Asymmetric auxiliary group
To provide a chiral reagent or a salt thereof. The chiral reagent has following chemical formula (I). In the formula (I), G 1 and G 2 are independently a hydrogen atom, a nitro group (—NO 2 ), a halogen atom, a cyano group (—CN), a group of formula (II) or (III), or both G 1 and G 2 taken together to form a group of formula (IV).
1. An oligonucleotide on a solid support having the structure of:
wherein:
G 1 is a hydrogen atom, a nitro group, a halogen atom, a cyano group, or a group of formula (II), (III) or (V);
G 2 is a nitro group, a halogen atom, a cyano group, or a group of formula (II), (III), or (V); or
both G 1 and G 2 are taken together to form a group of formula (IV);
wherein formula (II) is:
and
G 21 to G 23 are independently a hydrogen atom, a nitro group, a halogen atom, a cyano group or C 1-3 alkyl group;
wherein formula (III) is:
and
G 31 to G 33 are independently C 1-4 alkyl group, C 1-4 alkoxy group, C 6-14 aryl group, C 7-14 aralkyl group, C 1-4 alkyl C 6-14 aryl group, C 1-4 alkoxy C 6-14 aryl group, or C 6-14 aryl C 1-4 alkyl group;
wherein formula (IV) is:
and
G 41 to G 46 are independently a hydrogen atom, a nitro group, a halogen atom, a cyano group or C 1-3 alkyl group;
wherein formula (V) is:
and
G 51 to G 53 are independently a hydrogen atom, a nitro group, a halogen atom, a cyano group, C 1-3 alkyl group or C 1-3 alkyloxy group,
G 3 and G 4 are independently a hydrogen atom, C 1-3 alkyl group, C 6-14 aryl group, or both G 3 and G 4 are taken together to form a heteroatom-containing ring that has 3 to 16 carbon atoms;
G 5 is a protective group of a hydroxyl group;
each R 2 is independently hydrogen, —OH, —SH, —NR d R d , —N 3 , halogen, alkyl, alkenyl, alkynyl, alkyl-Y 1 —, alkenyl-Y 1 —, alkynyl-Y 1 —, aryl-Y 1 —, heteroaryl-Y 1 —, —OR b , or —SR b , wherein R b is a blocking moiety;
Y 1 is O, NR d , S, or Se;
R d is independently hydrogen, alkyl, alkenyl, alkynyl, aryl, acyl, substituted silyl, carbamate, —P(O)(R e ) 2 , or —HP(O)(R e );
R e is independently hydrogen, alkyl, aryl, alkenyl, alkynyl, alkyl-Y 2 —, alkenyl-Y 2 —, alkynyl-Y 2 —, aryl-Y 2 —, or heteroaryl-Y 2 —, or a cation which is Na + , Li + , or K + ;
Y 2 is O, S, or NR d wherein R d is independently hydrogen, alkyl, alkenyl, alkynyl, aryl, acyl, substituted silyl, or carbamate;
represents a solid support optionally with a linking moiety; and
each Bs is independently a group selected from the groups represented by following formula (VI) to (XI) or derivatives thereof:
2. The oligonucleotide of claim 1 , wherein G 3 and G 4 are taken together to form a heteroatom-containing ring that has 3 to 16 carbon atoms.
3. The oligonucleotide of claim 1 , wherein G 3 and G 4 are taken together to form a heteroatom-containing ring that has 4 carbon atoms.
4. The oligonucleotide of claim 1 , wherein G′ is a hydrogen atom, a nitro group, a halogen atom, a cyano group, or a group of formula (II), (III) or (V).
5. The oligonucleotide of claim 1 , wherein G 2 is a nitro group, a cyano group, or a group of formula (II), (III) or (V), or both G 1 and G 2 are taken together to form a group of formula (IV).
6. The oligonucleotide of claim 1 , wherein G 1 is a hydrogen atom.
7. The oligonucleotide of claim 1 , wherein each of G 1 and G 2 is a group of formula (II), wherein G 21 to G 23 are independently a hydrogen atom, a nitro group, a halogen atom, a cyano group, or C 1-3 alkyl group.
8. The oligonucleotide of claim 1 , wherein each of G 1 and G 2 is a group of formula (II), wherein each of G 21 to G 23 is a hydrogen atom.
9. The oligonucleotide of claim 1 , wherein G 2 is a group of formula (II), wherein G 21 to G 23 are independently a hydrogen atom, a nitro group, a halogen atom, a cyano group or C 1-3 alkyl group.
10. The oligonucleotide of claim 1 , wherein G 2 is a group of formula (II), wherein each of G 21 and G 22 is a hydrogen atom and G 23 is a nitro group.
11. The oligonucleotide of claim 1 , wherein G 2 is a group of formula (III), wherein G 31 to G 33 are independently C 1-4 alkyl group, C 6-14 aryl group, C 7-14 aralkyl group, C 1-4 alkyl C 6-14 aryl group, C 1-4 alkoxy C 6-14 aryl group, or C 6-14 aryl C 1-4 alkyl group.
12. The oligonucleotide of claim 1 , wherein G 2 is a group of formula (III), wherein G 31 to G 33 are independently C 1-4 alkyl group, C 6 aryl group, C 7-10 aralkyl group, C 1-4 alkyl C 6 aryl group, C 1-4 alkoxy C 6 aryl group, or C 6 aryl C 1-4 alkyl group.
13. The oligonucleotide of claim 1 , wherein G 2 is a group of formula (III), wherein G 31 to G 33 are independently C 1-4 alkyl group, or C 6 aryl group.
14. The oligonucleotide of claim 1 , wherein G 2 is a group of formula (III), wherein G 31 to G 33 are independently C 1-4 alkyl group.
15. The oligonucleotide of claim 1 , wherein G 2 is a group of formula (III), wherein G 31 and G 33 are C 6 aryl group and G 32 is C 1-4 alkyl group.
16. The oligonucleotide of claim 1 , wherein G 2 is a group of formula (III), wherein the C 1-4 alkyl group is a methyl group.
17. The oligonucleotide of claim 1 , wherein G 2 is a group of formula (III), wherein G 31 and G 33 are phenyl.
18. The oligonucleotide of claim 1 , wherein G 1 and G 2 are taken together to form a group of formula (IV), wherein G 41 to G 46 are independently a hydrogen atom, a nitro group, a halogen atom, a cyano group, or C 1-3 alkyl group.
19. The oligonucleotide of claim 1 , wherein G 1 and G 2 are taken together to form a group of formula (IV), wherein each of G 41 to G 46 is a hydrogen atom.
20. The oligonucleotide of claim 1 , wherein G 2 is a group of formula (V), wherein each of G 51 to G 53 are independently a hydrogen atom, a nitro group, a methyl group, or a methoxy group.
21. The oligonucleotide of claim 1 , wherein G 2 is a group of formula (V), wherein each of G 51 and G 53 is a hydrogen atom and G 53 is a 4-methyl group.
22. The oligonucleotide of claim 1 , wherein a R 2 is hydrogen.
23. The oligonucleotide of claim 1 , wherein a R 2 is halogen.
24. The oligonucleotide of claim 1 , wherein a R 2 is alkyl-Y 1 —, alkenyl-Y 1 —, alkynyl-Y 1 —, aryl-Y 1 —, or heteroaryl-Y 1 —.
25. The oligonucleotide of claim 1 , wherein a R 2 is alkyl-Y 1 —.
26. The oligonucleotide of claim 1 , wherein Y 1 is O.
27. The oligonucleotide of claim 1 , wherein G 5 is trityl, 4-monomethoxytrityl, 4,4′-dimethoxytrityl, 4,4′,4″-trimethoxytrityl, 9-phenylxanthin-9-yl (Pixyl) or 9-(p-methoxyphenyl)xanthin-9-yl (MOX).
28. The oligonucleotide of claim 1 , wherein G 5 is 4,4′-dimethoxytrityl.
29. The oligonucleotide of claim 1 , wherein Bs is independently an adenine, a thymine, a cytosine, a guanine, or a derivative thereof.
30. The oligonucleotide of claim 1 , wherein each Bs is independently selected from:
wherein each of R 8 to R 10 is independently C 1-10 alkyl, C 6 -C 10 aryl, C 6 -C 10 aralkyl, or C 6 -C 10 aryloxyalkyl.
31. The oligonucleotide of claim 30 , wherein R 8 is methyl, isopropyl, phenyl, benzyl, or phenoxymethyl.
32. The oligonucleotide of claim 30 , wherein R 9 and R 10 are C 1-4 alkyl group.