JPH0441469A - New monoacetamide-tetra-o-acetyle-inositols and production thereof - Google Patents

Abstract

NEW MATERIAL:Optically active 1D-2-acetamide-1,4,5, 6-tetra-O-acetyle-2- deoxy-3-O-methyl-a-ro-inositol. USE:Useful as a raw material of medical drug or agricultural chemical, etc., such as antibiotic or anticancer agent such as kanamycin or netilmicin. Said compound is obtained in a low cost and high yield because of able to be synthesized in simple and a small numbers or process without performing optical resolution. PREPARATION:The compound expressed by formula I is obtained by performing a process azidifying 3-position in L-quebrachitol expressed by formula II and reducing said azide group to acetylation and a process acetylation of hydroxyl groups at 1, 4, 5 and 6 positions in L-quebrachitol expressed by formula II.

Description

Detailed Description of the Invention <Industrial Application Field> The present invention provides a novel aminocyclitol, which is an optically active 1n-2-acetamido-1,4,
5,6-tetra-0-acetyl-2-deoxy-3-O
-Methyl-allo-inositol, 1n-1-acetamido-23,4,6-tetra-0-acetyl-1-deoxy-5-0-methyl-neo-inositol, 1D-3-
Acetamide-1245-tetra-0-acetyl-3-
Deoxy-6-〇-methyl-thyro-inositol, and 1L-1-acetamido-2,3,4,5-tetra-
0-acetyl-1-deoxy-6-0-methyl-myo-
Provides inositol.

In general, the present invention relates to a method for obtaining the novel aminocyclitol using L-quebratitol as a starting material through a step of optical resolution.

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

<Prior Art> Aminocyclitols generally refer to metal compounds in which the hydroxyl group of a cyclic alcohol is substituted with an amino group. The importance of aminocyclitols began to be recognized when one of them, streptomin, was discovered as a component of the antibiotic streptomycin. , several aminocyclitols have been shown to be included as important aminoglycoside antibiotic components.

In this way, aminocyclitol (amino sugar) is an important component of antibiotics, and is also a constituent sugar of glycoconsulgates that widely exist as structural polysaccharides in nature and play an important role in sustaining life. Therefore, attempts have been made to synthesize it using various methods.

To give an example, furan and acrylic acid are subjected to a Diels-Alder reaction to obtain a 111,4-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, using the naturally occurring salt ebrachitol as a starting material, was proposed by Paulsen et al.
Method 2' of obtaining optically active valienamine through 21 steps
Method 3' using benzene glycol as a starting material
Inositol disulfonate or cis-1,4-
There is a method 4) in which hydrazine is made to act on geboxito.

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

1985, L1518 2) H, Paulsen and F, R, He1
kar, LiebigsAnn, Chem, 1
981. pp, 2180-22033) M, Na
kajima, N, Kurihara, at a
l.

Liebigs Ann, Chem, 1965.
Vol, 689°9.243 4) F, W, Lichtenthalar, ”
Newer Methods of Preparation
ve Organic Chemistry, 1
968Vol1. TV, p, 155 S, Ogavra, Journal of the Organic Synthetic Chemistry Society, 19
[i9°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 multi-stage and complicated, and 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 is directed to aminocyclitol and its derivatives, which are contained in antibiotics such as kanamycin and hothymidine, and are thought to play an important part in their antibacterial activity. The purpose of the present invention is to provide a method for producing the four types of optically active novel aminocyclitol using different types of optically active novel aminocyclitol and L-quebratitol as starting materials, and which does not require an optical resolution process. do.

Means for Solving the Problems> The present invention provides optically active 1D-2 represented by the following formula (I).
-acetamido-1,4,56-tetra-0-acetyl-2-deoxy-3-O-methyl-allo-inositol, optically active 1D-1-acetamido-2,3, represented by the following formula (I+), 4,6-tetra-O-acetyl-
1-deoxy-5-〇-methyl-neo-inositol,
Optically active In-3-acetamido-1,2,4,5-tetra-O-acetyl-3- represented by the following formula (m)
Deoxy-6-〇-methyl-thyroinositol and optically active 1L-1-acetamido-2,3,4,5-tetra-0-acetyl-1 represented by the following formula (rV)
-deoxy-6-0-methyl-myo-inositol.

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

The present invention will be explained in detail below.

The compound of the present invention is an optically active 1D-2-acetamido-1,4゜5.6-tetra-0 represented by the above formula (I).
-Acetyl-2-deoxy-3-O-methyl-allo-inositol, optically active 1D represented by the above formula (II)
-1-acetamido-2,3,4,6-tetra-0-acetyl-1-deoxy-5-0-methyl-neo-inositol, an optically active 1D represented by the above formula (III)
-3-acetamido-1,2,4,5-tetra-0-acetyl-3-deoxy-6-0-methyl-thyro-inositol and optically active 1L represented by the above formula (IV)
-1-acetamido-2,3,4,5-tetra-0-acetyl-1-deoxy-6-0-methyl-myo-inositol.

1D-2-acetamido-1456-tetra-0-acetyl-2-deoxy-3-0methyl-
Arrow-inositol (I) has a specific optical rotation ([α]) of +8.5°, is insoluble in hydrocarbon solvents, and is soluble in alcohols, halogenated hydrocarbons, dimethylformamide, and the like.

1D-1-acetamido-2,3,4,6-tetra-0
-Acetyl-1-deoxy-5-0-methyl-neo-inositol (!■) has a melting point of 270-280°C and a specific optical rotation ([α). ) is +2.7°, and is a white solid that is insoluble in hydrocarbon solvents and soluble in alcohols, halogenated hydrocarbons, dimethylformamide, etc.

1D-3-acetamido-1,2,4,5-tetra-0
-Acetyl-3-deoxy-6-0-methyl-thyro-inositol (III') has a melting point of 144-145°C
, specific rotation ((α)D) is +14.6° It is a white solid having the properties of being insoluble in hydrocarbon solvents and soluble in alcohols, halogenated hydrocarbons, dimethylformamide, etc.

1L-1-acetamido-2,3,4,5-tetra-0
-Acetyl-1-deoxy-6-0-methyl-myo-inositol (rV) has a melting point of 189 to 190°C, a specific optical rotation ([α]D) of -39°, and is insoluble in hydrocarbon solvents.
It is a white solid that is soluble in alcohols, halogenated hydrocarbons, dimethylformamide, etc.

The above compound of the present invention (monoacetamide-tetra-〇-
Acetyl-inositol (acetyl-inositol) is a compound belonging to aminocyclitols, and may be synthesized by any method, but is preferably synthesized using ebrachitol, which has no optical activity, as a starting material. Since the starting material L-quebratitol is an optically active compound, only the optically active compound can be obtained. Moreover, since the compound can be further converted into other aminocyclitols or their conductors, it becomes a raw material for pharmaceuticals, agricultural chemicals, and the like. - Ebrachitol (L-(-)-2-0-Meth
yl-chiro-1nositol) is a monomethyl ether of inositol, and is widely found in quebracho bark, hevea brasiliensis sap, and other plants. 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-1,4,5,6-tetra-0-acetyl-2-deoxy-3-O-methyl-allo-inositol (I In the case of the manufacturing method of ), the 3-position of L-quebratitol is azidated, the azide group is reduced and acetylated, and the hydroxyl group at the 1.4, 5.6-position of L-quebratitol. A manufacturing method that involves a step of acetylating optically active 1D-1-acetamide, Do2.
3,4.6-tetra-0-acetyl-1-deoxy-5
The method for producing -0-methyl-neo-inositol (!I) includes the steps of azidating the 4-position of L-quebratitol, reducing the azide group, and acetylating the L-quebratitol.
- A production method that involves a step of acetylating the hydroxyl group at the 13.5.6 position of quebratitol, an optically active In-3-acetamide-1,2,4,5-tetra-0-acetyl-
3-deoxy-6-0-methyl-thyro-inositol (
In the case of the production method III), the step of azidating the 5-position of L-quebratitol and then reducing the azide group and acetylating it, and the step of acetylating the 5-position of L-quebratitol,
．． A manufacturing method that involves a step of acetylating the 6-position hydroxyl group,
In addition, optically active 1L-1-acetamide-2,3゜4
．． 5-tetra-0-acetyl-1-deoxy-6-0-
In the case of the production method of methyl-myo-inositol (■), the step of azidating the 1-position of L-quebratitol and then reducing the azide group and acetylating it, and the step of 3.4 of L-quebratitol , a manufacturing method that involves a step of acetylating the hydroxyl group at the 5 and 6 positions is preferred.

An example of a preferred manufacturing method will be described below based on the drawings.

Optically active 1D-2-acetamide-1゜4.5.6
-Synthesis of Tetra-0-acetyl-2-deoxy-3-O-methyl-allo-inositol (1)> This will be explained based on FIG. 1a and FIG. 1b.

In L-quebratitol 1, the 2-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 protected by a bridge-type protecting group. can be protected. Examples of such protecting groups include isopropylidene, cyclohexylidene, and benzylidene groups. and,
In the Hirohito reaction of protecting groups, 2,2-dimethoxypropane, acetone, cyclohexanone, or benzaldehyde is used.

When L-quebratitol 1 is reacted with a compound for introducing the bridge-type protecting group described above (2,2-dimethoxypropane in the example of FIG. 1a), preferably with a catalytic amount of tosylic acid, A compound in which only the hydroxyl group at the 5.6-position is protected with a bridge-type protection r (not shown), and a compound in which the hydroxyl group at the 3.4- and 5.6-positions are protected with a bridge-type protection group (in the example in Figure 1a, impropylidene) A mixture with compound 2 protected with (group) is obtained. Compound 2 is then extracted into the organic phase using an organic solvent such as ethyl acetate. In addition,
At this time, usually about 5 equivalents of bridge-type protecting group are used, but if this amount is increased to about 10 equivalents, compound 2
yield increases.

Next, when Compound 2 is reacted with acetic anhydride in the presence of pyridine, Compound 3 with very good crystallinity is obtained.
In Compound 2, since the remaining hydroxyl group is only at the 1st position, the hydroxyl group at the 1st position is selectively acetylated.

When Compound 3 is treated with about 60-80% acetic acid, stirred at room temperature, and then concentrated under reduced pressure, trans-isopropylidene (protecting groups at the 3 and 4 positions) is selectively removed and a compound is obtained. . Incidentally, the vacuum concentration is preferably carried out in a hot bath at about 20° C. in order to prevent the formation of a tetraol compound in which cis-isopropylidene (protecting groups at the 5 and 6 positions) is also removed at the same time.

In the presence of pyridine, p-toluenesulfonyl halide, alkylenesulfonyl halide,
When organic sulfonyl halides (tosyl halides) such as naphthylsulfonyl halide are reacted, 1a
In the example shown in the figure, a mixture of a compound with a p-toluenesulfonyl group introduced at the 3-position, a compound with a p-toluenesulfonyl group introduced at the 4-position, and a compound Y with a p-toluenesulfonyl group introduced at the 3- and 4-positions is obtained. This mixture of compound 2, compound 7 and compound 7 contains 60 to 8
When treated with about 0% acetic acid etc. under heating (approximately 60°C), the protecting group at position 5.6 is removed and a triol form (compound 8
Since a mixture of compound 9) and diol (compound 10) is obtained, compound 8, compound and compound - are obtained by means such as silica gel column chromatography.
L''- are isolated respectively.

Subsequently, a bridge-type protecting group (isopropylidene group in the example in Figure 1a) is again introduced into the hydroxyl group at the 5.6-position of compound 8, and the obtained compound is extracted with an organic solvent. Compound 12 is obtained by reacting with acetic anhydride below to acetylate the 4-position hydroxyl group.

Furthermore, when Compound 9 is treated in the same manner as Compound 8, Compound 11 is obtained.

When this compound 12 is reacted with an excess amount of an azidating agent such as sodium azide, potassium azide, ammonium azide, barium azide, etc. in the presence of 2-methoxymethanol, 0-p-toluenesulfonyl at the 3-position group is substituted with an azide group, and the 1- and 4-position hydroxyl groups are re-substituted with 4
: Obtained at a ratio of 1. Note that among the above-mentioned azidating agents, sodium azide is most preferable from the viewpoint of ease of handling. Compound 13 and compound 14 are each 1M by means such as silica gel column chromatography.

When compound 14 is reacted with acetic anhydride in the presence of pyridine, the 1- and 4-position hydroxyl groups are acetylated, and compound 1
8 is obtained. Note that this compound 18 is an allo-type compound resulting from S,2 reaction.

When this compound 18 is reacted with acetic anhydride in a hydrogen atmosphere, a compound 19 is obtained in which the azide group is reduced and acetylated to become an acetylamino group. In addition,
A nickel-based catalyst is usually used in this step.

Compound 19 is reacted with about 60 to 80% acetic acid or the like to remove the protective group and regenerate the hydroxyl group at the 5.6-position. Subsequently, when acetic anhydride is reacted in the presence of pyridine, 5.
The hydroxyl group at position 6 is acetylated, forming compound 20 (1D-
2-acetamido-1,4,5,6-tetra-O-acetyl-2-deoxy-3-O-methyl-allo-inositol) (I) is obtained.

On the other hand, when Compound 13 is reacted with acetic anhydride in the presence of pyridine, the hydroxyl groups at the 1st and 4th positions are acetylated and Compound 15 is obtained. This compound 15 is a product involving adjacent groups, and is an L-tyro type that retains the stereochemistry of compound 12.

When this compound 15 is reacted with acetic anhydride in a hydrogen atmosphere, a compound 16 in which the azide group is reduced and acetylated to become an acetylamino group is obtained. In addition,
A nickel-based catalyst is usually used in this step.

Compound 16 is reacted with about 60 to 80% acetic acid or the like to remove the protective group and regenerate the hydroxyl group at the 5.6-position. Subsequently, when acetic anhydride is reacted in the presence of pyridine, 5.
The hydroxyl group at position 6 is acetylated, resulting in compound 17 (1L-3
-acetamido-1,4,5,6-tetra-0-acetyl-3-deoxy-2-0-methyl-thyro-inositol) is obtained.

Optically active 1D-1-acetamide-2゜3.4.6
-Synthesis of Tetra-0-acetyl-1-deoxy-5-0-methyl-neo-inositol (II)> This will be explained based on Figure 1a and Nic diagram.

For example, by the method described above, a compound compound is obtained from L-quebratitol 1 through compound j.

Next, when the compound is reacted with acetic anhydride in the presence of pyridine to acetylate the 4-, 5-, and 6-position hydroxyl groups,
Compound 21 is obtained.

Compound 21 is reacted with an excess amount of an azidating agent such as sodium azide, potassium azide, ammonium azide, barium azide, etc. in the presence of 2-methoxymethanol, and further reacted with acetic anhydride in the presence of pyridine. When acetylation is carried out, three types of azides (Compound 22, Compound 25) are obtained in a ratio of about 7:7:1=4. By means such as silica gel column chromatography, 3[
The azide forms (Compound 22, Compound 23, Compound 24) of are isolated.

Subsequently, when the compound was reacted with acetic anhydride in a hydrogen atmosphere, the azide group was reduced and acetylated to form an acetylamino group, compound 26 (10-1-acetamido-2°3.4.6 -tetra-0-acetyl-1-
deoxy-5-0-methyl-neo-inositol) (I
I) is obtained.

In addition, if the compound list is processed in the same way, 1 unit (1L) of the compound
Compound 20 (1D- 2-acetamido-1,4,5゜6-
Tetra-0-acetyl-2-deoxy-3-O-methyl-arrowinositol) (I) is obtained.

Optically active 1D-3-acetamide-1゜2.4.5
-Synthesis of Tetra-0-acetyl-3-deoxy-6-0-methyl-thyro-inositol (III)> This will be explained based on FIGS. 1a and 1d.

For example, by the method described above, Compound 9 is obtained from L-quebratitol via Compound 9.

Next, when the compound is reacted with acetic anhydride in the presence of pyridine, the hydroxyl groups at the 3-, 5-, and 6-positions are acetylated, and Compound 27 is obtained.

This compound 27 is reacted with an excess amount of an azidating agent such as sodium azide, potassium azide, ammonium azide, barium azide, etc. in the presence of 2-methoxyethanol, and further reacted with acetic anhydride in the presence of pyridine. When acetylation is carried out, two types of azides (Compound 28 and Compound 29) are obtained.

In this reaction step, cyclic acetoxonium is formed at either the β, 4-position or the 4.5-position due to the involvement of adjacent groups, but experimental results indicate that the involvement of adjacent groups occurs at the 4- and 5-positions. It became clear that things took priority. Therefore, in this reaction step, compound 28 in which the methoxy tree is in the equatorial position is the main product.

By means such as silica gel column chromatography,
Two types of azides (Compound 28 and Compound 29) are isolated.

Subsequently, when compound 11 was reacted with acetic anhydride in a hydrogen atmosphere, the azide group was reduced and acetylated to form an acetylamino group, compound 30 (1D-3-acetamido-1゜2.4.5 -tetra-O-acetyl-3
-deoxy-6-O-methyl-thyro-inositol) (
III) is obtained.

In addition, when one compound is treated in the same way, one unit of the compound (1
L-3-acetamido-1,2゜4.6-tetra-0-
Acetyl-3-deoxy-5-〇-methyl-thyro-inositol) is obtained. .

Optically active 1L-1-acetamide-2゜3.4.5
-Synthesis of Tetra-0-acetyl-1-deoxy-6-0-methyl-myo-inositol (IV)> This will be explained based on FIG. 1a and FIG. 1e.

For example, Compound 2 is obtained from L-quebratitol 1 by the method described above.

Then, when compound S is reacted with an organic sulfonyl halide such as p-toluenesulfonyl halide, alkylenesulfonyl halide, naphthylsulfonyl halide, etc. in the presence of pyridine, p-) is obtained in the example of FIG. 1e.
Compound 32 in which a luenesulfonyl group is introduced at the 1-position is obtained.

When this compound 32 is reacted with an excess amount of an azidating agent such as sodium azide, potassium azide, ammonium azide, barium azide, etc. in the presence of dimethyl sulfoxide, the azide form (compound 33) and cyclohexene (compound 34) through an elimination reaction in a ratio of approximately 4:1.
obtained at a rate of

Compound 33 and compound 34 are each isolated by means such as silica gel chromatography.

Compound 33 is reacted with about 1 to 4 M hydrochloric acid to remove the protective group and regenerate the hydroxyl group at the 3, 4, 5, and 6 positions.
Subsequently, when acetic anhydride is reacted in the presence of pyridine,
The hydroxyl groups at positions 3, 4, 5, and 6 are acetylated to obtain a tetraacetyl compound (compound 35).

When this compound 35 is reacted with acetic anhydride in a hydrogen atmosphere, the azide group is reduced and acetylated to form an acetylamino group, compound 36 (1L-1-acetamido-2,3゜4.5-tetra -0-acetyl-1-deoxy-6-○-methyl-myoinositol) (IV
) is obtained.

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

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

(Example 1) l D-2-acetamide-1゜4.
5.6-tetra-0-acetyl-2-deoxy-3-O
-Methyl-allo-inositol (compound view) Synthesis of (I) Compound 20 using L-quebratitol as a starting material (
The synthesis process of I) will be explained based on Figure 14ia and 'S i b.

■ L-quebratitol (compound 1) 10.0 g (51.5 mmoJ2) with DMFloo
ml, 2,2-dimethoxypropane 3.1 mu (250
mmoβ) and 0.5 g of p-toluenesulfonic acid were 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 ml of ethyl acetate and 300 mA of water were added and shaken, and the reaction products were separated and extracted into an aqueous phase and an organic phase.

After drying the organic phase over anhydrous sodium sulfate, the sodium sulfate was filtered off, and the filtrate was concentrated under reduced pressure to give 1L-1,2:3.4-di-O-isopropylidene-5-0-methyl as a flame yellow syrup. -Thyro-inositol (compound 2) 6
．． 9g was obtained.

Add 50 mjZ of pyridine and 50 mj acetic anhydride to this syrup.
2 was added and stirred at room temperature for 26 hours.

Toluene was added to the reaction solution, and the mixture was azeotroped with toluene, and the reaction solution was concentrated under reduced pressure to obtain 7.54 g of brown crude crystals. This was recrystallized from ethanol to give 1L-1-0-acetyl-3,4:5,6-di-0-isopropylidene-2-0.
-Methyl-thyro-inositol (compound 3) 5.39
g (yield: 33%) was obtained.

Compound Rf=0.72 (MEK:Toluene=2:1 (V:V)
) Melting point 109-109.5℃ (ethanol) IR (n
eat) 1750cm6'(OAc)' HN M
R (90 MHz, CDCIls) δ = 5.55-5.43 (m, IH%H-6), 4, 4
0-4, 20 (m, 2H%H-1,2), 3, 80-3, 50 (m, 3H, H-3,4,5), 3.43 (s, 3H, OMe), 2 .14 (s, 3H, 0Ac), 1.50.1.45.1.36 (3s.

3H, 6H, 3H, 2xCMe,) elemental analysis Theoretical value (CIsH2407) C: 56.95%, H near, 65% Actual value C: 57.00%, H near, 48% [α].

+2.1° (c 1.03, CHCf13) Compound 3 obtained in ■■ 12. 8 to 71g (40,18mmou)
0% acetic acid was added and stirred at room temperature for 4 hours. By adding toluene to the reaction solution, azeotropically distilling it with toluene, and concentrating the reaction solution under reduced pressure, 1L-1-0-7ceti71/-5,6-0-i was obtained as a syrupy residue (12.2 g). ') Propylidene-2-0-methyl-thyro-inositol (compound 4) was obtained.

To this, p-toluenesulfonyl chloride 11.49
g (60,27mmoj2) and pyridine 80mJZ
was added and stirred at room temperature for 20 hours. After diluting the reaction solution with 300 mjl of ethyl acetate, diluted with distilled water (100 mn x 3
). 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 toluene, and the filtrate was concentrated under reduced pressure to obtain 18.5 g of a mixture of Compound 5, Compound 6, and Compound 7 as a pale yellow syrupy residue.

To this mixture was added 80 mρ of 80% acetic acid, and the mixture was stirred in an oil bath at 50°C for 16 hours. Toluene was added to the reaction solution, and the reaction solution was azeotroped with toluene, and the reaction solution was concentrated under reduced pressure to obtain 18.8 g of a mixture of Compound 8, Compound 9, and Compound 10 as a syrupy residue.

This was purified by silica gel column chromatography (ethyl acetate: toluene concentration 3.2 to 1.0) to form a foamy syrup.
3-0-(p-toluenesul (compound 8) 4.79 g (yield: 3 for compound 3)
1%).

Compound 8 Rf=0.29 (MEK:Toluene=1:1 (V:V)) Melting point Syrup elemental analysis theoretical value (C+sH220e S ・1/2H20)C:
48.11%, H: 5.80% Actual value C2 48.12%, H: 5.66% [α]. -39,4''' (c 2.86, CH30H) ■Compound 8 4.71 g (12,06 mmofl
), DMF 50mJZ, p-toluenesulfonic acid hydrate 200mg, 2,2-dimethoxypropane 7
, 41 mg (60,3 mmoA) was added, and the mixture was heated at 55°C.
The mixture was stirred in an oil bath for 23 hours. After neutralizing the reaction solution by adding sodium hydrogen carbonate, 300 mfL of ethyl acetate was added, and the mixture was washed with water (100 mA x 3). 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 toluene, and the filtrate was concentrated under reduced pressure to obtain 5.8 g of brown syrup.
To this were added 30 mjZ of pyridine and 20 ml of acetic anhydride, and the mixture was stirred at room temperature for 19 hours. Toluene was added to the reaction solution, and the reaction solution was azeotroped with toluene, and the reaction solution was concentrated under reduced pressure to obtain 6.50 g of brown syrup. This was purified by silica gel column chromatography (MEK: toluene ÷ 1:6) to produce a colorless syrup of 1L-1,4-di-acetyl-5.6-0-isopropylidene-2-0-methyl- 3-0-(p-toluenesulfonyl)-thyro-inositol (compound 1) 3.66 g (yield: 64%)
I got it.

Compound 12 Rf=0.49 (MEK: toluene=1:5 (V:
V)) Melting point syrup IR (neat) 1755 cm-' (OAc), 1
180cm-'(SO2)'H-NMR (90MHz%CDCJZa) δ = 7.80.7.30 (2d, each 2H1J
= 9, OHZ, 502 PhMe), 5,
59 (t, I H, Jl, 2 = J+,
=3, 0H,,H-1), 5, 37~5. 1 1 (m, IHL)!
-4), 4, 81 (dd, IH, J2.3 = 7.8Hz.

J 3,4 = 9, 5 Hz, H3)
, 4, 36-4, 14 (m, 21 (, H-5, 6), 3, 61 (dd, IH, H-2), 3,
19 (s, 3H, OMe), 2, 44
(s, 3H, PhMe) , 2 14 ,
2,04 (2s, each 3H, 2x OAc
).

1, 53, 1, 34 (2s, each 3 H, CM e 2
) Elemental analysis theoretical value (C21H2gor.S) C: 53.33%, H: 5.97% Actual value [α) o -65,6° (c O,94, CHCl5) ■ Compound 12
876 mg (1,86 mmoJ:l) of sodium azide 476 mg (7,32 mmofl) and 90
% 2-methoxyethanol aqueous solution (10 ml),
The mixture was heated under reflux in a 125°C oil bath for 20 hours. Toluene was added to the reaction solution, the mixture was azeotroped with toluene, the reaction solution was concentrated under reduced pressure, diluted with ethyl acetate, and the salt was filtered off. The filtrate was concentrated under reduced pressure to obtain 046 g of pale yellow syrup.

This was subjected to silica gel column chromatography (ethanol:toluene, and 1L-3-azido-3-deoxy-
5.6-0-isopropylidene-2-〇-methyl-thyroinositol (compound 13) and 1D-2-azido-2-deoxy-5.6-0-isopropylidene-3-O- as a colorless syrup. Methyl-allo-inositol (
Compound 1 4) 66 mg (yield: 13%) was obtained: C:
5301%, H:6.04%.

Compound dish Rf=0. 41 (Ethanol:Toluene 1:8 (V:V)) Melting point Syrup IR (neat) 3370cm-' (OH), 20
50cm-'(N,) Elemental analysis theoretical value (CtoHttNsOs) C: 46.33%, H: 6.61%, N: 16.21% Actual value C+46.11%, H: 6.39%, N: 16.41% [α)o -28,3 (c O,96, CHCfL,) (1) 1 mJ1 of picillin and 1 mJ2 of acetic anhydride were added to 1418 mg (69 μmoJl) of the compound, and the mixture was stirred at room temperature for 6 hours. Toluene was added to the reaction solution, and the mixture was azeotroped with toluene, and the reaction solution was concentrated under reduced pressure to obtain 23 mg of brown syrup. This was carried out using silica gel column chromatography (
Purification with ethyl acetate; hexane = 1:6) gave 1D-1,4-di-0-acetyl-2-azide as white crystals.
2-deoxy-5,6-0-isopropylidene-3-O
-Methyl-allo-inositol (compound 18) 19 mg
(80%). This was recrystallized from ethanol and used as an analytical sample.

Compound 18 Rf=0. 39 (ethyl acetate:hexane=1:3 (V:V)) Melting point 85-86°C (ethanol) IR (neat) 2110 cm-' (Ns), 17
50cm-'(OAc)'H-NMR (90MHz% CDCf3) δ = 5, 61 (ddd, IH, J,, = 3.0Hz.

J,, = 1.0Hz.

J, 6 = 4. 0Hz 1 H-1), 4
, 95 (dd, IH, Js, -3,0Hz.

J 4 , =7. 0H2,H-4) ,4,
42-4, 19 (m, 2H% H-5, 6), 4, 15 (ddd, IH, J2.3
=4, 0Hz, H-3), 3, 77 (dd, IH, H-2), 3,
46 (s, 3H, OMe)2, 19,
2, 17 (2s, each 3H, 2x OA
c), 1, 56, 1, 44 (2s, each 3 H, CM e 2
) Elemental analysis theoretical values (CI4H21N 30 y) C: 48.98%, H: 6.17%, N: 12.24% Actual values C: 49.14%, H: 6.06%, N: 12. 09% [α)o −89,1.

(co, 65, CHCI13) ■ Compound 18 44 mg (0,128 mmon
), 1 mA of ethanol, 0.1 mj2 of acetic anhydride, and 1 cup of a small spatula of Raney Nickel-74 (catalyst) were added, and the mixture was stirred under a hydrogen atmosphere (1 atm) for 2 hours. The catalyst 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 48 mg of a colorless syrupy residue.
This was purified by silica gel column chromatography (ethanol:toluene = 1 + 12) to give a colorless syrup of 1D-2-acetamido-1゜4-di-0-acetyl-2-deoxy-5,6-0-isopropylidene-
3-O-methyl-allo-inositol (compound 19) 3
7 mg (yield: 81%) was obtained.

Compound 19 Rf=O136 (ethanol; toluene = 1:6 (V:V)) Melting point Syrup JR (neat) 3300 cm-' (NH), 17
50 cm-' (OAc), 1660 cm-' (NAc), 2525 cm-' (NH) 'H-NMR (90 MHz, CDCu,') δ = 6, 07 (d, IH.

J2. N14=9 ・ 4, 97 (dd, IH.

J 34 = 3.　0Hz.

J4,5=4-5HZ%H-4)
, OHz, NH), 5, 07 (dd, IH.

J, 2 = 4.　0Hz.

J, 6 = 5. 0Hz, H-1), 4, 7
5 (ddd, IH, J23 = 3, 0Hz%
H-2), 4, 47-4, 12 (m, 2H, H-5, 6), 3, 70 (t, IH, H-3), 3,
42 (s, 3H% OMe), 2, 17,
2. 10. 2. 02 (3s, each 3H, 3xOAc
) , 1 , 51 , 1 , 36 (2S , each 3 H, CM e 2
) Elemental analysis theoretical value (C + sHzsN Oa) C: 53.47%, H near, 01%, N: 3.90% Actual value C: 53.21%, H: 6.98%, N: 3.76% (α)o −7,0.

(co, 30, CHCII 3 )■Compound 19
30 mg (0,083 mmojij), 80
% acetic acid was added, and the mixture was stirred in an oil bath at 60° C. for 12 hours. Toluene was added to the reaction solution, and the mixture was azeotroped with toluene, and the reaction solution was concentrated under reduced pressure to obtain 24 mg of a residue. To this were added 0.5 ml of pyridine and 0.5 ml of acetic anhydride, and the mixture was stirred at room temperature for 4 hours. Add toluene to the reaction solution,
The reaction solution was azeotroped with toluene and concentrated under reduced pressure to obtain a residue. This was purified by silica gel column chromatography (ethanol:toluene = 8), and the desired 1D-2-acetamide-1,4゜5.6-tetra-0-acetyl-2- Deoxy-3-O
-Methyl-allo-inositol (compound 20) (r)3
3 mg (yield: 98%) was obtained.

Compound 20 (1) Rf=0. 35 (Ethanol/Toluene=1:6 (V:V)) Melting point Syrup IR (neat) 3400cm-' (NH), 17
50cm-'(OAc), 1670cm-'(NAc), 1520cm-'(NH)' H-NMR(90MHz, CD Cj
2 s ) δ = 6.10 (d, IH.

J2. N) I=9.0H2, NH), 5.52-5.00 (m, 4H, H-1,4,5,6), 5.00-4. F O(m, IH
, H-2) , 3.78 (t, IH, J=3.0
Hz.

J=3.5Hz), 3.40 (s, 3H%OMe), 2.16.2. o7.2.03 (3s, 3H, 6H, 3H.

NHAc, 3XOAc), elemental analysis theoretical value (CItH26N Oto) C: 50. 62%, H: 6.25%, N: 3.47
% Actual value C: 50.34%, H: 6.31%, N: 3.34
% Cα)O+S,S.

(c 1.17, CHC1Ls) (Reference example 1) 1L-3-acetamido-1°4.5.6
-Synthesis of Tetra-0-acetyl-3-deoxy-2-0-methyl-thyro-inositol (Compound L) 2. Compound L was obtained according to Example 1-2 to 3. To 1.5 g of this compound 13, 6 ml of pyridine and 6 ml of acetic anhydride.
and stirred at room temperature for 6 hours. Toluene was added to the reaction solution, and the mixture was azeotroped with toluene, and the reaction solution was concentrated under reduced pressure to obtain 2.0 g of brown syrup. This was subjected to silica gel column chromatography (ethyl acetate:hexane=1:
6) to produce 1L-1,4-di0 as a white solid.
-acetyl-3-azido-3-deoxy-5,6-0-
1.52 g of isopropylidene-2-0-methyl-thyro-inositol (compound 15) was obtained.

■ Compound 151°52 g (4,44 mmojlj
) were added with 15 mA of ethanol, 2.1 mJZ of acetic anhydride, and 2 small spatulas of Raney Nickel-74 (catalyst), and the mixture was stirred under a hydrogen atmosphere (1 atm) for 22 hours. The catalyst 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 2.3 g of green syrup. This was purified by silica gel column chromatography (ethanol:toluene=1:12) to give 1L-3-acetamido-1,4-G-acetyl-3-deoxy-5,6-0-isopropylidene as white crystals. -2
-0-Methyl-thyro-inositol (compound 16)1.
58 g (yield: 99%) was obtained.

■Compound 16 40 mg (1,11mmoJ2)
1 mj2 of 75% acetic acid was added to the mixture, and the mixture was stirred at 55°C for 15 hours. Toluene was added to the reaction solution, and the mixture was azeotroped with toluene, and the reaction solution was concentrated under reduced pressure to obtain 38 mg of a white solid residue.

To this were added 1rr+Q of pyridine and 1n1L of acetic anhydride, and the mixture was stirred at room temperature for 18 hours. Toluene was added to the reaction solution, and the mixture was azeotroped with toluene, and the reaction solution was concentrated under reduced pressure to obtain 46 mg of a white solid residue. This was purified by silica gel column chromatography (ethanol:toluene=1=8) to obtain 1L-3-acetamido-1,4,5,6-tetra-0-acetyl-3-deoxy-2 as a white solid residue. -0-methyl-thyro-inositol (compound 1
7) 39 mg (yield: 89%) was obtained. This was recrystallized from ethanol and used as an analytical sample.

Compound 17 Rf=0.50 (ethanol:toluene=1:5 (V:V)) Melting point 187-188°C (ethanol) IR (neat)
3350cm-'(NH), 1750cm-'(OA
c), 1730 cm (OAC), 1650 cm-' (amide), 1550 cm-'(amide)' H-NMR (90 MHz, CD CIt
3) δ = 5°60 ~ 5.20 (m, 5H, H-1, 4, 5, 6, NH), 4.50 ~
4.15 (m, IH%H-3), 3, 55 (dd, IH%J,, =3.0Hz, J2.3 =
11.0Hz, H-2), 3.35(s, 3H, OMe
), 2, 19, 2.14, 2.03, 1.99.1. 98
(5s, each 3H, NHAc.

4xOAc) Elemental analysis theoretical value (CI7H23N O1°) C: 50.62%, H: 6.25%, N: 3.47% Actual value C: 50.53%, H: 6.03%, N: 3 .34
% [α] 0 -13.9'' (co, 79, cHcis) (Example 2) 1D-1-acetamide-2゜3.4.6
Synthesis of -tetra-0-acetyl-1-deoxy-5-0-methyl-neo-inositol (compound 26.) (fr) Starting from L-quebratitol, compound 26 (I
The synthesis step I) will be explained based on FIGS. 1a and 1c.

■According to Example 1, L-quebratitol (compound 1)
Compound 8 was synthesized from.

7 mJZ of pyridine and 7 m°C of acetic anhydride were added to 3.94 g (10.1 mmoj2) of Compound 8, and the mixture was stirred at room temperature for 16 hours. After adding methanol to the reaction solution under water cooling,
Toluene was added and the mixture was azeotroped with toluene, and the reaction solution was concentrated under reduced pressure.

The resulting residue was diluted with ethyl acetate at 250 m°C and added with 250 ml of IM hydrochloric acid. Saturated sodium bicarbonate solution 250mu, saturated salt solution 2
Washed sequentially with 50mu.

After drying the organic phase over anhydrous sodium sulfate, the sodium sulfate was filtered off. Toluene was added to the filtrate and azeotropically distilled with the toluene, and the filtrate was concentrated under reduced pressure.

The resulting residue was subjected to silica gel column chromatography (
Purified with ethyl acetate:toluene = 1:10), 1L-
1,4,5,6-tetra-0-acetyl-2-0-methyl-3-0-(p-toluenesulfonyl)-thyro-inositol (compound l) 4.03 g <Yield:
77%).

Compound 21 Rf=0.85 (Toluene:Ethyl acetate=1:2 (V:V)) Melting point Syrup IR (neat) 1750 cm-' (OAc)
, 1175 cm-' (502) 'H-NMR (90MH2, CDCf,) δ = 7.78.7.33 (2a%each 2H.

J=9.0H2,SO2), 5.61~5,11 (m, 4H,H-1,4,5,6), 4, 92
(t, IH.

J2.3 = J3.4 =9. 7Hz, H-3)
, 3, 51 (dd, I Hl J,, =3.4Hz% H-2), 3.06(S
, 3H, OMe) 2, 16, 2.11, 2.07, 1, 98 (4s,
each 3 H, 4x OA c ) Elemental analysis theoretical value (C22H2ao 12S ) C: 51.16%, ) I: 5.46% Actual value C: 51. ts %, H: 5.65% [α]
. -9,9゜(c 1.15, CHCn3) ■Compound l
412 mg (0,798 mmol 1L) and 284 mg (4J7 mmol 1L) of sodium azide and 9
Add 4mf of 0% 2-methoxyethanol aqueous solution,
The mixture was heated under reflux in a 20°C oil bath for 10 hours. Toluene was added to the reaction solution, and the mixture was azeotroped with toluene, and the reaction solution was concentrated under reduced pressure to obtain a brown solid residue.

Add 5 mJ2 of picillin and 5 mJL of acetic anhydride to this,
The mixture was stirred at room temperature for 4 hours. Toluene was added to the reaction solution, and the mixture was azeotroped with the toluene, and the reaction solution was concentrated under reduced pressure. Add 70 mj2 of ethyl acetate to the solution, and add distilled water (2 mj2) to it.
0mux2).

After drying the organic phase over anhydrous sodium sulfate, the sodium sulfate was filtered off. Toluene was added to the filtrate, azeotropically distilled with toluene, and the filtrate was concentrated under reduced pressure to obtain compound 22, compound
300 mg of syrupy residue, which is a mixture of Compound 24 and Compound 25, was obtained. This was purified by silica gel column chromatography (hexane: ethyl acetate = 3:1), and 1L-2,3,4,6-tetra-0-acetyl-1-azido-1-deoxy-5-0-methyl -Neo-inositol (Compound 22) 94 mg (Yield: 30
%), 1L-1,4,5,6-tetra-O-acetyl-
2-azido-2-deoxy-3-0-methyl-thyro-inositol (compound 23) 92 mg (yield: 30%) and 1n-1,4,5,6-tetra-0-acetyl-2
16 mg (yield: 5%) of -azido-2-deoxy-3-O-methyl-allo-inositol (compound 24) was obtained.

Compound Rf=0. 47 (hexane:ethyl acetate=2:1 (V:Vl) melting point
105-107℃ (ethanol) IR (neat)
2110cm"" (N3), 1750cm"" (OAc
) 'H-NMK (90MHz%CDCJ23) δ = 5, 62 (t, I H, Jl, 2 = J23
=2.5Hz, H-2), 5, 40-5, 05 (m, 3H, H-3, 4, 6), 4, 03 (dd, IH.

J, 6 = 1 1. 0Hz, H-4)3, 96
(t, IH.

J 4, = J, 6 = 2.　5Hz.

H-5), 3, 51 (s, 3H, OMe), 2,
18, 2, 14, 2, 07, 1, 98 (4s
, each 3 H, 4x OA c )
Elemental analysis theoretical value (C+sH2+Ns 09) C: 46.51%, H: 5.46%, N: 10.84% Actual value C: 46.7n%, H: 5.31%, N: 10.73% [α)'o +19.5° (c O, 80, CHC1L3) Compound 23 Rf = 0.50 (Hexane: Ethyl acetate = 2:1 (V:V)) Melting point
Syrup IR (+reat) 2100cm-'(N,,;1
760 cm-' (OAc) 'HNMR (90 MHz, CDC, Q3) δ = 5.55-5.00 (m, 4H, H-1,4,5,6), 3.90-3.48 (m, 2H,H-2,3), 3.45 (S,3H,OMe), 2.17.2,15.2.11.1,98 (4s %e
aeh3H, 4xOAc) Elemental analysis theoretical value (C1sH21N, Oe) C: 46.51%, H: 5.46%, N: 10.84% Actual value C: 46. 39%, H:5.2B%, N:
10.85% (α)o −4,1.

(c 1.04, CHCIts) Compound 2
4 Rf=0. 30 (Hexane: Ethyl acetate = 2:1 (V:V)) Melting point 1
75-176℃ (ethanol) IR (neat) 2
100cm-' (N3), 1 7 50cm-' (OA
c) 'HNMR (90MHz, CDCIts) δ = 5, 55~5, 05 (m, 4H%H', 4, 5, 6), 4, 3
0-4. 1 2 (m, 18% H-2)
, 3, 80 (t, IH.

J2=J54=3. 5 Hz sH-3), 3, 47 (s, 3H, OMe), 2,
19 , 2 , 14 , 2 , 09 , 2 , 01 (4s
% each 3 H, 4x OA c ) Elemental analysis theoretical value (C□IsH21N 30 *) C: 46.51
%, H: 5.46%, N: 10.84% Actual value C: 46.15%, H: 5.33%, N: 1
0.70% (α)D +24.7.

(cO,80,C)(C1Ls)■Compound 2
2 Add 1 ethanol to 35 mg (0.09 mmoJl)
mft, acetic anhydride 0.1 mJl, Raney Nickel-74
(Catalyst) One cup of small sorrel was added and stirred under hydrogen atmosphere (1 atm) for 1.5 hours. After filtering off the catalyst, the filtrate was subjected to silica gel column chromatography (ethanol:
Purify with toluene = 1:8) to obtain the desired 1D-1-
32 mg (yield: 88%) of acetamido-2,3,4,6-tetra-0-acetyl-1-deoxy-5-0-methyl-neo-inositol (compound 26) (H) was obtained.

Compound 26 (If) Rf=0. 37 (ethanol:toluene=1:5 (V:V)) Melting point 270-280°C (ethanol) IR (neat)
3260cm-'(NH), 1750cm-'(O
Ac), 1650cm-'(NAc), 1560cm-''(NAc)' HNMR(90MHz, CD CIls
) δ = 5, 60 (d, I H, Jl, NH-4, OHz, NH), 5.
50 (t, IH.

Jl, = J2.3 = 3.0Hz.

H-2), 5, 40 (dd, IH.

J 34 = 1 0.　0Hz.

H-3), 5, 15 (dd, IH, Jl, =1 2.0Hz
, J5. =3. OH2, H-6) 5, 0
8 (dd, IH.

Ja, =3. 0Hz, H4) ,4,
76 (ddd, 18% H-1), 3, 86
(t, IH, H-5), 3, 54 (
s, 3H, OMe), 2, 16, 2,
10, 1, 95, 1, 90 (4s,
3H, 6H, 3H, 3H.

NHAc, 4xOAc) Elemental analysis theoretical value (CIfH2SN Oto) C: 50.62%, H: 6.25%, N: 3.47% Actual value Confirmed by TLC, 'H-NMR and IR: C: 50.
53%, H: 6.15%, N: 3.47
% [α) a +2.7° (c O, 49, CHCA3) ■Compound 24
9, 7 mg (0,025 mmoJ2) and 0.5 mj of ethanol! , acetic anhydride 0.1 mA.

Add 1 small spatula of Raneynickel T4 (catalyst),
The mixture was stirred for 4 hours under a hydrogen atmosphere (1 atm). After the catalyst 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 19 mg of a pale green crystalline residue. This was purified by silica gel column chromatography (ethanol:toluene=1:8), and 1D-2-acetamido-1,4,5,6-tetra-〇-acetyl-
2-deoxy-3-O-methyl-allo-inositol (
Compound 20) (i) 8.4 mg (yield: 83%) was obtained. It should be noted that the obtained compound was Compound 20.

(Reference example 2) 1L-3-acetamide-1゜4.5.6
-Tetra-O-acetyl-3-deoxy-2-0-methyl-thyro-inositol (compound 17) Synthesis Example 2 - Compound 23 obtained according to ■ to ■ was mixed with ethanol, acetic anhydride, and Raney Nickel-T4 (catalyst). was added and stirred under a hydrogen atmosphere (1 atm). After the catalyst was filtered off, toluene was added to the filtrate and azeotroped with the toluene, and the filtrate was concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (ethanol:toluene concentration 1:8) to obtain 1L-3-acetamido-1,4,5,6-tetra-0-acetyl-3-deoxy-2-〇 -Methyl-thyroinositol (Compound 17) was obtained.

(Example 3) 10-3-acetamide-1°2.4.5
-Tetra-0-acetyl-3-deoxy-6-0-methyl-thyro-inositol (compound 1) (III) Synthesis of compound 30 (I) using L-quebratitol as a starting material
The synthesis step II) will be explained based on FIGS. 1a and 1d.

■According to Example 1, L-quebratitol (compound 1)
As a result, a mixture of compound and compound 10 was obtained. This was purified by silica gel column chromatography (ethyl acetate:toluene = 322-1:0) to produce 1L-1-0-7 cetyl-2-0-methyl-4-0-(p-) as a white solid. 3.36 g (yield: 21% based on compound 3) of tyro-inositol (compound AND) was obtained.

Compound 9 Rf=0.54 (MEK: Torson=1:1 (V:
V)) Melting point 162-163°C (ethanol) Elemental analysis theoretical value (CI8H2□09S) C: 49. 22%, H: 5.68% Actual value C: 49. oo%, H:5.66%[α
]o -23,4° (c 1.185, CH30H) ■Compound 9
6m of pyridine to 2.90g (7,431nmoj2)
and 6 mJ2 of acetic anhydride were added, and the mixture was stirred at room temperature for 15 hours. Toluene was added to the reaction solution, and the mixture was azeotroped with toluene, and the reaction solution was concentrated under reduced pressure to obtain a residue. Add this to ethyl acetate 2
The solution was diluted with 00mJ2 and washed sequentially with IM hydrochloric acid at 200mJ2, saturated sodium bicarbonate solution at 200mJ2, and saturated saline at 200mJ2. 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 an oily residue.

This was purified by silica gel column chromatography (ethyl acetate:toluene=1:8), and 1L-1,3,5
,6-tetra-0-acetyl-2-0-methyl-4-0
3.68 g (yield: 96%) of -(p-toluenesulfonyl)-thyro-inositol (compound l) was obtained.

Compound 27 Rf=0.77 (Toluene: Ethyl acetate=5:1 (V+V)) Melting point 1
29-131℃ (ethanol) IR (neat)
1775cm-"(OAc), 1175cm-'(
SO7) 'HNMR (90MH2, CDCJ23) δ = 7.70.7.28 (2d, each 2H%J = 9.0Hz.

SO2PhMe), 5.51-5.13 (m, 4H, H-1, 3, 5, 6), 5, 02 (t, IH.

Js, a = J4.5 = 9, 4 Hz
.

H-4), 3, 58 (dd, I H, J,, = 2.5Hz.

J2,3 = 9, 4 HZ, H-2)
, 3, 38 (s, 3H% OMe) , 2
, 44 (s, 3H, PhMe) , 2, 2
1, 2.16, 2.04, 1, 89 (4s %ea
ch 3 H, 4x OA c ) Elemental analysis theoretical value (C22H28012S) C: 51. ta%, H: 5.46% Actual value C: 51.23%, H: 5.08% [α].
-16,6° (c 1.23, CHCjZ3) ■ Compound 27
700 mg (1,36 mmol) with 480 mg (7,38 mmol2) of sodium azide and 90%
Add 7 mk of 2-methoxyethanol aqueous solution to 120
The mixture was heated under reflux for 20 hours in an oil bath at °C. Add toluene to the reaction solution, azeotrope the reaction solution with the toluene, and concentrate the reaction solution under reduced pressure.
1.11 g of brown solid residue was obtained.

Add 5m12 of picillin and 5mj2 of acetic anhydride to this,
Stirred at room temperature for 2.5 hours. Toluene was added to the reaction solution, and the mixture was azeotroped with the toluene, and the reaction solution was concentrated under reduced pressure. 150 ml of ethyl acetate was added thereto to precipitate it, and it was washed with distilled water (50 mρ 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 toluene, and the filtrate was concentrated under reduced pressure to obtain 600 mg of a syrupy residue, which was a mixture of Compound 28 and Compound 29.

This was purified by silica gel column chromatography (toluene:ethyl acetate = 6:1), and 1D-1
,2,4,5-tetra-O-acetyl-3-azido-3
-deoxy-6-0-methyl-thyro-inositol (compound 28) 392 mg (yield near 3%) and 1D-1
,2,4,6-tetra-0-acetyl-3-azido-3
84 mg (yield: 156%) of -deoxy-5-0-methyl-thyro-inositol (compound 29) was obtained.

Compound 28 Rf=0.33 (Toluene:Ethyl acetate=4:1 (V:V)) Melting point 9
1-93℃ (ethanol) IR (neat) 2110cm-' (N3), 17
55cm"" (OAc) 'HNMR (90MHz, CDCA3) δ = 5, 52 (dd, IH, J, 4, OHz.

J,, 6 = 3.0Hz, H-1), 5, 36 (dd, IH, J3.4 = 9.0Hz.

J4. S = 10.0Hz, H-4), 5, 14 (dd, 2H, tJs, s = 4. OHz.

J2. s = 1 0. 0Hz, H2, 5), 3,
34 (cod, IH% H-3), 3, 17
(dd, IH% H-6), 3, 50 (
s, 3H, OMe), 2, 16, 2.10, 2.0
8 (3s, 3H, 3H, 6H, 4xOAc) Elemental analysis theoretical value (CIsH21N 30 e) C: 46.51%, H: 5.46%, N: 10.84% Actual value C: 46.41%, H: 5.27%, N: 10.79% [α) o +13.7° (cl, o), CHCfs) Compound Rf = 0. 27 (Toluene:ethyl acetate=+:t(V:V)) Melting point 1
02-103℃ (ethanol) IR (neat) 2
110 cm-' (N3), 1755 cm (Act) 'H-NMR (90 MHz, CDC42s) δ = 5.48 (t, 2H.

Jl, 2 = J+, a = Js, a = 3.0Hz.

H-1,6), 5.8 (t.

J2. s = Js4 = 10.0Hz%H-3), 5.0
7 (dd, IH.

J4. , =s O, 0) (Z, H-5), 3.80 (
t, IH%H-4), 3.50 (dd, IH, H-2), 3.33 (s, 3H, OMe), 2.18.2.17.2.07 (3s, 3M, 6H , 3H, 4xOAc) Elemental analysis theoretical value (CIsH, +N s Oe) C: 46.51%, H: 5.46%, N: 10.84% Actual value C: 46.49%, H: 5.31 %, N: 10.88% [α) o +to, '7° (c O, 34, CHCf13) ■ Compound 28
To 105 mg (0,271 mmof) were added 1 ml of ethanol, 0.15 mJ2 of acetic anhydride, and 3 small spatulas of Raney Nickel-74 (catalyst), and the mixture was stirred under a hydrogen atmosphere (1 atm) for 4 hours. After filtering off the catalyst, the filtrate was purified by silica gel column chromatography (ethanol:toluene=1:10) to obtain the desired 10-
3-acetamido-1,2,4,5-tetra-O-acetyl-3-deoxy-6-〇-methyl-thyroinositol (compound 30) (III) 100 mg (yield: 91
%) was obtained.

Compound 30 (III) Rf=0. 39 (ethanol:toluene=1:8 (V:V)) Melting point 144-145°C (ethanol) IR (neat)
3360cm-'(NH), 3280cm-'
(NH), 1 750 cm-' (OAc), 1 670 cm-' (NHAc), 1550 cm-
'(NH) 'HNMR (90 MHz% CDC42s) δ = 5,04 (d, IH.

J 3. NH = 10, 0 Hz%NHA
c ) , 5 , 01 (dd, I H, Jl, 2 = 3.0Hz.

J, 6 = 4. 0Hz, H-1), 5, 30~
5, 10 (m, 3H% H-2,4,5), 4, 75-4.35 (m, IH, H-3)
, 3, 72 (dd, IH.

J, 6 = 2. 0Hz% H-6), 3.49
(s, 3H, OMe), 2, 36, 2.15, 2
．． 07, 2.04.1, 90 (5s, each
3H.

4XOAc%NHAc) elemental analysis Theoretical value (C+tH2sN　Oto) C: 50.62%, H: 6.25%, N: 3.47% Actual value C: 50.67%, H: 6.12%, N: 3.44% [α)D +14.6.

(c 1.28, CHCjLs) (Reference Example 3) 1L-1,3-di-0-acetyl-5,6
-0-isopropylidene-2-0-methyl-4-0-(
Synthesis of p-toluenesulfonyl)-thyroinositol (compound 11) 〛Compound 9 obtained according to Example 3-■
, DMF, p-toluenesulfonic acid hydrate, 2.
2-dimethoxypropane was added and stirred in a 55°C oil bath. After neutralizing the reaction solution by adding sodium hydrogen carbonate, ethyl acetate was added and the mixture was washed with water. 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 toluene, and the filtrate was concentrated under reduced pressure. Pyridine and acetic anhydride were added thereto, and the mixture was stirred at room temperature. Toluene was added to the reaction solution, the reaction solution was azeotroped with toluene, the reaction solution was concentrated under reduced pressure, and this was purified by silica gel column chromatography (MEK: toluene = 1:6) to obtain 1L-1,3-diO. -acetyl-5.6-〇-
Isopropylidene-2-0-methyl-4-O-(p-toluenesulfonyl)-thyro-inositol (Compound 1
1) was obtained.

(Reference Example 4) 1L-3-acetamide-1゜2.4.6
-Synthesis of Tetra-0-acetyl-3-deoxy-5-0-methyl-thyro-inositol (Compound 31) According to Example 3-■ to ■, Compound 28 and Compound 29
600 mg of syrup-like residue was obtained. This was subjected to silica gel column chromatography (toluene:
Purified with ethyl acetate = 6:1) to obtain 1L-3-azido-
1゜2.4.6-tetra-O-acetyl-3-deoxy-5-0-methyl-thyro-inositol (compound 29)
I got it.

Compound 29 36 mg (0,091 mmof)
To the mixture were added 1 mj2 of ethanol, 0.1 mjL of acetic anhydride, and 1 small spatula of Raney Nickel-74 (catalyst), and the mixture was stirred under a hydrogen atmosphere (1 atm) for 5 hours. After filtering off the catalyst, the filtrate was purified by silica gel column chromatography (ethanol:toluene=1:10), and 1L
32 mg (yield: 85.3%) of -3-acetamido-1,2,4,6-tetra-0-acetyl-3-deoxy-5-0-methyl-thyro-inositol (compound 31) was obtained.

Compound 31 Rf=0.30 (ethanol:toluene=1:5 (V:V)) Melting point 1
57-158℃ (ethanol) IR (neat) 3
370 cm-' (NH), 3300 cm-' (NH), 1750 cm-' (OAc), 1675 cm-' (NHAc), 1550 cm-' (NH) 'HNMR (90 MHz, CDCIts) δ = 5.66 (d, IH.

Js, 5H=10.0Hz%NH), 5, 44, 5, 30 (2dd% each IH.

Jl, 2 = Js, a = 3.　5Hz.

Jr, s = 4.　5Hz.

H-1, 6), 5, 13 (ddl 1H.

J 2. , =1 0.　01(z.

H-2), 5, 08 (t, IH.

J3.4 = J4. S = 10, OH
z 1H-4), 4, 53 (dt% 1 1ke-q, IH, H-3),
3, 64 (dd, IH% H-5), 3,
37 (s, 3H, OMe), 2, 16
, 2 , 13 , 2 , 08 , 2 , 00.1 , 9
0 (5s, each 3H% NHAC
.

4XOAC) Elemental analysis theoretical value (CIVH25N O+.) C: 50.62%, H: 6.25%, N: 3.47% Actual value C: 50.88%, H: 6.09%, N: 3
．． 44% [α] D -11,9''' (c 1.06, CHC1s) (Example 4)
1t, -1-acetamido-2゜3.4.5-tetra-
0-acetyl-1-deoxy-6-0-methyl-myo-
Synthesis of inositol (compound 36) (rV) Compound 36 (I
The synthesis step of V) will be explained based on FIGS. 1a and 1e.

■L-quebratitol (compound 1) 10.0g (DMFloomA at 51.5mm)
, 2,2-dimethoxypropane 31 mfl (25 [1 m
mol) 0.5 g of P-toluenesulfonic acid 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 bicarbonate,
The mixture was shaken with 300 mj2 of ethyl acetate and 300 mj2 water, and the reaction product was separated and extracted into an aqueous phase and an organic phase.

After drying the organic phase over anhydrous sodium sulfate, the sodium sulfate was filtered off, and the filtrate was concentrated under reduced pressure to give 1 L-1,2:3,4-di-0-isopropylidene- as a pale yellow syrup.
5-0-Methyl-thyro-inositol (Compound 2)6.
9g was obtained. This was purified by recrystallization from petroleum ether.

Compound 2 Rf=0.44 (MEK:Tolzen=2:1 (V:V))
1206 mg of the compound obtained in ■■ (0,7511
716 mg (3.75 ml) of P-)-luenesulfonyl chloride and 5 ml of pyridine were added to the mixture, and the mixture was stirred in an oil bath at 60° C. for 23 hours.

The reaction solution was added to 70 mJl of ethyl acetate! After diluting with water, it was washed with distilled water (20mj2x3).

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 toluene, and the filtrate was concentrated under reduced pressure to obtain a pale yellow oily residue.

This was purified by silica gel column chromatography (hexane:ethyl acetate + = -6:1, containing 1% triethylamine), and it was purified by silica gel column chromatography (hexane:ethyl acetate + = -6:1, containing 1% triethylamine). Methyl-6-0-(p-toluenesulfonyl)-thyro-inositol (compound 1)
317 mg (yield: 99%) was obtained.

Compound 32 Rf=0.31 (hexane:ethyl acetate=4:1 (V:V)) Melting point Syrup I R(neat) 1175cm-'(SO2)"
H-NMR (90MHz, CD CJ2s
) δ= 7.83.7. 34 (2d, each 2H.

J = 8, 0 Hz%502 PhMe), 5
．． 03 (t, IH, J8.a = Js, a = 3.5
H,,H-6), 4, 50-4, 20 (m, 2H1H-1,2), 3, 75-3, 50 (m, 3H,H-3,4,5), 3.25 ( s, 3H, OMe), 2, 44 (S, 3H, SO2PhMe)
, 1 , 42, 1 , 38, 1. 30 (3s
.

6 H, 3 H, 3 H, 2 ]
D -14,0@ (c 1.43, C, HCJ2s) ■Compound 32
120 mg (0,28 mmoJZ) with 91 mg (1,40 mmon) of sodium azide and DMSo
1mj2 was added thereto, and the mixture was stirred in a 120°C oil bath for 19 hours. After diluting the reaction solution with 60 mJ2 of ethyl acetate,
Washed with distilled water (20 mJ 1 x 2).

After drying the organic phase over anhydrous sodium sulfate, the sodium sulfate was filtered off. Toluene was added to the filtrate, azeotropically distilled with toluene, and the filtrate was concentrated under reduced pressure, leaving a residue of 82 mg
I got it. This was purified by silica gel column chromatography (toluene:ethyl acetate = 12:1, containing 1% triethylamine), and 1L-1-azido-1-deoxy-2,3:4,5-di-0-isopropylidene- 6-
o-Methyl-myo-inositol (compound 33) 59m
g (yield near 1%) and (IS.

4R, BS, 9R) -2-methoxy-6,611,,
11-tetramethyl-5,7,10゜12-tetraoxa-tricyclo[7,3゜0.04.8]dodec-2-
12 mg (yield: 217%) of ene (compound) was obtained.

Compound 33 Rf=0.48 (Toluene:Ethyl acetate=5:1 (V:V)) Melting point Syrup IR (neat) 2100cm-'(N3)' H
-NMR (90MHz, CDCIts
) δ = 4, 60~3. 25 (m, 6H.

)! -1, 2, 3, 4, 5, 6), 3, 53 (s, 3H, OMe), 1,
59, 1, 46, 1, 40 (3s, 3H,
6H,3H,2XCMe2) Elemental analysis theoretical value (C13H21N30s) C: 52.16%, H 7.07%, N: 14.04% Actual value C: 52.39%, H: 6.91%, N :13.78% [α)o +47.8° (cl, 12, CHCIls) Compound 34 Rf=0. 42 (Toluene: Ethyl acetate = 5:1 (V:V)) Melting point 7
0-73℃ IR (neat) 1645cm-'(C=C)'
H-NMR (90MH2, CDCf3) δ = 4, 95 (ddd, IH.

J,, = 1.0Hz.

J, 4 = 4.　0Hz.

J4. a”7.0Hz, H-4), 4, 66
(d d, IH.

J,,, =9. 5Hz, H-1), 4,
46 (dd, IH.

Ja, e”9.5Hz, H-8), 4, 14
(ddd, IH.

J, 9 = 9.　5Hz.

H-1,), 3, 82 (t, IH, H-9), 3,
67 (s, 31(,OMe), 1, 54
, 1 , 50 , 1 , 47 , 1 , 40 (4s %
each 3 H, 2x CM e 2 ) Elemental analysis theoretical value (CISH2゜05) C: 60.94%, H: 7.81% Actual value C: 60.69%, H near, 64% (α) o
-7,8° (co, 5, CHCl23') ■Compound 33° 60 mg (0,20mmon
), add 0.5 mA of ethanol and 1 nf of 2M hydrochloric acid,
The mixture was stirred in a 60°C oil bath for 1 hour. The reaction solution was sequentially azeotroped with ethanol and toluene and concentrated under reduced pressure to leave a residue of 46
mg was obtained. Add 2mjL of pyridine and anhydrous vinegar to this residue.
2 m 11 was added and stirred at room temperature for 2 hours. After diluting the reaction solution with 40ml of ethyl acetate, distilled water (5mJ
1X3).

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 toluene, and the filtrate was concentrated under reduced pressure to obtain 104 mg of a residue.

This was purified by silica gel column chromatography (toluene:ethyl acetate = 8:1), and 1L-2,3゜4.5-tetra-0-acetyl-1-azido-1-deoxy-6-〇-methyl 77 mg (yield: 99%) of rumioinositol (compound foot) was obtained.

Compound l to Rf = 0.48 (Toluene: Ethyl acetate = 5:1 (V:V)) Melting point 1
74.0-174.5℃ (ethanol) IR (neat) 2100cm-' (N3),
1760 cm-'(OAc)'H-NMR (90 MHz, CDCft3') δ = 5.55 (t, IH.

J+, = J2.3 = 2.5H,, H-2), 5, 47 (t, IH.

J3.4 = J4. ．． =1 0.　0Hz.

H-4), 5.10 (m, IH, H-5), 4, 91
(dd, IH% H-3,), 3, 87-3,
31 (m, 2H, H-1, 6), 3, 57 (s, 3H1OMe) 2, 19, 2
゜ 11, 2゜ o 2, 1, 98 (4s, egc
h3H,4xOAc) Elemental analysis theoretical value (CISH21N30s) C: 46.51%, H: 5.46%, N: 10.84% Actual value C: 46.24%, H: 5.37%, N: 10.81% [α)0 39° (c 1.175, CHCl5) ■ Compound 3
5 68 mg (0.18 mmoJl), ethanol 1 m fL% acetic anhydride 0.1 mfs Raney Nickel-7
4 (Catalyst) Add 2 small spatulas and heat under hydrogen atmosphere (1
The mixture was stirred for 3.5 hours at atmospheric pressure). After filtering off the catalyst, the filtrate was purified by silica gel column chromatography (ethanol:toluene=1:8) to obtain the desired 1L-1
-acetamido-2,3,4,5-tetra-0-acetyl-! -Deoxy-6-0-methyl-myo-inositol (Compound 36) (IV) was obtained.

Compound 36 (rV) Rf=0.36 (ethanol:toluene=t:a(v:v)) Melting point 1
89-190℃ (ethanol) IR (neat) 3
300cm-'(NH), 1750cm-'(OAc)
, 1650cm-' (NAc), 1550cm-'' (NH) 'H-NMR (90MHz, CD Cj2s
) δ = 5, 75~5. 45 (m, 11(,NH)
, 5, 53 (t, 1) (.

Jl, 2 = J2.3 ~ 3.　0Hz.

H-2), 5, 29 (m, 2H, J3.4 = J4.a = Js, a
=9. 0Hz, H-4, 5), 5, 02 (dd, IH, H-6), 3
, 45 (s, 3H, OMe) , 2 , 1
8, 2, 08, 2, 01, 1, 99.1,
95 (5s % each 3H, 4xOA
c.

NHAc) Elemental analysis theoretical value (CI7H2sN Or.) C: 50.62%, H: 6.25%, N: 3.47% Actual value C: 50.67%, H: 6.11%, N: 3
．． 45% [α)D +8.9” (c O,94, CHCl3) <Effects of the Invention> The present invention provides novel aminocyclitols, optically active 1D-2-acetamido-1,4,5, 6-tetra-O-acetyl-2-deoxy-3-O-methyl-
Allo-inositol, 1D-1-acetamido-2,3
,4,6-tetra-0-acetyl-1-deoxy-5-
〇-Methyl-neo-inositol, 1D-3-acetamido-1,2,4,5-tetra-0-acetyl-3-deoxy-6-0-methyl-thyro-inositol, and 1L-1-acetamido-2, 3,4,5-tetra-0
-Acetyl-1-deoxy-6-0-methyl-myo-inositol and methods for their production starting from L-quebratitol are provided.

The novel aminocyclitols of the present invention can be further converted into other aminocyclitols or converted into conductors, and can be used as pharmaceutical agents such as antibiotics such as kanamycin and netimicin, and anticancer drugs. It is a very useful compound as it can be used as a raw material for agricultural chemicals and other products.

Since the production method of the present invention uses ebrachitol as a starting material, which has no optical activity, there is no need to perform optical resolution.
In addition, compared to the conventional production method of aminocyclitol,
The number of steps is small and consists of simple steps.
Therefore, aminocyclitols can be provided at low cost and in high yield.

[Brief explanation of drawings]

$1a Figure shows 1L-1 from L-quebratitol,
It is a reaction route diagram leading to 3-di-0-acetyl-5,6-0-isopropylidene-2-0-methyl-4-〇-(p-toluenesulfonyl)-thyro-inositol. Figure 1b shows 1L-1-0-7 cetyl-2-〇-methyl-3-0-(p-toluenesulfonyl)-tyro-inositol to 1D-2-acetamide-1,4,5,6
FIG. 2 is a reaction route diagram leading to -tetra-O-acetyl-2-deoxy-3-O-methyl-allo-inositol (I). Figure 1C shows 1L-1-0-7 cetyl-2-〇-methyl-3-0-(p-toluenesulfonyl)-thyro-inositol to 1D-2-acetamido-1,4,5,
6-tetra-0-acetyl-2-deoxy-3-O-methyl-allo-inositol (I), 1n-1-acetamido-2,3,4,6-tetra-0-acetyl-1-deoxy-5 -0-methyl-neo-inositol (II
) and 1L-3-acetamido-1,4,5,6-tetra-0-acetyl-3-deoxy-2-0-methyl-
It is a reaction route diagram leading to tyro-inositol. Figure 1d shows 1D-3-acetamide-1,2,4,5
-tetra-0-acetyl-3-deoxy-6-0-methyl-thyro-inositol (III) and 1L-3-
FIG. 2 is a reaction route diagram leading to acetamido-1,2,4,6-tetra-0-acetyl-3-deoxy-5-〇-methyl-tyro-inositol. Figure 1e shows 1
L-1-acetamido-2,3,4,5-tetra-0-
FIG. 2 is a reaction route diagram leading to acetyl-1-deoxy-6-0-methyl-myo-inositol (rV). FIG, 1a ten FIG, lb F I G, lc ten FIG. 1e

Claims (12)

[Claims] (1) Optically active 1_D-2 represented by the following formula (I)
-acetamido-1,4,5,6-tetra-O-acetyl-2-deoxy-3-O-methyl-allo-inositol. ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・( I
) (2) Optically active 1_D-1- represented by the following formula (II)
Acetamide-2,3,4,6-tetra-O-acetyl-1-deoxy-5-O-methyl-neo-inositol. ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(II) (3) Optically active 1_D-3 represented by the following formula (III)
-acetamido-1,2,4,5-tetra-O-acetyl-3-deoxy-6-O-methyl-thyro-inositol. ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(III
) (4) Optically active 1_L-1- represented by the following formula (IV)
Acetamide-2,3,4,5-tetra-O-acetyl-1-deoxy-6-O-methyl-myo-inositol. ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(IV) (5) Optically active 1_D-2-acetamide-1,4 characterized by using L-quebratitol as a starting material
,5,6-tetra-O-acetyl-2-deoxy-3-
A method for producing O-methyl-allo-inositol. (6) A step of azidating the 3-position of L-quebratitol and then reducing the azide group to acetylate it, and a step of acetylating the hydroxyl groups at the 1, 4, 5, and 6-positions of L-quebratitol. An optically active 1_D- characterized by undergoing
A method for producing 2-acetamido-1,4,5,6-tetra-O-acetyl-2-deoxy-3-O-methyl-allo-inositol. (7) Optically active 1_D-1-acetamide-2,3 characterized by using L-quebratitol as a starting material
,4,6-tetra-O-acetyl-1-deoxy-5-
Method for producing O-methyl-neo-inositol. (8) 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 1-acetamido-2,3,4,6-tetra-O-acetyl-1-deoxy-5-O-methyl-neo-inositol. (9) Optically active 1_D-3-acetamide-1,2 characterized by using L-quebratitol as a starting material
,4,5-tetra-O-acetyl-3-deoxy-6-
A method for producing O-methyl-thyro-inositol. (10) A step of azidating the 5-position of L-quebratitol and then reducing the azide group and acetylating it;
Optically active 1_D characterized by passing through a step of acetylating the hydroxyl groups at positions 1, 3, 4, and 6 of quebratitol
A method for producing -3-acetamido-1,2,4,5-tetra-O-acetyl-3-deoxy-6-O-methyl-thyro-inositol. (11) Optically active 1_L-1-acetamide-2, characterized by using L-quebratitol as a starting material,
3,4,5-tetra-O-acetyl-1-deoxy-6
A method for producing -O-methyl-myo-inositol. (12) A step of azidating the 1-position of L-quebratitol and then reducing the azide group and acetylating it;
Optically active 1_L characterized by passing through a step of acetylating the hydroxyl groups at positions 3, 4, 5, and 6 of quebratitol
A method for producing -1-acetamido-2,3,4,5-tetra-O-acetyl-1-deoxy-6-O-methyl-myo-inositol.