SYNTHESIS OF CHIRAL AMINOCYCLITOLS VIA EPOXYEPIMINATION

Article abstract of DOI:10.1016/0957-4166(90)90041-8

Asymmetric Hetero-Diels-Alder reactions of cyclohexadienes 1 and (+/-)2 with the α-chloronitroso derivative of D-mannose 6 give the chiral dihydrooxazines 3-5.After N-functionalisation with the chloro-olefin 10 the N-vinyl-dihydrooxazines 11-13 thermally

Full text of DOI:10.1016/0957-4166(90)90041-8

Tetrahedron:
Vol. 1. No. 6, pp. 403415.1990
in Great Britain
Press plc
SYNTHESIS OF CAIRAL AMINOCYCLITOLS VIA
H. Braun,
Burger, G.
F. P. Schmidtchen*
Organisch Chemisches Institut, TU Miinchen
8046
FRG
J.
L. Vaerman,
H. G.
Lab. de Chimie Organique,
la Neuve, Belgique
Catholique de
(Received23
Abstract:
Asymmetric Hetero-Diels-Alder reactions of cyclohexadienes 1 and
with the a-chloronitroso derivative of D-mannose
give the chiral
dihydrooxazines
After N-functionalisation with the chloro-olefin 10
the N-vinyl-dihydrooxazines
The formation of
thermally rearrange to epoxyepimines
byproducts 18 and
indicates a
and acidic
cal mechanism.
Opening of oxirane and aziridine rings of
hydrolysis lead to chiral aminocyclitols.
Aminocyclitols form the aglycon part of numerous aminoglycoside
gentamycin and fortimycin. Although several
antibiotics e.g. streptomycin,
the access to
In this
routes to aminocyclitols were described in the past
chiral aminocyclitols remains limited to only a few examples
report a general enantiospecific total synthesis of
paper we
tols starting from chiral a-chloronitroso compounds and using the
This approach is advantageous
Diels-Alder and epoxyepimination reactions.
as it starts from easily obtainable materials and does not require tedious
separations of diastereomers or enantiomers.
From previous work on the Hetero-Diels-Alder reaction we had at our dispo-
and
in high chemical and optical yield by cycloaddition of the
and with the a-chloronitroso derivative of D-mannose
The corresponding enantiomeric dihydrooxazines can be obtained
using the a-chloronitroso derivative of D-ribose instead of
These are available
sal the chiral dihydrooxazines
dienes
For the conversion of dihydrooxazines to aminocyclitols the cleavage of
the N-O bond and the subsequent functionalization of the carbon-carbon
A reaction that allows to achieve both goals in
one step is the rearrangement of dihydrooxazines to epoxyepimines
The rearrangement is stereospecific with regard to the aziridine-
double bond is required.
deceased on September
1987
403

et al.
404
0
a
OCCH,
4
0
6
4
‘ C N
10
OCCH,
0
11
12
13
0
0
0
0
1 4
15
1 6

aminocyclitols
and oxirane rings being cis to each other.
However,
stituent
this reaction is strongly dependent on the nature of the
The chlorovinyl derivative that is formed by
fin addition to cyclohexadienes has been described earlier
whereas
captodative vinyl substituents (e.g. in
cently.
or
have been reported re-
In order to prepare derivative
zines and were allowed to react with the captodative chloro-olefin
In all three cases the N-functionalized dihydrooxazines 11-13 were ob-
the stereoisomeric bicyclic
tained in good to excellent yields as mixtures of
isomers. The isomers
the E-isomer exhibiting always the
the N-substituted dihydrooxazines 11-13
can easily be distinguished by the
coupling constants of the
proton to the
group
larger values.
Upon heating in toluene at
isomerised within 24 hours to the corresponding epoxyepimines
in
about 80% yield. In no case diastereomeric products could be detected.
From the reaction of the dihydrooxazines 11 and 12 the konduramine
tives
and
were isolated in minor yields together with a mixture of
The occurance of these bypro-
dimerisation products of the benzyl radical.
ducts supports the proposed biradical mechanism. The biradicals (e.g.
can react either intramolecularly to epoxyepimines 14-16 or abstract
hydrogen from the toluene solvent to give the konduramines
conversion of the epoxyepimines to aminocyclitols was carried out
starting from
opening was achieved by treating
room temperature. After acetylation the reaction yielded the oxirane
as the sole product. The configurational pattern of follows from the
magnitude of the coupling constants 1.6 Hz and = 9.6 Hz,
which prove the cis-relationship of the H-3 and H-4 protons and the trans
configuration of the H-4 and H-5 protons Thus, in this case again the
usually observed trans opening of aziridines is found
as an example.
and regioselective aziridine ring
with 2.5% aqueous acid at
Under forcing conditions (20% aqueous
the opening of the oxirane as
well as the aziridine rings of 14 took place simultaneously with
giving the inosamine hexa-acetate
after acetylation in 80%
hydrolysis,
The
of was confirmed by the respective
yield.
coupling constants.

406
et al.
NH
0
p r o d u c t s
1 7
1 8
1 9
1
4
R’O
0
2
0
21
2
4
=
,
0
S
’
“
‘ O C C H ,
0
2
2
3
2 2
=
=
5

407
aminocyclitols
For introduction of a second nitrogen function into the aminocyclitol
system the oxirane was treated with aqueous ammonia. Subsequent
acetylation afforded the expected product in 74% yield with the same
pattern on the cyclohexane ring as in
Acidic
hydrolysis and acetylation of
hexaacetate
the inosdiamine
the
gave
The desired target compounds
and
were readily obtained as
by
refluxing
the
hexaacetates
and
in
In conclusion we have found that the epoxyepimination of
Alder is a valuable access route to aminocyclitols.
Experimental part:
19.0
was suspended in 40 ml
and 3.85
Dihydrooxazine
g (38
3.34 g (19.0
stirred at room temp. under nitrogen until
action ethylacetate ca. 24
(5.0 g,
triethylamine was added resulting in a clear solution. Then
in 10 ml was added dropwise. The mixture was
indicated a complete re-
The mixture was extracted
several times with water, the organic phase was dried over
filtered
and evaporated. After chromatography (silica, n-hexane/ ethylacetate
an oily product was obtained consisting of the
isomers
The E-isomer was obtained in pure
hexane.
form by crystallization from ether/
(E-isomer): Yield: 5.71 g
crystals, m.p.
=
1380, 1250.
H-5, H-6);
2.05, 2.04
=
=
0.5,
MHz,
H-7); 5.33
2 x 1.32
3.5 Hz:
1 Hz.
two signals): 154.1 (C-l'); 130.6, 130.2 (C-5, C-6); 119.8
3050, 2980, 2200, 1745, 1600,
6 = 6.79
H-8); 5.03
H-4');
H-l'); 6.69-6.54
H-l); 4.53
H-4);
=
= 5.7 Hz;
= 1.7 Hz;
= 8 Hz;
= 7.8 Hz:
= 1.8 Hz;
MHz,
6 = 169.3
x c=o
75.2,
70.9, 66.8, 66.3 (C-l, C-7, C-8, C-2'): 56.4 (C-4); 47.2 (C-3'); 30.2
20.3, 20.2
31C
x
ester);
43
= 11.0 Hz.
366
94

408
(366.4)
C
C
55.72
55.39
H
6.05
6.03
7.64
7.66
found.
H
(360 MHz,
7.04
H-l'); 6.67-6.50
H-l);
(Z-isomer):
H-5, H-6); 5.61
2.02, 2.01
6 = 169.1, 169.0
H-4); 5.21-5.14
H-7, H-8); 4.76
2 x
H-4').
MHz,
x
153.7
130.1 (C-5, C-6); 121.5
73.3, 69.6, 66.3, 65.3 (C-l, C-7, C-8, C-2'); 54.2 (C-4); 49.7
20.0, 19.8 ester); = 5.9 Hz.
x
29.7 (C-4');
12
was suspended in 50 ml
Compound
(50 mmol) triethylamine was added and a clear solution was obtained. Sub-
sequent to the addition of 24.3 in 10 ml the mix-
ture was refluxed under nitrogen until
tion ethyl acetate ca.
were carried out as described with
(6.4 g, 24.3
Then 5.06
indicated a complete reac-
Work up and chromatography
The compound
The E-isomer could be crystallized from ether/
isomers.
was obtained as a
mixture of
hexane.
(E-isomer): Yield: 5.17 g (58%)
crystals, m.p.
= -19
= 0.5,
IR
3080, 3060, 2990, 2975, 2200,
1595, 1570, 1230, 1115, 980,
(360 MHz,
H-7); 5.02
6
6.75
H-l'); 6.64-6.59
H-8); 4.53
915, 740, 710.
H-5, H-6); 5.11
H-l); 4.66
H-4');
2.06
2 x
1.32
= 4.2 Hz;
2.17,
5.3 Hz;
= 2.9 Hz;
= 1.7 Hz;
1 Hz;
153.9 (C-1'); 130.3,
73.5, 72.9, 71.3, 70.3 (C-l, C-7, C-8,
ester);
57
= 1.1 Hz.
(90 MHz,
129.7 (C-5, c-6); 120.1
59.1 (C-4);
6 = 170.3, 169.3
X
47.1 (C-3'); 30.2 (C-4'); 20.8, 20.6
x
MS
m/z(%): 366
5.9); 310
94
= 11.4 Hz.
43
(366.4)
C 55.72
6.05 N 7.64
6.08 N 7.46
found.
C 55.88

Chiral
409
(Z-isomer):
H-5, H-6); 5.54
2.15, 2.04
MHz,
H-4); 4.90
6 = 7.05
H-7); 4.74
H-l'); 6.52-6.38
H-l); 4.51
2 x
x
1.28
H-4').
MHz,
6 = 169.4, 168.8
153.5 (C-1'); 130.5, 129.7 (C-5, C-6);
121.8
72.1, 70.8, 70.1, 69.7 (C-l, C-7, C-8, C-2'); 57.0 (C-4); 48.8
30.1
20.2, 20.1
x
ester);
= 5.6 Hz.
(C-3');
800 mg
of a
mixture of
and
were suspended in 10 ml
and 300 mg (3
triethylamine was added,
whereby a clear solu-
tion was obtained. Then 260 mg (1.5
in 2 ml
was added
indicated
and the mixture was stirred under nitrogen until
a complete reaction
ethylacetate
24
Work up and chro-
matography were carried out as described with
was
obtained as a mixture of E,Z isomers.
Yield:
430 mg (79%)
H-l');
colourless oil. 'H-NMR
MHz,
6 = 7.16, 6.81
H-4); 5.01, 4.62
1.43, 1.42
6.50
H-8); 2.19, 2.17, 2.08, 2.07
NMR MHz,
(C-l'); 130.5, 129.7, 129.6, 129.3 (C-5, C-6); 121.7, 119.8
74.0, 73.9, '73.8, 69.8, 69.0 (C-l, C-7, C-8, C-2'); 56.0, 54.0 (C-4);
H-5, H-6); 5.88, 4.48
H-l, H-7.
H-4').
169.9 (two signals), 169.2,
153.6
74.1,
49.9, 49.7 (C-3'); 30.4, 29.8 (C-4'): 20.6, 20.5, 20.4, 20.3
ester).
General procedure for the rearrangement of 11-13 to epoxyepimines:
A 0.1 m solution of
nitrogen for 24 h. In each case
three large spots
the products were separated by column chromatography. The
of the first fraction = 0.9) were identical in all cases:
7.0-7.6
or
was stirred at
in dry toluene under
showed
= 0.90, 0.20, 0.08). The toluene was evaporated and
1.0-1.7
The
analysis of this first
Second fraction = 0.20)
MHz,
fraction showed four products with m/z = 182.
Reaction of
(4.80 g, 13.1
IR (film): 2990, 2205, 1755, 1530,
colourless oil.
Yield: 3.85
1440, 1380, 1240, 1055.

410
(100).
310 (6); 43
366
5.8);
MS
m/z(%):
H
H
6.05
6.18
N 7.64
N 7.32
55.72
found.
c 55.77
(E-isomer)
(360 MHz,
3.68 (dd, H-21: 3.31
1.32
= 3.2 Hz;
117.4
52.0, 47.7, 47.2 (C-2, C-4, C-3'); 38.7, 37.7
7.20
H-4); 3.10
H-4');
= 6.2 Hz.
87.7 (C-2'); 67.7, 67.4 (C-5,
H-l'); 5.41
H-l); 2.60
= 2.9 Hz;
H-5); 5.05
H-6);
H-7); 2.10, 2.08
= 3.6 Hz;
2
=
MHz,
6
= 169.7
20.6
162.5
C-7); 30.3 (C-4');
ester);
= 11.2 Hz.
(Z-isomer)
(360 MHz,
3.65 (dd, H-2); 3.26
6 = 7.39
H-4); 3.03
H-4').
C-l'); 5.27
H-l); 2.60
H-5); 5.24
H-6);
H-7); 2.09, 2.02
6 = 169.7
2
1.42
MHz,
159.7 (C-1'); 119.8
51.0, 47.6 (C-2, C-4, C-3');
90.3 (C-2'); 67.9, 67.4 (C-5, C-6); 51.6,
40.7, 37.9 (C-l, C-7); 31.0 (C-4'); 20.8
ester);
5.8 Hz.
The third fraction was
from
diacetoxy-4-hydroxycyclohex-5-ene
crystals, m.p.
3360, 2980, 2195, 1745, 1625, 1380, 1250, 1055.
6 = 7.37 H-l'); 5.97 H-5); 5.89 NH);
H-3); 5.14 H-2); 4.31 H-4); 4.10
2.11, 2.07 1.35 H-4');
2.4 Hz; 10.0 Hz;
= 5.5 H = 1.9 Hz.
MHz, 155.3 (C-1'); 130.1,
127.8 (C-5, C-6); 122.4 72.0, 72.9, 68.8 (C-2, C-3, C-2'); 66.6
55.2 (C-l); 49.4 (C-3'); 30.6 (C-4'); 20.9, 20.8
=
Yield: 230 mg
0.5,
IR
(360 MHz,
H-6); 5.17
OH);
5.72
2 x
H-l); 2.81
7.2 Hz;
=
=
= 4.0 Hz:
=
2.5 Hz;
Z
;
= 9.0 Hz;
6 = 170.4, 170.2
= 0.5 Hz;
x
ester);
192
= 4.8 Hz. MS
m/z(%): 368
312
43
(368.5).
55.41
6.57 N 7.60
6.64 N 7.42
found.
C 55.08

aminocyclitols
411
Reaction of
(4.00 g, 10.9
second fraction
= 0.2):
The E-isomer was obtained in pure form by crystallization from
hexane:
(E-isomer); Yield: 3.09 g
= -10
3060, 2980, 2205, 1745, 1575, 1420, 1385, 1375, 1245, 1230.
'H-NMR (360 MHz, 6 = 7.10 H-l'); 5.18 H-6); 5.05
3.54 H-2); 3.10 H-7); 3.06 H-4); 2.98 H-l); 2.14,
2 x H-4'); = 3.5 Hz; = 3.9 Hz;
= 2.5 Hz; = 6.2 Hz.
162.0 (C-1'); 116.9
colourless crystals, m.p.
= 0.5,
IR
2.12
(90 MHz,
= 1.5 Hz;
=
9.2 Hz;
171.0, 169.6
x
88.6 (C-2'); 69.4, 69.3 (C-5, C-6); 53.2, 48.0, 47.3 (C-2, C-4, C-3');
37.5 (C-l, C-7); 30.6 (C-4'); 20.9, 20.7
ester);
=
41.7,
11.7 Hz.
MS
m/z(%): 366
(366.4).
310
57
43
C 55.72 H 6.05 N 7.64
C 55.42
found.
H 6.18 N 7.65.
'H-NMR (360 MHz,
H-5); 3.53 H-2);
H-l); 2.10, 2.09
170.3, 169.3
7.30
H-l'); 5.15
(Z-isomer):
5.02
H-4, H-7); 2.90
2 x
x
1.46
H-4').
MHz,
91.0 (C-2');
160.1 (C-1'); 119.7
70.7, 70.5 (C-5, C-6); 53.0, 49.6, 47.9 (C-2, C-4, C-3'); 40.7, 39.6 (C-l,
30.8 (C-4'); 20.8, 20.6
ester);
= 4.9 Hz.
C-7);
0.08) was crystallized from
The third fraction
diacetoxy-4-hydroxycyclohex-5-ene
Yield:
140 mg
colourless
crystals.
IR
=
= 0.5,
3420, 3340, 2980, 2200, 1740, 1620, 1230, 1040, 770
6 = 7.19 H-l'); 5.98 H-5); 5.78
H-2, H-3); 4.30 H-l); 2.81
Hz;
(360 MHz,
H-6, NH); 5.02
H-4); 4.25
H-4'):
2.14, 2.12
= 5.2 Hz:
2 x
1.39
=
OH):
= 2.6 Hz:
= 10.2 Hz;
= 5.0 Hz;
=
5.7 Hz;
= 13.3 Hz;
171.1, 169.9
72.6, 70.5, 69.8, 69.0 (C-2, C-3, C-4, C-2'); 54.0
= 1.9;
= 1.0 Hz.
MHz,
x
155.2 (C-l'); 133.4, 123.6 (C-5, C-6);
49.7
122.3
30.7 (C-4'); 20.8, 20.7
7.8); 312
ester);
57
= 4.6 Hz. MS
(C-3');
m/z(%): 368
192
43

(368.5)
55.41 H 6.57 N 7.60
55.29 H 6.57 N 7.63
(350 mg,
found.
Reaction of
C
Second fraction
= 0.2):
260
Yield:
mg
oil; IR (film): 2995,
m/z(%): 366
2200, 1745, 1575,
1435, 1375,
1235, 1050, 900. MS
4.8); 310
43
(368.5)
C
55.72
55.54
6.05 N 7.64
6.10 N 7.36
found.
(E-isomer)
(360 MHz,
3.77 (dd, H-21; 3.36
7.25
H-l'); 5.39
H-5); 4.88
H-4); 3.06
H-l); 2.43
H-7); 2.10.
not distinguishable from the Z-isomer); 1.34
H-4',
2.09
2 x
= 2.8 Hz;
= 6.2 Hz.
= 4.0 Hz;
(90 MHz,
1 Hz;
= 9.8 Hz;
=
x
2.5 Hz;
170.5, 170.0
160.0 (C-l'); 120.0
49.2, 48.9 (C-2, C-4, C-3'); 40.8, 39.6 (C-l, C-7); 31.0 (C-4'); 20.8
= 11.2 Hz.
87.6 (C-2'); 70.8, 69.7 (C-5, C-6); 54.9,
ester);
(Z-isomer)
'H-NMR (360 MHz,
6 = 7.47
H-l'); 5.39
H-l); 2.37
H-5); 4.90
H-7); 2.10,
3.72 (dd, H-2); 3.36
H-4); 2.99
not distinguishable from the E-isomer); 1.43
2.09
4').
2 x
MHz,
170.5, 170.1
x
162.5 (C-1');
70.6, 69.4 (C-5, C-6); 55.0, 50.5, 47.3 (C-2,
120.0
87.6 (C-2');
4, C-3'); 40.2, 38.4 (C-l, C-7); 30.3 (C-4'); 20.8
= 5.0 Hz.
ester);
1.0 g (2.7 mmol)
was dissolved in 10 ml
3 ml of 2.5%
was
indica-
added and the mixture was stirred at room temperature until
ted a complete reaction
ca. 30
The mixture
was neutralized with sodium carbonate.
the residue was acetylated with 10 ml
The solvents were evaporated and
After
evaporation i.
the residue was extracted with
filtered and evaporated.
The organic
phase was dried over
Crude
was purified
and crystal-
by column chromatography (silica, n-hexane/ethylacetate
lized from ether/n-hexane.

413
Yield:
0.5,
IR
colourless crystals,
=
0.91 g
= -165
3335, 2990, 2195, 1760, 1630, 1380, 1250, 1230, 1045.
NH]; 5.42
H-5); 3.49 H-6); 3.27
(360 MHz,
7.37
H-l'); 5.89
5.16
H-l);
H-2); 4.82
2.17, 2.09, 2.04
= 3.8 Hz:
= 1.9 Hz.
155.2 (C-l'); 122.0
55.1 (C-l, C-6, C-3'); 49.4 (C-5); 30.6 (C-4');
H-4); 3.99
3 x
1.35
H-4');
1
Hz;
= 1.6 Hz:
= 9.6 Hz:
= 2.1 Hz;
= 3.6 Hz:
x
MHz,
6 = 169.6, 169.5, 169.0
70.0, 68.8, 68.5, 66.4 (C-2, C-3,
C-2'); 55.7,
55.3,
20.4 (3 x
328
ester);
43
= 4.7 Hz. MS
m/z(%): 426
20.7, 20.6,
370
0.65 g (1.8 mmol)
was dissolved in 10 ml
Then 3 ml of 20%
for 7d.
crystallization
as colourless crystals m-p.
was added and the mixture was stirred at room temp.
Work up and
acetylation as
=
with
from
described
followed by
yielded 560 mg (73%)
0.5,
2980, 1755, 1665, 1550, 1380, 1230.
H-3, NH); 5.33 H-l); 5.24
4.90 (ddd, H-5); 2.19, 2.17, 2.16, 2.06, 2.00, 1.95
MHz,
IR
3410, 3300,
6
5.58
H-4); 5.22
H-6); 5.16
6 x
3.0
170.1, 169.9, 169.5, 169.2, 169.0
(c-l, C-2, C-3, C-4, C-6); 46.0 (C-5); 23.2, 20.8, 20.8, 20.7, 20.5
H-2);
=
=
3.4 Hz:
=
3.2
H
Z
;
=
11.2
Hz;
=
Hz;
= 3.5 Hz.
(90 MHz,
171.1,
x
70.2, 68.6, 67.6, 67.2, 66.1
x
MS
m/z(%): 432
(431.4)
C 50.12
C 50.03 H 5.64 N 3.24
0.7); 209
183
43
H 5.84 N 3.25
found.
340 mg (0.8
was dissolved in 10 ml
The solution
was saturated with ammonia and stirred for 5d at room temperature.
mixture was evaporated and the residue was acetylated ml
30 The excess of was removed in
was purified by column chromatography (silica, ethylacetate) and crystal-
lized from /n-hexane.
The
Crude

414
colourless crystals,
= -51
Yield: 310 mg
0.5,
(film): 3320, 2970, 2195, 1750, 1670, 1620, 1370, 1220, 1045.
7.35
5.71 (br, H-2); 5.36
(ddd, H-4); 3.94
ester, amide); 1.37
H-l'); 6.35
H-5); 5.30
5.80
(360 MHz,
H-3); 5.22
H-1); 4.64
5 x
H-6); 2.30, 2.26, 2.12, 2.09
H-4');
= 3.4 Hz;
168.7
= 3.1 Hz;
= 3.2 H
MHz,
71.5, 70.5, 69.4,
Z
;
=
=
= 10.8 Hz.
3.9 Hz;
6 = 169.6,
155.6 (C-l'); 122.4
68.2, 64.5 (C-l, C-2, C-3, C-5, C-2'); 53.6 (C-3'); 49.4, 49.1 (C-4, C-6);
30.6 (C-4'); 23.3, 20.8, 20.5
ester, amide).
471 (3.2); 43
MS
m/z(%): 527
(527.6)
C 52.36 H 6.30 N 7.96
C 52.02 H 6.24 N 7.85
found.
To 200 mg (0.4
dissolved in 5 ml
3 ml of 20%
were
added and the solution was stirred for 6d at room temp.. Work up and
carried out as described with
tylation were
Crystallization from
yielded 130 mg
= 0.5,
as colourless crystals, m.p.
= -20
3280, 2980, 1745, 1660, 1540, 1370, 1230, 1050.
IR (film):
MHz,
5.10
327
6.55, 6.45
2 x NH); 5.56
4.53 (H-5
5.17
(H-2, H-3, H-4, H-6);
= 10.0 Hz;
317
70.4, 69.5, 69.5, 67.3 (C-2, C-3, C-4, C-6); 49.4, 46.8 (C-l, C-5);
23.1, 22.9, 21.1, 21.0, 20.9, 20.8 MS m/z(%): 431
=
= 4.9 Hz.
171.0, 170.9, 170.8, 170.6, 170.5
MHz,
x
208
43
0.5);
(430.4)
C 50.23 H 6.09 N 6.51
H 6.21 N 5.96
found.
c 50.04
General procedure for the deacylation of
and
was passed through 20 ml
and the mixture was refluxed for 48-72 h. The
the residue was dissolved in and the product
was precipitated by the addition of ether.
Reaction of
A stream of gaseous
tion was added to
This solu-
or
solvent was evaporated,
mg, 2.8
yielded

415
aminocyclitols
(360 MHz,
6
= 3.99
H-6): 3.94
H-5);
3.5 Hz.
H-2); 3.82
MHz,
H-l);
3.73 (m,
H-3, H-4); 3.43
3.2 H
Z
;
6
= 3.0 Hz;
10.1 Hz;
= 74.6, 74.2, 69.7, 67.9,
66.7 (C-l,
C-2, C-3, C-4, C-6); 51.0 (C-5).
Reaction of
mg, 2.1
yielded
(40 mg, 77%) as
inositole-dihydrochloride
solid,
=
(360 MHz,
= 0.5,
6
= 4.29
4.05
3.86
MHz,
(H-2, H-3,
H-4, H-6); 3.52
H-l, H-5).
66.7,
65.4, 63.4 (C-2, C-3, C-4, C-6); 55.1, 49.8 (C-l, C-5).
This work was supported by DFG (Sonderforschungsbereich
and Fonds der Chem. Industrie. A generous gift of starting materials
by ICI is gratefully acknowledged.
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