1,1-diborylalkyl-1-metal compounds, preparation method thereof, and their applications toward synthesis of 1,1-diboronate ester compounds

1. A compound represented by Chemical Formula 1:

wherein, in Chemical Formula 1,

R 1 and R 2 are independently *—B(R 41 )(R 42 ), wherein R 41 and R 42 are independently hydrogen, a hydroxy, a C1-C30 alkyl, or a C1-C30 alkoxy, or are linked with each other to form a ring;

R 3 is hydrogen, a C1-C30 alkyl, a C1-C30 alkoxy, a C2-C30 alkenyl, a C2-C30 alkynyl, a C3-C30 cycloalkyl, a C3-C30 heterocycloalkyl, a C6-C30 aryl, or a C2-C30 heteroaryl;

M is a zinc group metal;

X 1 is a halogen;

the alkyl, the alkoxy, and the ring formed by linking with each other of R 41 and R 42 and the alkyl, the alkoxy, the alkenyl, the alkynyl, the cycloalkyl, the heterocycloalkyl, the aryl, and the heteroaryl of R 3 may independently be further substituted with at least one substituent selected from a halogen, a hydroxy, a cyano, a C1-C30 alkyl, a C1-C30 haloalkyl, a C1-C30 alkoxy, a C1-C30 aminoalkyl, a C3-C30 cycloalkyl, a C3-C30 heterocycloalkyl, a C6-C30 aryl, and a C2-C30 heteroaryl; and

the heterocycloalkyl and the heteroaryl of R 3 independently comprise at least one heteroatom selected from B, N, O, S, Se, —P(═O)—, —C(═O)—, Si, and P.

2. The compound of claim 1 , wherein R 1 and R 2 are independently hydroxyboronyl, pinacolboronyl ester, 2-pyrazol-5-yl aniline boronyl, benzo[1,3,2]dioxaborole, or 2,3-dihydro-1H-naphtho[1,8-de][1,3,2]diazaborinine.

3. The compound of claim 1 , which is represented by Chemical Formula 9:

wherein, in Chemical Formula 9,

R 3 is hydrogen, a C1-C30 alkyl, a C2-C30 alkenyl, a C3-C30 cycloalkyl, or a C3-C30 heterocycloalkyl;

M is a zinc group metal;

X 1 is a halogen;

the alkyl, the alkenyl, the cycloalkyl, or the heterocycloalkyl of R 3 is further substituted with at least one substituent selected from a halogen, a hydroxy, a cyano, a C1-C30 alkyl, a C1-C30 haloalkyl, a C3-C30 cycloalkyl, a C3-C30 heterocycloalkyl, a C6-C30 aryl, and a C2-C30 heteroaryl; and

the heterocycloalkyl and the heteroaryl of R 3 independently comprise at least one heteroatom selected from B, N, O, S, Se, —P(═O)—, —C(═O)—, Si, and P.

4. The compound of claim 1 , wherein R 3 is hydrogen, a C1-C7 alkyl, or a C2-C7alkenyl, or

the alkyl or the alkenyl of R 3 is further substituted with at least one substituent selected from a C1-C7 alkyl, a C1-C7 haloalkyl, a C3-C12 cycloalkyl, a C3-C12 heterocycloalkyl, a C6-C12 aryl, and a C6-C12 heteroaryl.

5. The compound of claim 1 , wherein M is Zn.

6. The compound of claim 1 , wherein X 1 is Br or Cl.

7. The compound of claim 1 , wherein M-X 1 is Zn—Br or Zn—Cl.

8. A method of preparing a compound of Chemical Formula 1, comprising

performing a dehydrogenation reaction of a compound of Chemical Formula 6 under a lithium base to prepare a compound of Chemical Formula 7, and reacting the compound of Chemical Formula 7 with a compound of Chemical Formula 8:

wherein, in Chemical Formulae 1 and 6 to 8,

R 1 and R 2 are independently *—B(R 41 )(R 42 ), wherein R 41 and R 42 are independently hydrogen, a hydroxy, a C1-C30 alkyl, or a C1-C30 alkoxy, or are linked with each other to form a ring;

R 3 is hydrogen, a C1-C30 alkyl, a C1-C30 alkoxy, a C2-C30 alkenyl, a C2-C30 alkynyl, a C3-C30 cycloalkyl, a C3-C30 heterocycloalkyl, a C6-C30 aryl, or a C2-C30 heteroaryl;

M is a zinc group metal;

X 1 is a halogen;

the alkyl, the alkoxy, and the ring formed by linking with each other of R 41 and R 42 and the alkyl, the alkoxy, the alkenyl, the alkynyl, the cycloalkyl, the heterocycloalkyl, the aryl, and the heteroaryl of R 3 may independently be further substituted with at least one substituent selected from a halogen, a hydroxy, a cyano, a C1-C30 alkyl, a C1-C30 haloalkyl, a C1-C30 alkoxy, a C1-C30 aminoalkyl, a C3-C30 cycloalkyl, a C3-C30 heterocycloalkyl, a C6-C30 aryl, and a C2-C30 heteroaryl; and

the heterocycloalkyl and the heteroaryl of R 3 independently comprise at least one heteroatom selected from B, N, O, S, Se, —P(═O)—, —C(═O)—, Si, and P.

9. The method of claim 8 , wherein the lithium base is selected from butyl lithium, lithium dicyclohexylamide, lithium tetramethylpiperidide, lithium isopropylcyclohexylamide, and lithium diisopropylamide.

10. A method of preparing a 1,1-diboronate ester compound, comprising:

reacting a halogenated aromatic compound or a halogenated vinyl compound; a compound of Chemical Formula 1; and a monodentate ligand-containing transition metal compound under a solvent to prepare a compound of Chemical Formula 2:

wherein, in Chemical Formulae 1 and 2,

R 1 and R 2 are independently *—B(R 41 )(R 42 ), wherein R 41 and R 42 are independently hydrogen, a hydroxy, a C1-C30 alkyl, or a C1-C30 alkoxy, or are linked with each other to form a ring;

R 3 is hydrogen, a C1-C30 alkyl, a C1-C30 alkoxy, a C2-C30 alkenyl, a C2-C30 alkynyl, a C3-C30 cycloalkyl, a C3-C30 heterocycloalkyl, a C6-C30 aryl, or a C2-C30 heteroaryl;

M is a zinc group metal;

X 1 is a halogen;

A is not present or is an aromatic ring;

R 11 is hydrogen, a halogen, a hydroxy, a cyano, a C1-C30 alkyl, a C1-C30 alkoxy, a C2-C30 alkenyl, a C2-C30 alkynyl, a C6-C30 aryl, a C2-C30 heteroaryl, —O—Si(R 31 ) 3 , or —C(O)—R 32 , wherein R 31 and R 32 are independently hydrogen, a hydroxy, a C1-C30 alkyl, or a C1-C30 alkoxy;

n is an integer ranging from 1 to 3, and when n is 2 or 3, each R 11 is the same or different;

the alkyl, the alkoxy, and the ring formed by linking with each other of R 41 and R 42 , the alkyl, the alkoxy, the alkenyl, the alkynyl, the cycloalkyl, the heterocycloalkyl, the aryl, and the heteroaryl of R 3 , the aromatic ring of A, and the alkyl, the alkoxy, the alkenyl, the alkynyl, the aryl, and the heteroaryl of R 1 are independently further substituted with at least one substituent selected from a halogen, a hydroxy, a cyano, a C1-C30 alkyl, a C1-C30 haloalkyl, a C1-C30 alkoxy, a C1-C30 aminoalkyl, a C3-C30 cycloalkyl, a C3-C30 heterocycloalkyl, a C6-C30 aryl, and a C2-C30 heteroaryl; and

the heterocycloalkyl and the heteroaryl of R 3 and the heteroaryl of R 11 independently include at least one heteroatom selected from B, N, O, S, Se, —P(═O)—, —C(═O)—, Si, and P.

11. The method of claim 10 , wherein the reaction is performed at about 25° C. to about 100° C.

12. The method of claim 10 , wherein the monodentate ligand-containing transition metal compound is a composite of a compound selected from [Rh(COD)Cl] 2 , [Rh(COD) 2 ]X (X═BF 4 , ClO 4 , SbF 6 , or CF 3 SO 3 ), [Ir(COD)Cl] 2 , [Ir(COD) 2 ]X (X═OMe, BF 4 , ClO 4 , SbF 6 , or CF 3 SO 3 ), Ru(COD)Cl 2 , [Pd(CH 3 CN) 4 [BF 4 ] 2 , Pd 2 (dba) 3 , and [Pd(C 3 H 5 )Cl] 2 , and a phosphine-based compound.

13. The method of claim 12 , wherein the phosphine-based compound is selected from triphenylphosphine, tri-ortho-tolyl phosphine, tri-meta-tolyl phosphine, tri-para-tolyl phosphine, tris(4-trifluoromethylphenyl) phosphine, diphenyl(para-tolyl) phosphine, cyclohexyldiphenyl phosphine, tris(2,6-dimethoxyphenyl) phosphine, tris(4-methoxyphenyl) phosphine, trimesitylphosphine, tris-3,5-xylylphosphine, tricyclohexyl phosphine, tribenzyl phosphine, benzyldiphenyl phosphine, and diphenyl-normal-propyl phosphine.

14. The method of claim 10 , wherein R 1 and R 2 are independently hydroxyboronyl, pinacolboronylester, 2-pyrazol-5-yl aniline boronyl, benzo[1,3,2]dioxaborole, or 2,3-dihydro-1H-naphtho[1,8-de][1,3,2]diazaborinine.

15. The method of claim 10 , wherein the solvent is selected from aprotic solvents.

16. A method of preparing a 1,1-diboronate ester compound, comprising:

reacting a compound of Chemical Formula 5; a compound of Chemical Formula 1; and a monodentate ligand-containing transition metal compound under a solvent to prepare a compound of Chemical Formula 4:

wherein, in Chemical Formulae 1, 4, and 5,

R 1 and R 2 are independently *—B(R 41 )(R 42 ), wherein R 41 and R 42 are independently hydrogen, a hydroxy, a C1-C30 alkyl, or a C1-C30, or are linked with each other to form a ring;

R 3 is hydrogen, a C1-C30 alkyl, a C1-C30 alkoxy, a C2-C30 alkenyl, a C2-C30 alkynyl, a C3-C30 cycloalkyl, a C3-C30 heterocycloalkyl, a C6-C30 aryl, or a C2-C30 heteroaryl;

M is a zinc group metal;

X 1 is a halogen;

R 21 is hydrogen, a halogen, a hydroxy, a cyano, a C1-C30 alkyl, a C1-C30 alkoxy, a C2-C30 alkenyl, a C2-C30 alkynyl, a C6-C30 aryl, a C2-C30 heteroaryl, —O—Si(R 31 ) 3 , or —C(O)—R 32 , wherein R 31 and R 32 are independently hydrogen, a hydroxy, a C1-C30 alkyl, or a C1-C30 alkoxy;

Boc is tert-butoxycarbonyl;

the alkyl, the alkoxy, and the ring formed by linking with each other of R 41 and R 42 and the alkyl, the alkoxy, the alkenyl, the alkynyl, the cycloalkyl, the heterocycloalkyl, the aryl, and the heteroaryl of R 3 , and the alkyl, the alkoxy, the alkenyl, the alkynyl, the aryl, and the heteroaryl of R 21 are independently further substituted with at least one substituent selected from a halogen, a hydroxy, a cyano, a C1-C30 alkyl, a C1-C30 haloalkyl, a C1-C30 alkoxy, a C1-C30 aminoalkyl, a C3-C30 cycloalkyl, a C3-C30 heterocycloalkyl, a C6-C30 aryl, and a C2-C30 heteroaryl; and

the heterocycloalkyl and the heteroaryl of R 3 and the heteroaryl of R 21 independently comprise at least one heteroatom selected from B, N, O, S, Se, —P(═O)—, —C(═O)—, Si, and P.

17. The method of claim 16 , wherein the reaction is performed at about 10° C. to 35° C.

18. The method of claim 16 , wherein the monodentate ligand-containing transition metal compound may be a composite of a compound selected from Rh(COD)Cl] 2 , [Rh(COD) 2 ]X (X═BF 4 , ClO 4 , SbF 6 , or CF 3 SO 3 ), [Ir(COD)Cl] 2 , [Ir(COD) 2 ]X (X═OMe, BF 4 , ClO 4 , SbF 6 , or CF 3 SO 3 ), Ru(COD)Cl 2 , [Pd(CH 3 CN) 4 [BF 4 ] 2 , Pd 2 (dba) 3 , and [Pd(C 3 H 5 )Cl] 2 , with an aminophosphone-based compound.

19. The method of claim 18 , wherein the aminophosphone-based compound is the following L1:

20. The method of claim 16 , wherein R 1 and R 2 are independently hydroxyboronyl, pinacolboronylester, 2-pyrazol-5-yl aniline boronyl, benzo[1,3,2]dioxaborole or 2,3-dihydro-1H-naphtho[1,8-de][1,3,2]diazaborinine.