OH), 7.21 (lOH, s, Ph).
0.96 (6H, t, Me), 1.14 (6H, s, Me), ca. 1.3-1.7 13C-NMR 6 7.8, 20.3, 28.0, 76.8.
3_f (=$):
mp 49.5-51
(4H, m, methylene),
39: mp 58-59 "C; 'H-NMR B 0.85
"C; 'H-NMR 6
2.06
(2H, s, OH);
(3H, d, Me), 0.92
(3H, d, Me), 1.07 (3H, s, Me), 1.66""(3H, s, Me), 1.79 (lH, broad s, OH), 1.5-2.1 m, methine),
2.52 (lH, broad s, OH), 7.1-7.6
52 "C); 'H-NMR 6 0.96 (4H, m, methylene), 76-76.5
“C
"C); 'H-NMR 6 1.53 (6H, s, Me), 2.24 (ZH, broad s, ;jH), 3.76 (6H, s,
1.16 (6H, s, Me), 1.1-1.9
methylene),
conversions.
h ti
2G3
2.15 (2H, s, OH), 2.29 (6H, s, Me), 6.9-7.3
OMe), 6.6-7.2
Ph
1) m-CPBA
"C (lit., mp 120 "C); 'H-NMR 6 1.56 (6H, s,-Me),
7:15 (lOH, s, Ph).
(lit., mp 168-169
chemical
82
(13C-NMR)
3a: mp 117.5-118.5
H
-;rp
2a
1041 (1973).
by the following
HO
---Ph
Ph--H
Lett.,
(5H, m, Ph).
(TH,
3i_: mp 51-52 "C (lit., mp
(6H, t, Me), 1.12 (3H, s, Me), 1.13 (3H, s, Me), ca. 1.2-1.9
1.83 (2H, broad s, OH); 13C-NMR
6 7.7, 19.8, 28.4, 76.8.
"C; 'H-NMR 6 0.80 (3H, t, Me), 1.19 (3H, s, Me), ca. 1.2-2.0
3_j;:.mp
(2H, m, methylene),
1.63 (3H, s, Me), 1.83 (lH, broad s, OH), 2.65 (lH, broad s, OH), 7.1-7.6
(5H, m, Ph).
3k: mp 94.5 "C; 'H-NMR 6 0;93 (3H, t, Me), 0.98 (3H, s, Me), 1.59 (3H, s, Me), ca. ..,_ l.l-1,9 (2H, m, methylene), 1.81 (lH, broad s, OH), 2.62 (lH, broad S, OH), 7.2-7.5 (5H, m, Ph). 8.
E. J. Corey, R. L. Danheiser,
9.
Selective
desulfurization
and S. Chandrasekaran,
of only thiolane
10.
Two isomers are formed from meso-sulfides
11.
More sterically furization.
12.
Pergamon
in "Comprehensive
Press, Oxford, in
Japan
41, 260 (1976).
and one isomer from d,l-sulfides.
2,5-diethyl-3,4-dihydroxy-3,4_diphenylthiolane
The desulfurization
S. G. Wilkinson
(Received
crowded
J. Org. Chem.,
ring could not be attained":
17
under forced conditions Organic
1979, p, 666. January
1987)
Chemistry,"
gave a complex
resisted
desul-
mixture.
Vol. 1, J. F. Stoddart
Ed.,
STEREOSELECTIVE SYNTHESIS OF erythro- AND threo-1,2-DIOLS FROM DIKETO SULFIDES VIA cis-3,&DIHYDROXYTHIOLANES -
Juzo Nakayama,* Shoji Yamaoka, and Masamatsu Hoshino Department of Chemistry, Faculty of Science, Saitama University, Urawa, Saitama 338, Japan
Summary: Intramolecular reductive coupling reaction of a series of diketo sulfides
(1) by a low-valent
titanium
leads to &-3,4_dihydroxythiolanes Desulfurization
of 2 by Raney nickel
or threo-1,2-diols
reagent
at 0 "C in tetrahydrofuran
(2) exclusively in ethanol
in 67-89% yields.
affords
either erythro-
or
(3) in 51-82% yields.
Diketo sulfides (1) are readily accessible compounds.
Symmetrically
substituted 1 are obtained by reaction of a-haloketones with sodium sulfide and unsymmetrically substituted ones are by reaction of a-haloketones with a-mercaptoketones. l-4 We previously reported that treatment of 1 at 0 "C or so by a low-valent titanium reagent (prepared from titanium(IV) chloride and zinc powder in tetrahydrofuran) 5 leads to 3,4-dihydroxythiolanes now found that two hydroxy groups of 2 are in d-configuration
(2).3
We
each other
in any case and hence desulfurization of 2 by Raney nickel gives rise to either erythro- or threo-1,2-diols (3) depending on the substituents on the thiolane ring. Thus, intramolecular reductive coupling reaction of diketo sulfides la-c _- I by the foregoing low-valent titanium reagent at 0 "C in tetrahydrofuran 6 afforded cc&-3,4-diaryl-3,4-dihydroxythiolanes __ 2a-c _ exclusively in good yields. Desulfurization of __ 2a-c _ by Raney nickel in refluxing ethanol gave the 7. corresponding erythro(meso)-1,2-diols 3a-c ~__ _ in good yields. HO R
OH
TiC14-Zn
Raney-nickel ,P+ EtOH, refl.
THF, 0 'C la
: R = C6H5
b : R = 4-MeC6H4 c : R = 4-MeOC6H4
2a b c
: 82% : 78% : 67%
1799
HO
OH
3a : 75% b c
: 82% : 82%
1800
The exclusive explained
as
titanium(I1) zinc,
to
produced
2a-c _.” .
a cyclic after
a-3,4-dihydroxythiolanes
Reduction
a titanium(II1)
rise
c&-diols
of
below.
chloride,
affords
4 gives
formation
depicted
of
one
by reduction species
of
of
(4).
titanium(IV)
Intramolecular
titanium(IV)
derivative 8 hydrolysis.
alkaline
2a-c may best be _P. I groups of ;a-c by S chloride with
carbonyl
(S), I
cycloaddition
which
should
of
lead
to
TiC12 Tic12
la-c
)
R<:yR
)
R._'$R
"2'
~
2a_c
S
4
Diketo reaction.
sulfide
also
afforded
Desulfurization
accompanied thus
Id
5
by
providing
the
c&-diol
2d on reductive
2d by Raney nickel __ reductive desulfurization
in
of
concomitant
refluxing of
ethanol
the
erythro-5,6-dihydroxy-5,6_dimethyldecane
coupling was
thiophene
(3d)7 __
in
9
rings,
71% yield.
EtOH, refl. Id
Diketo isomers.
2d
89%
sulfides
If are obtained as a mixture .le.._ and -.., of a mixture of meso- and &l-isomers
Reduction
affords
2e and 2f which are a mixture of __ __ that there exist three isomers in 2e and __ 10 cis each other). However, desulfurization only
erythro-isomers
ethanol
2f _-
of
m-
and d_,l_-
of
le and If __ __ isomers (note
geometrical
even
if
two hydroxy
groups
of
these
isomeric
mixtures
it
required
Raney
prolonged
nickel
HO
probably
OH
TiC14-Zn
because
THF, 0 "C
Me le
EtOH, refl.
: R = Ph
f:
only
erythro-isomers of
substituted
3g7 was __
satisfactorily
diketo
Et
Et 3e
: 51%
71%
f
: 81%
were
t-o-isomers
OH
: 82%
f:
preparation
unsymmetrically
threo-1,2-diol
2e
R = Me
Although instances,
HO
Raney-Ni
synthesized is
also
sulfide synthesized.
in
the
foregoing
possible.
Thus,
lg, -I
substituted
highly
are gave
refluxing
reason. R
from
three
3e and 3f,7 although __ _-. of a large excess of
and the use 11
steric
3d
71%
starting
in of
1801
HO
OH
TiC14-Zn e-
e -w
THF, 0 "C
HO
Raney-Ni
OH
EtOH, refl. 79%
72%
19
39
29
Finally effort was made to elaborate both erythro- and threo-isomers -~ Thus, starting from sulfides __ lh and
starting from different diketo sulfides.
11, erythro-1,2-diols ~IJ (=zf) and 3j7 __ were satisfactorily synthesized, while the corresponding threo-isomers 3i 3k7 were cleanly prepared from __ and ..W sulfides W_ li and a?. lk, respectively. E
HO Et._._
TiC14-Zn THF, 0 'C *
H 67%
lh
Me
S
OH mm..Et Raney-Ni EtOH, refl. 76%
2h
as above
-
as above
HO
69%
lj
X _-Me
HO
---Et -
as above
tf S 2j HO
Me
Et
-
H
Ph ---F-4 Me 77% 3j
OH as above
3:
HO
2k
Me
Ph--Et
Me 77%
--.-Et
OH
HO
Me lk
OH
Et----
OH
Ph--
as above *
YYY S
3h(=3f)
75%
li
Et
OH
Me
Me
Ph
HO
80%
3k
One of general methods for the preparation of 1,2-aiols involves pinacolic reduction of carbonyl compounds.12
This method, however, leads to
a mixture of erythro- and threo-isomers, when applied to aldehydes and unsymmetrically substituted ketones, and usually cannot be applied to the preparation of constitutionally unsymmetrical 1,2-dials (cross-coupling reaction between different carbonyl compounds). Diketo sulfides 1 are prepared from ketones as starting material. The net result of the present conversion, therefore, implies that stereospecific pinacolic reduction, not only between same carbonyl compounds but also between different carbonyl compounds, could be attained. In summary, the method developed here provides a novel selective synthesis of both erythro- and threo-1,2-diols, whose 12 preparation hitherto required pure E- or Z-olefins.
1802
References
and Notes
1.
Y. Miyahara,
J. HeterocycZ.
2.
J. Nakayama,
H. Motoyama,
&em., 16, 1147 (1979). IH. Machida, M. Shimomura, and M. Hoshino,
HeteroeycZes,
22, 1527 (1984). 3.
?a") J. Nakayama,
H. Machida,
R. Saito, and M. Hoshino,
H. Machida,
and M. Hoshino,
Tetrahedron
26, 1983 _-.
Lett.,
(1985). (b) J. Nakayama, 4.
E. Vedejs, Schwartz,
T. H. Everlein,
D. J. Mazur,
D. L. Varie,
J. S. Stults,
Tetrahedron
C. K. McClure,
R. G. Wilde,
Lett.,
2'6, 1981 (1985).
D. A. Perry, R. Ruggeri,
and S. Wittenberger,
E.
J. Org. them.,
51, 1556 (1986). 5.
7: Mukaiyama,
6.
CA-Configuration
T. Sato, and J. Hanna, &em. of 2a is also established
HO
OH __
7.
mp and 'H-NMR
'
m-CPBA
Ph---
---Ph
data (CDC13 as solvent)
3b: mp 136-137
S
of 1,2-diols
3a-k are as follows.
"C (lit., mp 134-135
2.24 (2H, s, OH),
"C); 'H-NMR 6 1.51 (6H, s, Me),
(BH, m, benzene
rings).
3c: mp 169-171
(8H, m, benzene
139 "C (lit., mp 138 "C);
rings).
3_d: viscous
oil; 'H-NMR 6 0.92
(6H, t, Me),
(12H, m, methylene), 2.0 (2H, broad s, OH). 3e: mp 138NW ’ H-NMR 6 0.60 (6H, t, Me), 1.2-2.6 (4H, double quartet,
2.12 (2H, s, OH), 7.21 (lOH, s, Ph).
0.96 (6H, t, Me), 1.14 (6H, s, Me), ca. 1.3-1.7 13C-NMR 6 7.8, 20.3, 28.0, 76.8.
3_f (=$):
mp 49.5-51
(4H, m, methylene),
39: mp 58-59 "C; 'H-NMR B 0.85
"C; 'H-NMR 6
2.06
(2H, s, OH);
(3H, d, Me), 0.92
(3H, d, Me), 1.07 (3H, s, Me), 1.66""(3H, s, Me), 1.79 (lH, broad s, OH), 1.5-2.1 m, methine),
2.52 (lH, broad s, OH), 7.1-7.6
52 "C); 'H-NMR 6 0.96 (4H, m, methylene), 76-76.5
“C
"C); 'H-NMR 6 1.53 (6H, s, Me), 2.24 (ZH, broad s, ;jH), 3.76 (6H, s,
1.16 (6H, s, Me), 1.1-1.9
methylene),
conversions.
h ti
2G3
2.15 (2H, s, OH), 2.29 (6H, s, Me), 6.9-7.3
OMe), 6.6-7.2
Ph
1) m-CPBA
"C (lit., mp 120 "C); 'H-NMR 6 1.56 (6H, s,-Me),
7:15 (lOH, s, Ph).
(lit., mp 168-169
chemical
82
(13C-NMR)
3a: mp 117.5-118.5
H
-;rp
2a
1041 (1973).
by the following
HO
---Ph
Ph--H
Lett.,
(5H, m, Ph).
(TH,
3i_: mp 51-52 "C (lit., mp
(6H, t, Me), 1.12 (3H, s, Me), 1.13 (3H, s, Me), ca. 1.2-1.9
1.83 (2H, broad s, OH); 13C-NMR
6 7.7, 19.8, 28.4, 76.8.
"C; 'H-NMR 6 0.80 (3H, t, Me), 1.19 (3H, s, Me), ca. 1.2-2.0
3_j;:.mp
(2H, m, methylene),
1.63 (3H, s, Me), 1.83 (lH, broad s, OH), 2.65 (lH, broad s, OH), 7.1-7.6
(5H, m, Ph).
3k: mp 94.5 "C; 'H-NMR 6 0;93 (3H, t, Me), 0.98 (3H, s, Me), 1.59 (3H, s, Me), ca. ..,_ l.l-1,9 (2H, m, methylene), 1.81 (lH, broad s, OH), 2.62 (lH, broad S, OH), 7.2-7.5 (5H, m, Ph). 8.
E. J. Corey, R. L. Danheiser,
9.
Selective
desulfurization
and S. Chandrasekaran,
of only thiolane
10.
Two isomers are formed from meso-sulfides
11.
More sterically furization.
12.
Pergamon
in "Comprehensive
Press, Oxford, in
Japan
41, 260 (1976).
and one isomer from d,l-sulfides.
2,5-diethyl-3,4-dihydroxy-3,4_diphenylthiolane
The desulfurization
S. G. Wilkinson
(Received
crowded
J. Org. Chem.,
ring could not be attained":
17
under forced conditions Organic
1979, p, 666. January
1987)
Chemistry,"
gave a complex
resisted
desul-
mixture.
Vol. 1, J. F. Stoddart
Ed.,