POLYMERIC SALEN COMPOUNDS AND METHODS THEREOF

• US 20090030172A1
• Filed: 03/13/2006
• Published: 01/29/2009
• Est. Priority Date: 03/14/2005
• Status: Active Grant

• Current Assignee: Georgia Tech Research Corporation (University System of Georgia)
• Original Assignee: Georgia Tech Research Corporation (University System of Georgia)
• Inventors: Weck, Marcus, Zheng, Xiaolai, Holbach, Michael Johannes, Jones, Christopher W.
• Granted Patent: US 8,207,365 B2
• Time in Patent Office: Days
• US Class Current: 528/271
• CPC Class Codes: B01J 2231/487 by hydrolysis
• CPC Class Codes: B01J 2531/0216 Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp
• CPC Class Codes: B01J 2531/0252 Salen ligands or analogues, e.g. derived from ethylenediamine and salicylaldehyde
• CPC Class Codes: B01J 2531/845 Cobalt
• CPC Class Codes: B01J 31/1666 the linkage established via an olefin metathesis reaction
• CPC Class Codes: B01J 31/1683 the linkage being to a soluble polymer, e.g. PEG or dendrimer, i.e. molecular weight enlarged complexes
• CPC Class Codes: B01J 31/2243 At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
• CPC Class Codes: C07F 13/00 Compounds containing elements of Groups 7 or 17 of the Periodic Table
• CPC Class Codes: C07F 15/06 Cobalt compounds

Abstract

The present disclosure provides a polymerizable compound of the formula (I)

where the R₁, R₂, R′₁, R′₂, X₁ to X₈, Y₁, Y₂, M and L have any of values as defined in the specification. The disclosure also provides an oligomer, a homo-polymer, or a co-polymer of compound of the formula (I). The disclosure also provides methods for preparing the compound of the formula (I) and methods for preparing polymers of the compound of the formula (I), and to methods and intermediates useful for preparing them. The disclosure also provides methods for the use of the polymers of formula (I) as chiral catalysts in enantioselective preparative processes.

Claims

1. A polymerizable chiral compound of formula (I)

2. The compound of claim 1, wherein X₁, X₂, X₃, X₄, X₅, X₆, X₇, X₈, Y₁ and Y₂ are independently H, C₁-C₆ alkyl, and C₁-C₆ alkoxy, and at least one X₁, X₂, X₃, X₄, X₅, X₆, X₇, X₈, Y₁ and Y₂ is -L′

-Z-P.

3. The compound of claim 1, wherein

X₁, X₃, X₄, X₅, X₆, X₇ and X₈ are independently H or t-butyl;

Y₁ and Y₂ are H;

R₁ and R₁₂ are a carbocycle or heterocycle comprising 4 to 10 atoms, when R₂ and R′

₁ are H, or R₁ and R₁₂ are H, when R₂ and R′

₁ are a carbocycle or heterocycle comprising 4 to 10 atoms;

R₃ is a single carbon-carbon bond; and

X₂ is -L′

-Z-P.

4. The compound of claim 1, wherein

X₁, X₃, X₆, and X₈ are H;

X₄, X₅, and X₇ are t-butyl;

Y₁ and Y₂ are H;

R₁ and R′

₂ are a —

(CH₂)₄—

, when R₂ and R′

₁ are H, or R₁ and R′

₂ are H, when R₂ and R′

₁ are a —

(CH₂)₄—

;

R₃ is a single carbon-carbon bond;

X₂ is -L′

-Z-P where

L′

is a single carbon-carbon bond or —

(C≡

C)_k—

Ar—

, where k is 1;

Z is —

C(═

O)O—

or —

O—

C(═

O)—

;

P is C₂-C₆ alkenyl, cycloalkenyl, or polycycloalkenyl;

M is Co, Mn, or mixtures thereof; and

L is absent, or a counterion selected from F, Cl, Br, I, —

O(C═

O)alkyl, —

O—

S(═

O)₂—

R′

₄, wherein R′

₄ is aryl, arylC₂-C₆ allyl, heteroaryl, C₁-C₆ alkyl, cycloallyl, heterocycle, PF₆, B(Ar)₄, or B(halo)₃, where halo is F, Cl, Br, or I;

or a salt or hydrate thereof.

5. The compound of claim 1, wherein

P is ethylenyl, cyclooctenyl, or norbonenyl;

M is Co or Mn; and

L is absent or a halide anion selected from F, Cl, Br, and I;

or a salt or hydrate thereof.

6. A homopolymer of the compound of claim 1 of the formula:

7. The homopolymer of claim 6 of the formula:

8. The homopolymer of claim 6 of the formula:

9. The homopolymer of claim 6 of the formula:

10. A copolymer of the formula:

{(A)_m-(B)_p}

where

A is the polymerized compound of claim 1 of formula (I);

B is a co-polymerized monomer;

m is an integer from 1 to about 1,000; and

p is an integer from 1 to about 10,000.

11. The copolymer of claim 10 where

A is the polymerized compound of claim 1 of formula (I);

B is a co-polymerized monomer of at least one olefin, perfluorinated olefin, silane or siloxane substituted olefin, diene, alkenylaryl, acylate, or mixtures thereof;

m is an integer from 10 to about 100; and

p is an integer from 10 to about 1,000.

12. The copolymer of claim 10 of the formula:

13. The copolymer of claim 10 of the formula:

14. A method for preparing a homo-polymer of the compound of formula (I) of claim 1, comprising:

heating the compound of formula (I) with a free radical initiator.

15. A method for preparing an oligomeric-ring or macrocyclic-ring homo-polymer of the compound of formula (I) of claim 1, comprising:

reacting the compound of formula (I) with a 3°

Grubbs catalyst.

16. A method for preparing a co-polymer of the compound of formula (I) of claim 1, comprising:

heating the compound of formula (I) with a free radical initiator and at least one monomer selected from olefin, diene, alkenylaryl, acylate, or mixtures thereof.

17. A method of preparing a chiral epoxide or chiral 1,2-diol by stereoselective hydrolysis of a racemic epoxide of the formula

18. A method of preparing an asymmetric epoxide from an unsaturated substrate comprising:

contacting the unsaturated substrate with a catalytic amount of a chiral homo-polymer or chiral copolymer of the compound of formula (I) of claim 1, wherein

X₁, X₃, X₆, and X₈ are H;

X₄, X₅, and X₇ are t-butyl;

Y₁ and Y₂ are H;

R₁ and R′

₂ are a —

(CH₂)₄—

, when R₂ and R′

₁ are H, or R₁ and R′

₂ are H, when R₂ and R′

₁ are a —

(CH₂)₄—

;

R₃ is a single carbon-carbon bond;

X₂ is -L′

-Z-P where

L′

is —

(C≡

C)_k—

Ar—

, where k is 1;

Z is —

C(═

O)O—

or —

O—

C(═

O)—

;

P is C₂-C₆ alkenyl, cycloalkenyl, or polycycloalkenyl;

M is Mn; and

L is absent, or a counterion;

or a salt or hydrate thereof.

19. A single-pot method for preparing the compound of formula (I) of claim 1, comprising:

reacting a salicylaldehyde compound of the formula (A);

20. The method of claim 19 wherein formula (I) is