Substituted paracyclophane derivatives in asymmetric catalysis
AssigneeJohnson Matthey PLC
InventorsBeatriz Dominguez, William Patrick Hems, Antonio Zanotti-Gerosa
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Abstract
A substituted paracyclophane is described of formula (I) wherein X1 and X2 are linking groups comprising between 2 to 4 carbon atoms, Y1 and Y2 are selected from the group consisting of hydrogen, halide, oxygen, nitrogen, alkyl, cycloalkyl, aryl or heteroaryl, Z1, Z2 and Z3 are substituting groups that optionally contain functional groups, a, b, c, d, e and f are 0 or 1 and a+b+c+d+e+f=1 to 6. Preferably X1 and X2 are —(C2H4)— and a+b+c+d+e+f=1 or 2. The substituted paracyclophane provides transition metal catalysts that demonstrate high activity and selectivity for asymmetric reactions
Claims16
A substituted paracyclophane of formula (I)
- wherein X1 and X2 are linking groups comprising between 2 to 4 carbon atoms, Y1 and Y2 are selected from the group consisting of hydrogen, halide, oxygen, nitrogen, alkyl, cycloalkyl, aryl and heteroaryl, and Z1, Z2 and Z3 are substituting groups selected from the group consisting of:
- (i) C1-C30 branched or linear alkyl, aryl, aralkyl or alkaryl groups,
- (ii) functional groups selected from the group consisting of halide, hydroxyl, alkoxy, carbonyl, carboxyl, anhydride, methacryl, epoxide, vinyl, nitrile, nitro, sulphate, sulphonyl, silyl, mercapto, amino, amine, imine, amide and imide, and
- (iii) C1-C30 branched or linear alkyl, aryl, aralkyl or alkaryl groups bearing thereon one or more of said functional groups,
- wherein —a, b, c, d, e and f are 0 or 1, and (a+b+c+d+e+f)=1 to 6.
A method for preparation of a substituted paracyclophane of (I) by,
- (a) performing a substitution reaction on a pseudo-ortho dibromoparacyclophane to form an Intermediate substituted pseudo-ortho dibromoparacyclophane of formula (II), and
- (b) reacting the-substituted pseudo-ortho dibromoparacyclophane with a phosphorus compound comprising P(Y1Y2), wherein X1 and X2 are linking groups comprising between 2 to 4 carbon atoms, Y1 and Y2 are selected from the group consisting of hydrogen, halide, oxygen, nitrogen, alkyl, cycloalkyl, aryl and heteroaryl, and Z1, Z2 and Z3 are substituting groups selected from the group consisting of:
- (i) C1-C30 branched or linear alkyl, aryl, aralkyl, or alkaryl groups,
- (ii) functional groups selected from the group consisting of halide, hydroxyl, alkoxy, carbonyl, carboxyl, anhydride, methacryl, epoxide, vinyl, nitrile, nitro, sulphate, sulphonyl, silyl, mercapto, amino, amine, imine, amide and imide, and
- (iii) C1-C30 branched or linear alkyl, aryl, aralkyl or alkaryl groups bearing thereon one or more of said functional groups,
- wherein a, b, c, d, e and f are 0 or 1, and (a+b+c+d+e+f)=1 to 6.
A substituted pseudo-ortho dibromoparacyclophane of formula (III)
- wherein X1 and X2 are linking groups comprising between 2 to 4 carbon atoms, Z1, Z2 and Z3 are substituting groups at least one of which comprises a functional group selected from the group consisting of hydroxyl, alkoxy, carboxyl, anhydride, methacryl, epoxide, vinyl, nitrile, nitro, sulphate, sulphonyl, mercapto, sulphide amino, amine, imine, and imide, a, b, c, d, e and f are 0 or 1, and (a+b+c+d+e+f)=1 to 6.
A metal complex comprising the reaction product or a metal compound and a substituted paracyclophane of formula (I)
- wherein X1 and X2 are linking groups comprising between 2 to 4 carbon atoms, Y1 and Y2 are selected from the group consisting of hydrogen, halide, oxygen, nitrogen, alkyl, cycloalkyl, aryl and heteroaryl, and Z1, Z2 and Z3 are substituting groups selected from the group consisting of:
- (i) C1-C30 branched or linear alkyl, aryl, aralkyl or alkaryl groups,
- (ii) functional groups selected from the group consisting of halide, hydroxyl, alkoxy, carbonyl, carboxyl, anhydride, methacryl, epoxide, vinyl, nitrile, nitro, sulphate, sulphonyl, silyl, mercapto, amino, amine, imine, amide and imide, and
- (iii) C1-C30 branched or linear alkyl, aryl, aralkyl or alkaryl groups bearing thereon one or more of said functional groups,
- wherein a, b, c, d, e and f are 0 or 1, and (a+b+c+d+e+f)=1 to 6.
Dependencies are inferred from the claim text.