A new synthesis of cis-diol from alkene using iodine-ammonium cerium(IV) nitrate

Article abstract of DOI:10.1055/s-2005-916040

The reaction mixtures of 5α-cholest-2-ene with iodine-ammonium cerium(IV) nitrate [CAN(IV)] were converted with potassium hydroxide in methanol-water to give the more hindered 2β,3β-diol in high yield. Cyclohexene and cycloheptene similarly reacted to the corresponding cis-diols in good yield. It was found that this reaction intermediate proceeds to give trans-iodoacetate via trans-iodonitrate. This new synthetic method provided several advantages over the Prevost reaction. Georg Thieme Verlag Stuttgart.

Full text of DOI:10.1055/s-2005-916040

PAPER
2861
A New Synthesis of cis-Diol from Alkene Using Iodine-Ammonium
Cerium(IV) Nitrate
a
a
a
a
a
a
S
C
ynthesis of cis-D
.
iol from
A
lk
A
ene
U
sing Iodine
k
-Ammonium
i
C
erium
r
(IV)
N
i
a
trate Horiuchi,* Gong Dan, Masaki Sakamoto, Kazuhiko Suda, Shigeru Usui, Okihiko Sakamoto,
a
a
a
b
Shinya Kitoh, Satoshi Watanabe, Takamitsu Utsukihara, Sukekatsu Nozaki
a
Department of Chemistry, Rikkyo (St. Paul’s) University, Nishi-Ikebukuro, Toshima-Ku, Tokyo 171-8501, Japan
Fax +81(3)39852397; E-mail: horiuchi@rikkyo.ac.jp; E-mail: cahoriuchi@nifty.com
Faculty of Pharmaceutical Science, Josai University, Sakado, Saitama 350-0295, Japan
b
Received 15 November 2004; revised 22 January 2005
tion of a,b-unsaturated cyclohexenones with iodine–ceri-
Abstract: The reaction mixtures of 5a-cholest-2-ene with iodine–
ammonium cerium(IV) nitrate [CAN(IV)] were converted with po-
um(IV) ammonium nitrate (CAN) in alcohols.14
tassium hydroxide in methanol–water to give the more hindered In the present paper, we report that the reaction of 5a-
2
b,3b-diol in high yield. Cyclohexene and cycloheptene similarly
cholest-2-ene (1), cyclohexene (2), cycloheptene (3) and
-methyl-1-cyclohexene (4) with iodine–CAN is applica-
ble to the synthesis of the corresponding highly hindered
reacted to the corresponding cis-diols in good yield. It was found
that this reaction intermediate proceeds to give trans-iodoacetate
via trans-iodonitrate. This new synthetic method provided several
advantages over the Prevost reaction.
1
as well as usual cis-diols.
The reaction of cyclohexene (2), cycloheptene (3), and 1-
methyl-1-cyclohexene (4) with iodine and CAN(IV) or
CAN(III) in acetic acid yielded the corresponding cis-di-
ols. The results are summarized in Table 1.
Key words: iodine–ammonium cerium(IV) nitrate, cis-diols, trans-
iodoacetate, trans-iodonitrate
It is known that cis-hydroxylation of olefins is one of the
most useful methods using osmium-catalyzed reactions.1
However, this reaction can not be applied to the synthesis
of more hindered cis-diols.
From these results, it was concluded that the iodine added
is almost completely consumed, and two moles of olefins
are used for one mole of iodine and CAN. It is considered
that the reaction generates trans-iodonitrate and then
trans-iodoacetate by acetic acid. Next, trans-iodoacetate
forms the 1,3-dioxolan-2-ylium ion intermediate. By add-
ing water, the resulting orthoester undergoes ring opening
to the cis-diol monoacetate. It was found that this reaction
gives trans-iodonitrate as useful synthetic intermediates.
In addition, it is interesting that cyclohexane-1,2-diol
monoacetate is obtained preferentially by control of reac-
tion times.
Much work has been reported on the cis-hydroxylation of
olefins using the Prevost reaction and its Woodward mod-
2
ification. These reactions are important methods to ob-
3
tain vic-diols on the more hindered b-face of 5a-steroid.
4
Cambie et al. reported that the reaction of olefins with io-
dine–thallium(I) carboxylate gave the cis-hydroxy acetate
5
whereas Mangoni et al. described a convenient method
for the preparation of 5a-cholestane-2b,3b-diol using po-
6
tassium iodate. Also, Glotter and Schwartz reported that
In order to clarify the reaction pathway, the following ex-
periment was attempted. Trans-iodonitrate 5b reacted in
acetic acid–water (9:1) under reflux for five hours and
the reaction of 5a-cholest-2-ene with thallium(III) acetate
in acetic acid gave 5a-cholestane-2b,3b-diol diacetate and
7
2
a
3
-acetate. Moreover, Corey and Das described a new
trans-iodoacetate 5a, cis-diol monoacetate 5c, and cis-
diol diacetate 5d2a were obtained. Moreover, prolonged
reaction times gave the corresponding cis-diol monoace-
tate and cis-diol diacetate (Scheme 1).
method involving the reaction of trans-2-bromocyclohex-
anol with cyanoacetic acid.
We have been investigating a novel iodination method us-
8
ing iodine–copper(II) acetate in acetic acid. Some of the
In conclusion, the described method is simple and conve-
nient for the synthesis of cis-diols. It is particularly note-
worthy that this reaction may provide a new synthetic
method for highly hindered cis-diols, that is more conve-
nient than the methods available so far.
methods involve the synthesis of steroidal trans-iodo ace-
9
,10
tates and more hindered cis-diols like 2a,3a-diol of 5a-
steroid. However, these procedures suffer from draw-
backs such as the consumption of the produced iodide re-
leasing copper(I) iodide. In a previous paper, we
described a novel a-iodination of ketones in acetic acid or
Melting points were measured on a Yanako MP-500 melting point
apparatus and are uncorrected. IR spectra were recorded on a Jasco
1
1
methanol; a new alkoxyiodination and nitratoiodination
of olefins and 1,3-diene;12,13 and new oxidative aromatiza-
1
13
FT-IR 230 spectrometer. H and C NMR spectra were measured
on a JEOL GSX 400 spectrometer in CDCl with TMS as internal
3
standard. GC-MS (EI) analyses were performed on a Shimazu
GCMS-QP5050 with an ionizing energy of 70eV. CI-MS
(
isobutene reagent gas) were recorded on a Shimazu GCMS-
SYNTHESIS 2005, No. 17, pp 2861–2864
x
x.
x
x
.
2
0
0
5
Advanced online publication: 12.10.2005
DOI: 10.1055/s-2005-916040; Art ID: F16704SS
Georg Thieme Verlag Stuttgart · New York
QP5050 with an ionizing energy of 300eV.
©

2
862
C. A. Horiuchi et al.
PAPER
Table 1 Products and Isolated Yield in the cis-Hydroxylation of Olefin with Iodine–Cerium Salt
Entry
1
Substrate
Cerium Salta Time (h) Temp (°C) Product
Isolated Yield (%)
5b
875,6
C H
8
17
CAN(IV)
10
Reflux
C8H17
HO
HO
H
H
1
1
2
3
CAN(III)
CAN(IV)
10
Reflux
C H
5a
5b
709
8
17
AcO
I
H
1
2.5
50
8
C H
88
17
O2NO
I
H
4
5
6
1
1
CAN(III)
CAS(IV)
CAN(IV)
18
10
10
Reflux
Reflux
Reflux
5b
826
56
5b
524c
OH
OH
2
2
6b
7
8
CAN(IV)
CAN(IV)
2.5
50
I
I
Quant. (1:1)
Quant.4c
OAc
ONO2
6
a
6b
2
5
Reflux
OAc
OH
OH
7
OH
c
9
CAN(IV)
CAN(IV)
10
Reflux
8015
3
3
8b
I
1
0
2.5
50
I
Quant. (1:1)
OAc
ONO2
8
Me
a
8b
1
1
2
Me
CAN(IV)
CAN(IV)
10
Reflux
Reflux
354a
OH
OH
4
4
9b
Me
1
16.5
754a
OH
OAc
1
0c
a
CAN(IV): (NH ) Ce(NO ) ; CAN(III): (NH ) Ce(NO ) ; CAS(IV): (NH ) Ce(SO ) .
4
2
3 6
4 2
3 5
4 2
4 3
Substrate (1 mol equiv), iodine (0.5 mol equiv), Ce salt (0.5 mol equiv), and AcOH–H O (9:1) were employed.
2
b
Reaction mixtures were hydrolyzed.
Synthesis 2005, No. 17, 2861–2864 © Thieme Stuttgart · New York

PAPER
Synthesis of cis-Diol from Alkene Using Iodine-Ammonium Cerium(IV) Nitrate
2863
CH3
CH3 C8H17
CH3
CH3 C8H17
CH3
CH3 C H17k
8
ONO2
ONO –
I+
2
H
H
I+
H
1
H
I
5b
H
CH3COOH
H3C
CH3
CH3 C8H17
H2O
CH3
CH3 C H
H3C
CH3
CH3 C H
8 17
8
17
OAc
C
O
O
+
C
O
O
H
I
H
H
HO
H
H
H
H
+
5c
H
H
5a
CH3
OH
CH3
CH3 C8H17
OH
H
KOH
MeOH–H2O
AcO
H
HO
H
5c'
H
+
H
H
5
OAc
CH3
H
AcO
H
5d
H
Scheme 1
1
3
Synthesis of cis-Diols: 5a-Cholestane-2b,3b-diol (5, Entry 1);
Typical Procedure
C NMR (100 Mz, CDCl ): d = 12.09 (CH ), 14.41 (CH ), 18.66
3 2 3 3 2
3
3
3
(CH ), 20.83 (CH ), 22.56 (CH ), 22.82 (CH ), 23.86(CH ), 24.10
A mixture of 5a-cholest-2-ene (1) (500 mg, 1.349 mmol), I (171
(CH ), 27.14 (CH), 27.33 (CH ), 28.01 (CH), 28.19 (CH ), 31.58
2 2 2
2
mg, 0.675 mmol), CAN (370 mg, 0.675 mmol), and AcOH–H O
(CH ), 33.61 (CH ), 34.98 (CH), 35.59 (CH ), 35.78 (CH), 35.83
2
2
2
2
(9:1, 50 mL) was stirred under reflux for 10 h. After cooling, the re-
(CH ), 36.16 (CH ), 39.50 (CH ), 39.81 (CH ), 41.70 (CH), 42.58
2 2 2 2
action mixture was concentrated under reduced pressures, poured
(C), 54.54 (CH), 56.27 (CH), 74.80 (C), 83.85 (CH).
into water, and extracted with Et O (50 mL). The ethereal solution
2
HRMS: m/z calcd for C H INO : 559.2525; found: 559.2516.
2
7
46
3
was washed with a sat. solution of NaHCO , dried (Na SO ), and
3
2
4
filtered. Subsequently the solvent was removed. The reaction mix-
Cis-1,2-cyclohexanediol (6)
Needles. Mp 95–97 °C (Lit. 97–98 °C).
tures 5c, 5c′, 5d in MeOH (50 mL) were treated with KOH (50 mg)
4c
in H O (2.5 mL) under reflux for 0.5 h. Afterwards the reaction mix-
2
–
1
IR (KBr): 3400, 3275, 1080 cm .
tures were poured into water, and extracted with Et O (50 mL). The
2
ethereal solution was washed with water, dried, and evaporated.
Crystallization of the residue from MeOH gave plates of 5a-choles-
tane-2b,3b-diol (5, 491 mg).
(
2S)-2-Iodocyclohexyl Nitrate (6b)
Yellow oil.
–
1
6
IR (NaCl): 1636, 1280 cm .
Mp 174–177 °C (Lit. 175–176 °C).
1
–
1
H NMR (400 MHz, CDCl ): d = 1.45–1.70 (m, 4 H), 1.84 (m, 1 H),
3
IR (KBr): 3400, 1050 cm .
2
.05 (m, 1 H), 2.27 (m, 1 H), 2.41 (m, 1 H), 4.13 (sext, J = 8.8, 4.0
Hz, 1 H), 5.10 (sext, J = 8.8, 4.0 Hz, 1 H).
Reaction of trans-Iodoacetate 5b in AcOH–H O (9:1)
2
A mixture of 3a-iodo-2b-nitrato-5a-cholestane (5b, 200 mg) and
13
C NMR (100 MHz, CDCl ): d = 22.99 (CH ), 25.82 (CH ), 26.33
3
2
2
AcOH–H O (9:1, 20 mL) was stirred under reflux for 5 h. After
2
(CH), 29.42 (CH ), 36.90 (CH ), 84.94 (CH).
2 2
evaporation of the solvent the residue was dissolved in Et O (50
2
HRMS: m/z calcd for C H INO : 270.9706; found: 270.9637.
6
10
3
mL), neutralized with a solution of NaHCO (3 × 5 mL). Subse-
3
quently the ethereal solution was removed under reduced pressure.
Cis-1,2-cyclohexanediol monoacetate (7c)4c
Yellow oil.
The resulting oil was purified by column chromatography on silica
9
gel (n-hexane–Et O (4:1, 250 mL) to give trans-iodoacetate 5a (25
2
2
a
–1
mg), cis-diol monoacetates 5c , 5c′ (140 mg), and cis-diol diacetate
IR (NaCl): 3450, 1730, 1200 cm .
2
a
1
5
d
(10 mg).
HNMR (400 MHz, CDCl ): d = 2.09 (s, 3 H), 3.88 (br s, 1 H), 4.0–
3
4
.1 (m, 1 H), 4.85–4.95 (m, 1 H).
3
a-Iodo-2b-nitrato-5a-cholestane (5b)
13
CNMR (100 MHz, CDCl ): d = 21.22 (CH ), 23.57 (CH ), 27.06
2 2 2
3
3
2
Needles; mp 131–132 °C.
(
CH ), 31.59 (CH ), 31.77 (CH), 37.86 (CH ), 76.68 (CH), 169.88
–
1
IR (KBr): 1630, 1288 cm .
(CO).
1
H NMR (400 MHz, CDCl ): d = 4.65 (m, J = 9.6 Hz, 1 H), 5.36 (m,
HRMS: m/z calcd for C H O : 158.0943; found: 168.0985.
3
8
14
3
J = 9.6 Hz, 1 H).
Synthesis 2005, No. 17, 2861–2864 © Thieme Stuttgart · New York

2
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C. A. Horiuchi et al.
PAPER
1
5
Cis-1,2-cycloheptanediol (8)
References
1
5
Needles. Mp 45–46 °C (Lit. 45 °C).
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6
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2S)-2-Iodocycloheptyl Acetate (8a)
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Yellow oil.
–
1
IR (NaCl): 1728, 1246 cm .
1
H NMR (400 MHz, CDCl ): d = 1.40–1.80 (m, 7 H), 1.89 (m, 1 H),
3
2
.15 (m, 1 H), 2.06 (s, 3 H), 2.30 (m, 1 H), 4.27 (sept, J = 8.1, 4.0
Hz, 1 H), 5.12 (sept, J = 8.0, 4.0, 1 H).
1
(
3
C NMR (100 MHz, CDCl ): d = 21.22 (CH ), 21.82 (CH ), 26.53
2 2 2 2
3
3
2
(
(
CH ), 27.18 (CH ), 31.23 (CH), 35.77 (CH ), 36.48 (CH ), 81.09
CH), 169.79 (CO).
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P. S.; Woodgate, P. D. J. Chem. Soc. 1974, 1858.
HRMS: m/z calcd for C H IO : 282.0118; found: 282.0120.
9
15
2
(
b) Cambie, R. C.; Gash, D. M.; Rutledge, P. S.; Woodgate,
P. D. J. Chem. Soc. 1977, 1157. (c) Cambie, R. C.;
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1976, 1660.
(
2S)-2-Iodocycloheptyl Nitrate (8b)
Yellow oil.
(
–
1
IR (NaCl): 1636, 1280 cm .
1
H NMR (400 MHz, CDCl ): d = 1.50–1.80 (m, 6 H), 1.85 (m, 1 H),
3
2
.05 (m, 1 H), 2.20 (m, 1 H), 2.26 (m, 1 H), 4.32 (sept, J = 8.0, 3.4
Hz, 1 H), 5.35 (sept, J = 8.0, 3.4 Hz, 1 H).
1
(7) Corey, E. J.; Das, J. Tetrahedron Lett. 1982, 23, 4217.
(
8) (a) Horiuchi, C. A.; Satoh, J. Y. Synthesis 1981, 312.
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2, 2919. (c) Horiuchi, C. A.; Satoh, J. Y. J. Chem. Soc.,
3
C NMR (100 MHz, CDCl ): d = 22.03 (CH ), 26.60 (CH ), 27.53
3
2
2
(
6
(
CH), 30.02 (CH ), 30.14 (CH ), 36.43 (CH ), 90.33 (CH).
2 2 2
HRMS: m/z calcd for C H INO : 284.9863; found: 284.9882.
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62, 2919.
7
12
3
1
-Methylcyclohexane-cis-1,2-diol (9)4a
Yellow oil.
IR (NaCl): 3500, 1050 cm .
–
1
1
-Methylcyclohexane-cis-1,2-diol 2-Acetate (10c)4a
Yellow oil.
–
1
IR (NaCl): 3504, 1738, 1250 cm .
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(11) (a) Horiuchi, C. A.; Kiji, S. Chem. Lett. 1988, 31.
1
H NMR (400 MHz, CDCl ): d = 1.18 (s, 3 H), 1.20–1.48 (m, 4 H),
3
1
.50–1.90 (m, 4 H), 2.10 (s, 3 H), 2.55 (br s, 1 H), 4.60–4.70 (m, 1
H).
1
(
4
b) Horiuchi, C. A.; Kiji, S. Bull. Chem. Soc. Jpn. 1997, 70,
21.
3
C NMR (100 MHz, CDCl ): d = 21.05 (CH ), 22.53 (CH ), 25.83
2 3 2 2
3
3
2
(
(
CH ), 27.09 (CH ), 28.33 (CH ), 37.47 (CH ), 70.70 (C), 77.81
(
12) (a) Horiuchi, C. A.; Nishio, Y.; Gong, D.; Fujisaki, T.; Kiji,
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CH), 170.57 (CO).
HRMS (CI-MS): m/z calcd for C H O : 172.1088; found:
1
9
16
3
72.1088.
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(
(
1957, 79, 6287.
Synthesis 2005, No. 17, 2861–2864 © Thieme Stuttgart · New York