JPH041164A - 2-aceamidochiroinositols and production thereof - Google Patents

Abstract

NEW MATERIAL:Optically active 1D-2-acetamido-1,3,4,5-tetra-O-acetyl-2-deoxy-6- O-methyl-chiro-inositol shown by formula I. USE:Useful as a raw material for drugs such as antibiotics and anti-cancer drugs and agricultural chemicals. PREPARATION:A compound shown by formula I is obtained by a process of subjecting the fourth order of L-quebrachitol to azide formation, reducing the azide group and acetylating and a process of acetylating hydroxyl groups of the 1, 3, 5 and 6 positions of L-quebrachitol. Optically active 1L-2- acetamido-1,3,4,6-tetra-O-acetyl-2-deoxy-5-O-methyl-chiro-inositol shown by formula II is a new compound and is obtained by a process of subjecting the 5-position of L-quebrachitol to azide formation, reducing the azide group and acetylating and a process of acetylating hydroxyl of the 1, 3, 4 and 6 positions of L- quebrachitol.

Description

Detailed Description of the Invention <Industrial Application Field> The present invention is a novel aminocyclitol, an optically active 1D-2-acetamido-1°3.4.5-tetra-O-acetyl-2 -deoxy-6-0-methyl-thyro-inositol and 1L-2-acetamido-1,3
,4゜6-tetra-0-acetyl-2-deoxy-5-
The present invention relates to a method for obtaining the novel aminocyclitol using 0-methyl-thyro-inositol and L-quebratitol as starting materials without going through an optical resolution step.

Aminocyclitols are useful as synthetic raw materials for medicines such as antibiotics and anticancer agents, and agricultural chemicals.

<Conventional technology> Aminocyclitol (amino sugar) is a constituent sugar of glycoconsugates that widely exist in nature as a structural polysaccharide and plays an important role in sustaining life, and is also a constituent of important antibiotics. There have been attempts to synthesize it using various methods.

To give an example, furan and acrylic acid are subjected to a Diels-Alder reaction (1) to obtain a 1,4-androcyclohexane compound, which is decomposed with seasick acid to cleave the anhydro ring, and then subjected to azidation, reduction, etc. A method for obtaining amino sugars was proposed by Paulsen et al., using the naturally occurring salt ebrachitol as a starting material,
Method for obtaining optically active valienamine through 21 steps 2),
Method 3I using benzene glycol as starting material
Inositol disulfonate or cis-1,4
-Method 4 where hydrazine acts on diepoxide.

References 1) S, Ogawa and Y, 5hibat
a, Chew, Letter.

1985, p, 1518 2) H, Paulsen and F, R
, Helker, LiebigsAnn, Cb
em, 1981. pp, 2180-2203
3) M, Nakajil I+a, N, Ku
rihara, et al.

Liebigs Ann, Chem, 19
65. Vol, 689°p, 243 4) F, W, Lichtenthaler,
”Newer Methods of Prepa
rative Organic Chemistry
y, 1968°Vol, IV, p, 1
55 S, Ogawa, Journal of Organic Synthetic Chemistry, 196
9°Vol, 27. p, 731 <Problems to be Solved by the Invention> As mentioned above, methods for synthesizing aminocyclitols are known. However, all of these known methods have problems in that the synthesis process is complicated or that they require an optical resolution process. As a result, both methods have the problem of low yields.

The present invention has been made in view of the above facts, and 2.
A variety of new optically active aminocyclitols and L-
A novel optically active aminocycline with 1 and 2 different types using quebratitol as a starting material and without the need for an optical resolution process! The purpose of this invention is to provide a method for manufacturing Nodo-J.

<Means for Solving the Problems> The present invention provides optically active 1D-2 represented by the following formula (I).
-acetamido-1,3,4,5-tetra-0-acetyl-2-deoxy-6-0-methyl-thyro-inositol and optically active 1L-2- represented by the following formula (n)
Acetamide-1,3,4,6-tetra-0-acetyl-2-deoxy-5-0-methyl-thyro-inositol is provided.

NnAc The present invention also provides an optically active 1D-2-acetamido-1,3,4,5-tetra-O-acetyl-2-deoxy-6 characterized by using L-quebratitol as a starting material. -O-methyl-thyro-inositol (I) and optically active 1L-2-acetamide-1,3,4゜6-
A method for producing tetra-0-acetyl-2-deoxy-5-0-methyl-thyro-inositol (n) is provided.

The present invention will be explained in detail below.

The compound of the present invention is an optically active 1D-2-acetamido-1,3゜4.5-tetra-0 represented by the above formula (I).
-Acetyl-2-deoxy-6-0-methyl-thyro-inositol and the optically active LL-2-acetamido-1,3,4,6-tetra-O represented by the above formula (If)
-acetyl-2-deoxy-5-0-methyl-thyro-inositol.

1D-2-acetamido-1,3,4,5-tetra-O
-Acetyl-2-deoxy-6-O-methyl-thyro-inositol (I) has a specific optical rotation ([α]2゛) of +33
．． 9°, it is a colorless syrup that is insoluble in hydrocarbon solvents and soluble in alcohols, halogenated hydrocarbons, dimethylformamide, etc.

1L-2-acetamido-1,3,4,6-tetra-O
-Acetyl-2-deoxy-5-0-methyl-thyro-inositol (n) has a melting point of 193-194°C, a specific optical rotation ([α]o) of -33.2°, and is insoluble in hydrocarbon solvents. It is a white crystalline solid that is soluble in alcohols, halogenated hydrocarbons, dimethylformamide, etc.

The above-mentioned compound (2-acetamidothyroinositol) of the present invention belongs to the aminocyclitol class, and is preferably synthesized using ebrachitol, which has no optical activity, as a starting material. Since ebrachitol, which is a starting material, is an optically active compound, only the optically active compound can be obtained. In addition, the compound can be further converted into other aminocyclitols or derivatives thereof, and thus serves as a raw material for pharmaceuticals, agricultural chemicals, and the like.

L-quebratitol (L-(-)-2-0-Methyl-
Chiro-1 nositol is a monomethyl ether of inositol and is widely found in the bark of Hevea brasiliensis, the sap of Hevea brasiliensis, and other seeds. Therefore, ebrachitol derived from these plants may be used as a starting material.

A method for collecting L-quebratitol from such plants is described, for example, in Japanese Patent Application No. 168562/1983 and Japanese Patent Application No. 161922/1999, in which ebrachitol is collected from Hevea rubra.

According to the latter, L-quebratitol can be obtained by dissolving the concentrate or dry product of natural rubber serum (the remaining aqueous solution after removing the coagulated rubber in the natural rubber manufacturing process) in methanol, and concentrating the solution. However, it can be easily collected by crystallizing L-quebratitol. All of the quebratitol thus collected is of the optically active L type.

As mentioned above, the production method of the present invention uses L- as a starting material.
It is characterized by the use of quebratitol, but the optically active 1D-2-acetamido-1,3,4,5-tetra-O-acetyl-2-deoxy-6-0-methyl-thyro-inositol (I ) In the case of the production method, the 4-position of L-quebratitol is azidated, the azide group is reduced and acetylated, and the hydroxyl group at the 1.3, 5.6-position of L-quebratitol. A production method that involves a step of acetylating 1L-2-acetamide;
In the case of the method for producing 1,3゜4.6-tetra-0-acetyl-2-deoxy-5-O-methyl-thyro-inositol (II), after azidating the 5-position of L-quebratitol, A preferred production method includes a step of reducing the azide group and acetylating it, and a step of acetylating the hydroxyl group at the 1,3.4+6 positions of L-quebratitol.

An example of a preferred manufacturing method will be explained below based on FIG. 1.

<Optically active 1D-2-acetamide-13,4,5-
Tetra-0-acetyl-2-deoxy-6-0-methyl-thyro-inositol (I) and 1L-2-acetamido-1°3.4.6-tetra-0-acetyl-2-deoxy-5-0 -Methyl-thyro-inositol (II)
Synthesis> On L-quebratitol, the 2nd position is methyl etherified and becomes a methoxy group, so two adjacent hydroxyl groups (the hydroxyl group at the 3rd and 4th positions and the hydroxyl group at the 5th and 6th positions) are combined into a bridge type. Can be protected with protecting groups. Examples of such protecting groups include isopropylidene group, cyclohexylidene group, and benzylidene group.

In the reaction for introducing a protecting group, 22-dimethoxypropane, acetone, cyclohexanone, or benzaldehyde is used, respectively.

When a compound (2,2-dimethoxypropane in the example shown in Figure 1) for introducing the above-mentioned bridge-type protecting group into L-quebratitol 1 is used, only the hydroxyl group at the 5.6-position is bridged. A compound λ protected with a type protecting group (impropylidene group in the example in Figure 1) and the 3.4-position and 5.6-position
A mixture with a compound article having a protected hydroxyl group is obtained. Therefore, using water and an organic solvent such as ethyl acetate, the compound 2 is extracted into the aqueous phase and the compound 2 is extracted into the organic phase.

After concentrating compound λ, when compound E is reacted with acetic anhydride in the presence of pyridine, the hydroxyl groups at positions 1, 3, and 4 are acetylated. Subsequently, when about 60 to 80% acetic acid or the like is applied, the protective group at the 5 and 6 positions is removed and a compound having regenerated hydroxyl groups is obtained.

When this compound B is reacted with an organic sulfonyl halide such as 1)-toluenesulfonyl halide, alkylenesulfonyl halide, naphthylsulfonyl halide, etc. in the presence of pyridine, in the example shown in Figure 1, the p-toluenesulfonyl group replaces the oxygen atom. Compounds introduced at the 5-position can be obtained through this method.

Looking at this compound, sodium azide, potassium azide,
When an azidizing agent such as ammonium azide or barium azide is reacted and 2-methoxyethanol is reacted at the same time, two types of tetra-0-acetyl bodies (compound 7 and compound 7) are obtained. After extracting this mixture with an organic solvent such as ethyl acetate, compound 1 and compound 2 are each isolated by means such as silica gel column chromatography.

Here, the reactions leading to compound identification and compound 7 will be explained with reference to FIG. 2.

Reactions from one compound to another and to compound E are due to the involvement of adjacent groups. That is, the compound is in equilibrium with the other compound, then compound i becomes a compound 50a having a cyclic acetoxonium ion, and this compound 50a is in equilibrium with the same compound 50b having a cyclic acetoxonium ion.

The cyclic acetoxonium ion moiety of these compounds 50a and 50b undergoes a nucleophilic substitution reaction when attacked by azide ions, and the ring opens transaxially, so that from compound 50a, via compound 12, compound E is formed. Furthermore, compound 6 is produced from compound 50b via compound 12.

Note that Compound 50b is more advantageous due to the steric hindrance of the methoxy group, and therefore, the compound 50b is obtained as the main product.

When reacting acetic anhydride in ethanol on the compound,
When the azide group is reduced, the compound is co-acetylated to become an acetylamino group (to-2-acetamido-1,3,4,5-tetra-O-acetyl-2-deoxy-6-0 -methyl-thyro-inositol) is obtained.

Note that a nickel-based catalyst is usually used in this step.

Similarly, when compound E is reacted with acetic anhydride in ethanol, the azide group is reduced and acetylated to form an acetylamino group (LL-2-acetamido-1,3゜4.6-tetra -O-acetyl-2-deoxy-5-0-methyl-thyro-inositol) is obtained. Note that a di-Sikel type catalyst is usually used in this step.

The above is a preferred example of the production method of the present invention, and in each step, operations such as extraction, concentration, desalting, purification, etc. are usually performed as necessary.

<Example> EXAMPLES The present invention will be specifically explained below with reference to Examples.

(Example) 1D-2-acetamide-1,3°4.5-
Tetra-0-acetyl-2-deoxy-6-0-methyl-thyro-inositol (compound 8) (I) and 1L-
Synthesis of 2-acetamido-1,3,4,6-tetra-O-acetyl-2-deoxy-5-0-methyl-thyro-inositol (compound top) (■) Using L-quebrachitol as a starting material The synthesis steps for the compound and its components will be explained based on FIG.

■ L-quebratitol (compound) 1D, 0g (51.5mmoρ) and DMF l 00
mβ, 2,2-dimethoxypropane 31 mA (250 mA
0.5 g of p-toluenesulfonyl chloride was added (the reaction solution had a pH of about 4), and the mixture was stirred at room temperature for 16 hours. After neutralizing by adding sodium hydrogen carbonate, 300 m℃ of ethyl acetate and 300 mn of water were added and shaken, and 1 L-5,6-0-impropylidene-2-0-methyl-thyro- inositol (compound z),
1 L 1,2:3,4-di-0-isopropylidene-5-0-methyl-thyro-inositol (on compound) was extracted into the organic phase, respectively.

The aqueous phase was concentrated under reduced pressure (sequentially azeotropically with ethanol, n-butanol, and toluene) to obtain Compound 1 as a salt-containing syrup. After desalting this with a silica gel short column, the syrup was mixed with 1D0 mρ of pyridine and L acetic anhydride.
oomβ was added and stirred at room temperature for 7 hours. Toluene was added to the reaction solution, and the reaction solution was azeotroped with toluene and concentrated under reduced pressure. Ethyl acetate was added thereto to dilute the solution, and the salt was filtered off. Toluene was added to the filtrate, and the mixture was azeotroped with the toluene, and the filtrate was concentrated under reduced pressure to obtain a brown syrup.

Add 20mj2 of 80% acetic acid to this brown syrup,
Stirred in a 5°C oil bath for 24 hours.

8.6 g of brown syrup was obtained by adding toluene to the reaction solution, azeotropically distilling the reaction solution with the toluene, and concentrating the reaction solution under reduced pressure. This was carried out using silica gel column chromatography (
Purified with ethyl acetate:toluene = 3:2 (v:v)) to produce 1L-1,3,4-tri〇-acetyl-2-0-methyl-thyro-inositol (compound hill) as a white solid.
s, 62 g (yield: 35%) was obtained.

This was crystallized with ethanol and used as an analytical sample.

Compound hill Rf = 0.36 (MEK: ) Jt, En = 1: 1 (V:
V)) Melting point 122-124°C (ethanol) I
R(neat) 3470 cm-' (OH), 1
750cm-'(OAc)' H-NMR (90MHz, CD CI2
s) δ = 5, 50 (t, IH, J=3.5Hz, H-1), 5, 30
~5.05 (m, 2H, H-3,4), 4, 1 5~3. 50 (m, 4H), 3,
47 (s, 3H1OMe), 3, 30-3
．． 1D (m, IH), 2, 13, 2.08
, 2.05 (3g% each 3H13xOAc) Elemental analysis theoretical value (C,, H,, O,) C: 48.75%, H: 6.29% Actual value C: 48.44%, H: 6. 12% [αlo -75,4@ (c 1.01, CH(,9,) ■Compound 4 1.05g (3,28mmoρ), p
-Toluenesulfonyl chloride 1.25g (6,
56 mmon) and 1 Dm12 of pyridine and stirred at room temperature.
Stir for hours. The reaction solution was diluted with 300 mQ of ethyl acetate, and then washed with water (200 ml x 2). After drying the organic phase over anhydrous sodium sulfate, the sodium sulfate was filtered off. Toluene was added to the filtrate, and the mixture was azeotroped with the toluene, and the filtrate was concentrated under reduced pressure to obtain 1.9 g of brown syrup.

This was subjected to silica gel column chromatography (MEK).
: Toluene = 1:6 (v:v)) to produce 1L-1,3,4-tri-acetyl- as a colorless syrup.
1.4 g (yield: 90%) of 2-0-methyl-5-0-(p-toluenesulfonyl)-thyro-inositol (compound article) was obtained.

Compound article Rf=0. 44 (MEK: Tor xn = 1: 3 (V: V
) )IR(neat) 3470cm-'(OH
), 1750cm-' (OAc), 1 1 80cm-'(Sow)'H-NMR
(90MHz, CDCβ3)δ = 7, 80~7. 20 (m, 4H, Ph)
, 5, 54 (t, IH, J, , = J, ,
~3, 5Hz, H-1), 5, 4 2 (t, I H, Jx 4''
J4. s ~9, 0Hz, H-4), 5, 19 (t, IH, J,, ~9.
0Hz, H-3), 4, 74 (dd, I Hl J-,s ~3.0Hz, H'5), 4,
24 (ddd% q-1ike, IHlJ,
,,~3. 2Hz, H-6), 3, 70
(dd, IH, H-2), 3, 35 (
s, 3H1OMe), 2, 92 (d%
IH, OH), 2, 46 (s, 3H, P
hMe), 2, 15, 2, 01, 1, 73
(3s, each 3H13xOAc) Elemental analysis theoretical value (C,.H2,O,,S) C: 50.63%, H: 5.52% Actual value C: 50.37%, H: 5.83% [ a]o
66.1 @ (c2.90, CHCI2.) ■Compound 5 419mg (0,883 mmo Q) and sodium azide 230mg (3,5
3 mmoj2) and 4 mρ of 90% 2-methoxyethanol aqueous solution were added, and the mixture was heated under reflux in a 125° C. oil bath for 20 hours. After cooling to room temperature, toluene was added to the reaction solution, azeotropically distilled with the toluene, and the reaction solution was concentrated under reduced pressure to obtain a brown solid 5.
．． 3g was obtained. Add to this 3 mβ of pyridine and 3 m of acetic anhydride.
ρ was added thereto, and the mixture was stirred at room temperature for 23 hours.

The reaction solution was added dropwise to 30 mβ of ice water, and 70 m of ethyl acetate was added.
1. Extracted with. Add the organic phase to more water (30m 12)
After washing with water, it was dried with anhydrous sodium sulfate. After filtering off the sodium sulfate, toluene was added to the filtrate, and the filtrate was azeotroped with the toluene and the filtrate was concentrated under reduced pressure to obtain a brown syrup.
．． 37g was obtained. This was purified by silica gel column chromatography (MEK:) toluene = 1:1D (v:v)), and 1D-1,3,4,5-tetra-O-acetyl-2-azide-2 was purified as a white solid. -deoxy-6-O
-Methyl-thyro-inositol (compound 6) 147 mg
(Yield: 43%) and LL as colorless syrup.
48 mg (yield: 14%) of -1,3,4,6-tetra-0-acetyl-2-azido-2-deoxy-5-0-methyl-thyro-inositol (Compound E) was obtained. Compound Dan was crystallized with ethanol and then used as an analytical sample.

Compound temperature Rf=0. 34 (MEK: 't-luene = 1: 1D (V
: V)) Melting point 83.0-83.5°C (ethanol) IR (neat) 211D cm-' (Nx
), 1'760cm-' (OAc) 'H-NMR (90MHz, CDCj2-) δ: 5.50-5.05 (m, 4H, H-1,3,4,5), 3,94 (dd , IH,J,, =3.4Hz.

Jr, s = 1D. 2Hz% H-2), 3.
83 (t, IH, J+, s = Js, a
=3, 3Hz% H-6), 3.50 (s, 3H, OMe), 2, 12.2
．． 1o, 2. o6.2.00 (4s, each
3H, 4X OA c ) Elemental analysis theoretical value (C + sH * 1N a 09) C: 46.51%, H: 5.46%, N: 1D. 84% Actual value C: 46. 18%, H:5.31%, N:1
D. 77% [α]. +28.9° (c 1.07, cHcI2a) Compound Rf=0. 26 (MEK: Toluene = 1: 1D (V:
V)) Melting point Syrup I R(neat) 211D cm-' (Ns
), 1760cm-'(OAc)' H-NMR (90MHz %CD CRm
) δ = 5.53 ~ 5.20 (m, 4H, H-1, 3, 4, 6) 3, 94 (dd, IH, J,,, = 3.0Hz, Jx, s
= 1D. 0Hz, H2) 3.62~3.45 (
m, IH, H-5), 3, 35 (s, 3H
1OMe), 2, 16, 2.15, 2.1D, 2.
07 (4s, each 3H14XOAc) Elemental analysis theoretical value (C,, H,, N, 09) C: 4ei, 51%, I (: 5.46%, N: 1D.8
4% Actual value C: 47.09%, H: 5.38%, N: 1D. 27
% [αlo -41,2° (c 1.37, CHCρ,) ■ Add 6 mj2 of ethanol and 0.2 m of acetic anhydride (2, Raney Nickel-T4 (catalyst) 1 small spatula to 147 mg of compound (0.38 mn + o℃). , initial pressure 55
Shake in a Parr reduction apparatus at psi for 139 hours.
The catalyst was separated by zeolite filtration, toluene was added to the filtrate, and the filtrate was azeotroped with the toluene and the filtrate was concentrated under reduced pressure to form a green syrup.
．． 2g was obtained. This was subjected to silica gel column chromatography (ethanol:toluene=1:1D (v:v
)) to give 1D-2-acetamido-1,3,4,5-tetra-O-acetyl- as a colorless syrup.
2-deoxy-6-0-methyl-thyro-inositol (
89 mg (yield: 58%) of the compound was obtained.

Compound (I) Rf=0.25 (ethanol:toluene=1:1
D (V:V)) Melting point syrup IR (neat) 3360cm-' (NH), 32
80 cm-' (NH), 1750 cm-' (OAc), 1660 cm-' (amide) H-NMR (270 MHz% CDC(2,) δ = 5.65 (d, I H, J z, s, 4 = 8, 8
Hz, NHAc), 5.50 (t, I H, J 1.s = J 34”1
D. 0Hz, H-3), 5.26 (t, IH, J, □”Jl, l!=3.1H
z, H-1) 5.13 (t, IH, J4.5 = 1D, OHz, H-3), 5.08 (dd, IH, Ja, a = 3.1Hz, H-5), 4. 66 (ddd, IH, H-2), 3.74 (t
, IH, H-6), 3.52 (s, 3H1OMe), 2, 18, 2 08, 2.04, 2, 01.1,
93 (5s, each 3H, NHAc
, 4xOAc) Elemental analysis theoretical values (C17H2, NO1o) C: 50.63%, H: 6.25%, N: 3.47% Actual values C: 50.97%, H: 6.18%, N+3. 1
2%, [α]. +33.9゜ (C0,72, CHCj2s) ■To 96 mg of compound (0.25 mmo℃), add 3 mI2 of ethanol, 0.13 mn of acetic anhydride, and 1 small spatula of Raney Nickel-T4 (catalyst), and initial pressure 55 ps.
The mixture was shaken for 16 hours using a Parr reduction apparatus. The catalyst was separated by zeolite filtration, toluene was added to the filtrate, the filtrate was azeotroped with the toluene, the filtrate was concentrated under reduced pressure, and a green white knob of 0.12
I got g. This was subjected to silica gel column chromatography (ethanolide J renin = 1:1D (v:v
)) to give 80 mg of 1L-2-acetamido-1,3,4,6-tetra-0-acetyl-2-deoxy-5-0-methyl-thyro-inositol (compound product) as white crystals. rate: 80%). This was recrystallized from ethanol and used as an analytical sample.

Compound article (n) Rf=0.29 (ethanol:toluene=1:1
D (V:V)) Melting point 193-194°C (ethanol) IR (neat
) 3280cm-' (NH), 1750cm-'
(OAc), 1660 cm-' (amide), 1550 cm-' (amide) H-NMR (90 MHz, CDCff,) δ = 5, 73 (d, I H, J * NH = 9,
OHZ, NHAc), 5, 50 (t, IH, J+, s ”Js,
a = 3, 5Hz, H-6), 5, 27 (t, I H, J-4" J 4.
a = 9, 5Hz, H-2), 5.17(t, IH, J,, = 3.5Hz,
H-5), 5, 12 (t, IH, Jr, s = 9.
5Hz, H-3), 4, 77-3. 96 (m, IH, H-2)
, 3, 47 (dd, IH% H-5), 3
, 35 (s, 3H, OMe) , 2, 16,
2.06, 2.03, 1, 90 (4s, 6H13
H, 3H, 3H1NHAc, 4xOAc) Elemental analysis theoretical value (C,, H,, NO, 0) C: 50.63%, H: 6.25%, N: 3.47% Actual value C・50 45 %, H:5.15%, N・3
, 47%; 5-tetra-O-acetyl-2-deoxy-6-0-methyl-
Thyro-inositol and optically active 1L-2-acetamido-1,3,4,6-tetra-O-acetyl-2-
Deoxy-5-0-methyl-thyro-inositol and L
- Processes for their production starting from quebratitol are provided.

The novel aminocyclitols of the present invention can be used as raw materials for pharmaceuticals such as antibiotics and anticancer drugs and agricultural chemicals by being further converted into other aminocyclitols or derivatives thereof. Therefore, it is a very useful compound.

Since the production method of the present invention uses optically active L-quebratitol as a starting material, there is no need for optical resolution (
In addition, compared to the conventional production method of aminocyclitol,
The number of steps is small (consisting of simple steps).
Therefore, aminocyclitols can be provided at low cost and in high yield.

[Brief explanation of the drawing]

Figure 1 shows that L-quebratitol to 1o-2-acetamido-1,3,4,5-tetra-0-acetyl-2-
Deoxy-6-0-methyl-thyro-inositol and 1L-2-acetamido-1,3,4,6-tetra-0
- Acetyl-2-deoxy-5-0-methyl-thyro-inositol is a reaction route diagram. Figure 2 shows 1L-1,3,4-tri-acetyl-2
-0-methyl-5-0-(p-toluenesulfonyl)
-Thyro-inositol to 1o-1,3,4,5-tetra-O-acetyl-2-azido-2-deoxy-6-0
-Methyl-thyro-inositol and 1L-1,3゜4
．． It is a reaction route diagram leading to 6-tetra-0-acetyl-2-azido-2-deoxy-5-0-methyl-thyro-inositol. Ts: -5Ox (ΣCH3 NuyaF I G. 6' Eng.

Claims (6)

[Claims] (1) Optically active 1_D-2-acetamido-1,3,4,5-tetra- represented by the following formula (I)
O-acetyl-2-deoxy-6-O-methyl-thylo-
Inositol. ▲There are mathematical formulas, chemical formulas, tables, etc.▼……(I) (2) Optically active 1_L-2-acetamido-1,3,4,6-tetra- represented by the following formula (II)
O-acetyl-2-deoxy-5-O-methyl-thylo-
Inositol. ▲There are mathematical formulas, chemical formulas, tables, etc.▼……(II) (3) Optically active 1_D-2-acetamide-1,3 characterized by using L-quebratitol as a starting material
,4,5-tetra-O-acetyl-2-deoxy-6-
A method for producing O-methyl-thyro-inositol. (4) A step of azidating the 4-position of L-quebratitol and then reducing the azide group to acetylate it; and a step of acetylating the hydroxyl groups at the 1, 3, 5, and 6-positions of L-quebratitol. An optically active 1_D- characterized by undergoing
A method for producing 2-acetamido-1,3,4,5-tetra-O-acetyl-2-deoxy-6-O-methyl-thyro-inositol. (5) Optically active 1_L-2-acetamide-1,3 characterized by using L-quebratitol as a starting material
,4,6-tetra-O-acetyl-2-deoxy-5-
A method for producing O-methyl-thyro-inositol. (6) A step of azidating the 5-position of L-quebratitol and then reducing the azide group to acetylate it; and a step of acetylating the hydroxyl groups at the 1, 3, 4, and 6-positions of L-quebratitol. An optically active 1_L- characterized by undergoing
A method for producing 2-acetamido-1,3,4,6-tetra-O-acetyl-2-deoxy-5-O-methyl-thyro-inositol.