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US 2020/0048272 A1Published application
3-phenyl-2,3,4,8,9,10-hexahydropyrano[2,3-f]chromene derivative and method for synthesizing optical isomer thereof
AssigneeGlaceum Inc.
InventorsSang Ku YOO, Jin Wook CHUNG, In Geun JO, Ji Young KIM, Jeong Ho IM, Ku Suk KANG, Jin Young KIM
Life of this patent
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Abstract
The present invention relates to a method for synthesizing a 3-phenyl-2,3,4,8,9,10-hexahydropyrano[2,3-f]chromene derivative and an optical isomer thereof, and an intermediate Compound which may be used for the synthesis method, and when the method and the intermediate Compound are used, the 3-phenyl-2,3,4,8,9,10-hexahydropyrano[2,3-f]chromene derivative and the optical isomer thereof may be effectively synthesized.
Claims19
A method for synthesizing a 3-phenyl-2,3,4,8,9,10-hexahydropyrano[2,3-f]chromene derivative of Chemical Formula (I), the method comprising:
- a) coupling a Compound represented by Chemical Formula 1 with a Compound represented by Chemical Formula 2 to form a Compound of Chemical Formula 3;
- b) reducing the Compound of Chemical Formula 3 to form a Compound of Chemical Formula 4;
- and
- c) cyclizing the Compound of Chemical Formula 4 to form a Compound of Chemical Formula 5:
- [Reaction Formula 1]
- wherein,
- R1 and R2 are each independently hydrogen atom;
- hydroxy group;
- straight or branched C1 to C6 alkyl group unsubstituted or substituted with halogen atom, straight or branched C1 to C5 alkyl group, straight or branched C1 to C5 alkoxy group, or straight or branched C1 to C3 thioalkyl group;
- halogen atom;
- straight or branched C1 to C6 alkoxy group unsubstituted or substituted with halogen atom, straight or branched C1 to C5 alkyl group, straight or branched C1 to C5 alkoxy group, or straight or branched C1 to C3 thioalkyl group;
- straight or branched C1 to C4 thioalkyl group unsubstituted or substituted with halogen atom, straight or branched C1 to C5 alkyl group, straight or branched C1 to C5 alkoxy group, or straight or branched C1 to C3 thioalkyl group;
- allyloxy group unsubstituted or substituted with halogen atom, straight or branched C1 to C5 alkyl group, straight or branched C1 to C5 alkoxy group, or straight or branched C1 to C3 thioalkyl group;
- or aryloxy group unsubstituted or substituted with halogen atom, straight or branched C1 to C5 alkyl group, straight or branched C1 to C5 alkoxy group, or straight or branched C1 to C3 thioalkyl group;
- R3 is hydrogen atom or C1 to C2 alkyl group or C1 to C2 alkoxy group;
- R4 and R5 are each independently hydrogen atom or C1 to C6 alkyl group;
- P is a protecting group selected from straight or branched C1 to C4 alkyl group unsubstituted or substituted with halogen atom, straight or branched C1 to C5 alkyl group, straight or branched C1 to C5 alkoxy group, or straight or branched C1 to C3 thioalkyl group;
- benzyl group unsubstituted or substituted with halogen atom, straight or branched C1 to C5 alkyl group, straight or branched C1 to C5 alkoxy group, or straight or branched C1 to C3 thioalkyl group;
- allyl group unsubstituted or substituted with halogen atom, straight or branched C1 to C5 alkyl group, straight or branched C1 to C5 alkoxy group, or straight or branched C1 to C3 thioalkyl group;
- tert-butyldimethylsilyl group;
- tert-butyldiphenylsilyl group;
- methylphenylsilyl group;
- trimethylphenylsilyl group;
- MeSO2 and p-TsSO2;
- n is 1 to 3;
- and
- two or more OPs are the same or different from each other.
24 more elements
A Compound represented by the following Chemical Formula 3, or a solvate thereof:
- [Chemical Formula 3]
- wherein,
- R1 and R2 are each independently hydrogen atom;
- hydroxy group;
- straight or branched C1 to C6 alkyl group unsubstituted or substituted with halogen atom, straight or branched C1 to C5 alkyl group, straight or branched C1 to C5 alkoxy group, or straight or branched C1 to C3 thioalkyl group;
- halogen atom;
- straight or branched C1 to C6 alkoxy group unsubstituted or substituted with halogen atom, straight or branched C1 to C5 alkyl group, straight or branched C1 to C5 alkoxy group, or straight or branched C1 to C3 thioalkyl group;
- straight or branched C1 to C4 thioalkyl group unsubstituted or substituted with halogen atom, straight or branched C1 to C5 alkyl group, straight or branched C1 to C5 alkoxy group, or straight or branched C1 to C3 thioalkyl group;
- allyloxy group unsubstituted or substituted with halogen atom, straight or branched C1 to C5 alkyl group, straight or branched C1 to C5 alkoxy group, or straight or branched C1 to C3 thioalkyl group;
- or aryloxy group unsubstituted or substituted with halogen atom, straight or branched C1 to C5 alkyl group, straight or branched C1 to C5 alkoxy group, or straight or branched C1 to C3 thioalkyl group;
- R3 is hydrogen atom or C1 to C2 alkyl group or C1 to C2 alkoxy group;
- R4 and R5 are each independently hydrogen atom or C1 to C6 alkyl group;
- P is a protecting group selected from straight or branched C1 to C4 alkyl group unsubstituted or substituted with halogen atom, straight or branched C1 to C5 alkyl group, straight or branched C1 to C5 alkoxy group, or straight or branched C1 to C3 thioalkyl group;
- benzyl group unsubstituted or substituted with halogen atom, straight or branched C1 to C5 alkyl group, straight or branched C1 to C5 alkoxy group, or straight or branched C1 to C3 thioalkyl group;
- allyl group unsubstituted or substituted with halogen atom, straight or branched C1 to C5 alkyl group, straight or branched C1 to C5 alkoxy group, or straight or branched C1 to C3 thioalkyl group;
- tert-butyldimethylsilyl group;
- tert-butyldiphenylsilyl group;
- methylphenylsilyl group;
- trimethylphenylsilyl group;
- MeSO2 and p-TsSO2;
- n is 1 to 3;
- and
- two or more OPs are the same or different from each other.
20 more elements
A Compound represented by the following Chemical Formula 4, or a solvate thereof:
- [Chemical Formula 4]
- wherein,
- R1 and R2 are each independently hydrogen atom;
- hydroxy group;
- straight or branched C1 to C6 alkyl group unsubstituted or substituted with halogen atom, straight or branched C1 to C5 alkyl group, straight or branched C1 to C5 alkoxy group, or straight or branched C1 to C3 thioalkyl group;
- halogen atom;
- straight or branched C1 to C6 alkoxy group unsubstituted or substituted with halogen atom, straight or branched C1 to C5 alkyl group, straight or branched C1 to C5 alkoxy group, or straight or branched C1 to C3 thioalkyl group;
- straight or branched C1 to C4 thioalkyl group unsubstituted or substituted with halogen atom, straight or branched C1 to C5 alkyl group, straight or branched C1 to C5 alkoxy group, or straight or branched C1 to C3 thioalkyl group;
- allyloxy group unsubstituted or substituted with halogen atom, straight or branched C1 to C5 alkyl group, straight or branched C1 to C5 alkoxy group, or straight or branched C1 to C3 thioalkyl group;
- or aryloxy group unsubstituted or substituted with halogen atom, straight or branched C1 to C5 alkyl group, straight or branched C1 to C5 alkoxy group, or straight or branched C1 to C3 thioalkyl group;
- R3 is hydrogen atom or C1 to C2 alkyl group or C1 to C2 alkoxy group;
- R4 and R5 are each independently hydrogen atom or C1 to C6 alkyl group;
- P is a protecting group selected from straight or branched C1 to C4 alkyl group unsubstituted or substituted with halogen atom, straight or branched C1 to C5 alkyl group, straight or branched C1 to C5 alkoxy group, or straight or branched C1 to C3 thioalkyl group;
- benzyl group unsubstituted or substituted with halogen atom, straight or branched C1 to C5 alkyl group, straight or branched C1 to C5 alkoxy group, or straight or branched C1 to C3 thioalkyl group;
- allyl group unsubstituted or substituted with halogen atom, straight or branched C1 to C5 alkyl group, straight or branched C1 to C5 alkoxy group, or straight or branched C1 to C3 thioalkyl group;
- tert-butyldimethylsilyl group;
- tert-butyldiphenylsilyl group;
- methylphenylsilyl group;
- trimethylphenylsilyl group;
- MeSO2 and p-TsSO2;
- n is 1 to 3;
- and
- two or more OPs are the same or different from each other.
20 more elements
A 3-phenyl-2,8-dihydropyrano[2,3-f]chromene Compound represented by the following Chemical Formula 5, or a solvate thereof:
- [Chemical Formula 5]
- wherein,
- R1 and R2 are each independently hydrogen atom;
- hydroxy group;
- straight or branched C1 to C6 alkyl group unsubstituted or substituted with halogen atom, straight or branched C1 to C5 alkyl group, straight or branched C1 to C5 alkoxy group, or straight or branched C1 to C3 thioalkyl group;
- halogen atom;
- straight or branched C1 to C6 alkoxy group unsubstituted or substituted with halogen atom, straight or branched C1 to C5 alkyl group, straight or branched C1 to C5 alkoxy group, or straight or branched C1 to C3 thioalkyl group;
- straight or branched C1 to C4 thioalkyl group unsubstituted or substituted with halogen atom, straight or branched C1 to C5 alkyl group, straight or branched C1 to C5 alkoxy group, or straight or branched C1 to C3 thioalkyl group;
- allyloxy group unsubstituted or substituted with halogen atom, straight or branched C1 to C5 alkyl group, straight or branched C1 to C5 alkoxy group, or straight or branched C1 to C3 thioalkyl group;
- or aryloxy group unsubstituted or substituted with halogen atom, straight or branched C1 to C5 alkyl group, straight or branched C1 to C5 alkoxy group, or straight or branched C1 to C3 thioalkyl group;
- R3 is hydrogen atom or C1 to C2 alkyl group or C1 to C2 alkoxy group;
- R4 and R5 are each independently hydrogen atom or C1 to C6 alkyl group;
- P is a protecting group selected from straight or branched C1 to C4 alkyl group unsubstituted or substituted with halogen atom, straight or branched C1 to C5 alkyl group, straight or branched C1 to C5 alkoxy group, or straight or branched C1 to C3 thioalkyl group;
- benzyl group unsubstituted or substituted with halogen atom, straight or branched C1 to C5 alkyl group, straight or branched C1 to C5 alkoxy group, or straight or branched C1 to C3 thioalkyl group;
- allyl group unsubstituted or substituted with halogen atom, straight or branched C1 to C5 alkyl group, straight or branched C1 to C5 alkoxy group, or straight or branched C2 to C3 thioalkyl group;
- tert-butyldimethylsilyl group;
- tert-butyldiphenylsilyl group;
- methylphenylsilyl group;
- trimethylphenylsilyl group;
- MeSO2 and p-TsSO2;
- n is 1 to 3;
- and
- two or more OPs are the same or different from each other.
20 more elements
A method for synthesizing an optical isomer of a 3-phenyl-2,3,4,8,9,10-hexahydropyrano[2,3-f]chromene derivative of Chemical Formula (I), the method comprising:
- A) coupling a Compound represented by Chemical Formula 1 with a Compound represented by Chemical Formula 2 to form a Compound of Chemical Formula 3;
- B) reducing the Compound of Chemical Formula 3 to form a Compound of Chemical Formula 4;
- C) cyclizing the Compound of Chemical Formula 4 to form a Compound of Chemical Formula 5;
- and
- D) subjecting the Compound represented by Chemical Formula 5 to an asymmetric hydrogenation reaction to form an optical isomer Compound of Chemical Formula 6a (R-form) or 6b (S-form):
- [Reaction Formula 2]
- wherein,
- R1 and R2 are each independently hydrogen atom;
- hydroxy group;
- straight or branched C1 to C6 alkyl group unsubstituted or substituted with halogen atom, straight or branched C1 to C5 alkyl group, straight or branched C1 to C5 alkoxy group, or straight or branched C1 to C3 thioalkyl group;
- halogen atom;
- straight or branched C1 to C6 alkoxy group unsubstituted or substituted with halogen atom, straight or branched C1 to C5 alkyl group, straight or branched C1 to C5 alkoxy group, or straight or branched C1 to C3 thioalkyl group;
- straight or branched C1 to C4 thioalkyl group unsubstituted or substituted with halogen atom, straight or branched C1 to C5 alkyl group, straight or branched C1 to C5 alkoxy group, or straight or branched C1 to C3 thioalkyl group;
- allyloxy group unsubstituted or substituted with halogen atom, straight or branched C1 to C5 alkyl group, straight or branched C1 to C5 alkoxy group, or straight or branched C1 to C3 thioalkyl group;
- or aryloxy group unsubstituted or substituted with halogen atom, straight or branched C1 to C5 alkyl group, straight or branched C1 to C5 alkoxy group, or straight or branched C1 to C3 thioalkyl group;
- R3 is hydrogen atom or C1 to C2 alkyl group or C1 to C2 alkoxy group;
- R4 and R5 are each independently hydrogen atom or C1 to C6 alkyl group;
- P is a protecting group selected from straight or branched C1 to C4 alkyl group unsubstituted or substituted with halogen atom, straight or branched C1 to C5 alkyl group, straight or branched C1 to C5 alkoxy group, or straight or branched C1 to C3 thioalkyl group;
- benzyl group unsubstituted or substituted with halogen atom, straight or branched C1 to C5 alkyl group, straight or branched C1 to C5 alkoxy group, or straight or branched C1 to C3 thioalkyl group;
- allyl group unsubstituted or substituted with halogen atom, straight or branched C1 to C5 alkyl group, straight or branched C1 to C5 alkoxy group, or straight or branched C1 to C3 thioalkyl group;
- tert-butyldimethylsilyl group;
- tert-butyldiphenylsilyl group;
- methylphenylsilyl group;
- trimethylphenylsilyl group;
- MeSO2 and p-TsSO2;
- n is 1 to 3;
- and
- two or more OPs are the same or different from each other.
25 more elements
An optical isomer Compound represented by the following Chemical Formula 6a (R-form) or 6b (S-form), or a solvate thereof:
- [Chemical Formula 6a]
- [Chemical Formula 6b]
- wherein,
- R1 and R2 are each independently hydrogen atom;
- hydroxy group;
- straight or branched C1 to C6 alkyl group unsubstituted or substituted with halogen atom, straight or branched C1 to C5 alkyl group, straight or branched C1 to C5 alkoxy group, or straight or branched C1 to C3 thioalkyl group;
- halogen atom;
- straight or branched C1 to C6 alkoxy group unsubstituted or substituted with halogen atom, straight or branched C1 to C5 alkyl group, straight or branched C1 to C5 alkoxy group, or straight or branched C1 to C3 thioalkyl group;
- straight or branched C1 to C4 thioalkyl group unsubstituted or substituted with halogen atom, straight or branched C1 to C5 alkyl group, straight or branched C1 to C5 alkoxy group, or straight or branched C1 to C3 thioalkyl group;
- allyloxy group unsubstituted or substituted with halogen atom, straight or branched C1 to C5 alkyl group, straight or branched C1 to C5 alkoxy group, or straight or branched C1 to C3 thioalkyl group;
- or aryloxy group unsubstituted or substituted with halogen atom, straight or branched C1 to C5 alkyl group, straight or branched C1 to C5 alkoxy group, or straight or branched C1 to C3 thioalkyl group;
- R3 is hydrogen atom or C1 to C2 alkyl group or C1 to C2 alkoxy group;
- R4 and R5 are each independently hydrogen atom or C1 to C6 alkyl group;
- P is a protecting group selected from straight or branched C1 to C4 alkyl group unsubstituted or substituted with halogen atom, straight or branched C1 to C5 alkyl group, straight or branched C1 to C5 alkoxy group, or straight or branched C1 to C3 thioalkyl group;
- benzyl group unsubstituted or substituted with halogen atom, straight or branched C1 to C5 alkyl group, straight or branched C1 to C5 alkoxy group, or straight or branched C1 to C3 thioalkyl group;
- allyl group unsubstituted or substituted with halogen atom, straight or branched C1 to C5 alkyl group, straight or branched C1 to C5 alkoxy group, or straight or branched C1 to C3 thioalkyl group;
- tert-butyldimethylsilyl group;
- tert-butyldiphenylsilyl group;
- methylphenylsilyl group;
- trimethylphenylsilyl group;
- MeSO2 and p-TsSO2;
- n is 1 to 3;
- and
- two or more OPs are the same or different from each other.
21 more elements
Dependencies are inferred from the claim text.