Phosphine derivative and polymer thereof and transition metal complex comprising the same

• US 6,465,594 B1
• Filed: 03/30/2000
• Issued: 10/15/2002
• Est. Priority Date: 03/30/1999
• Status: Active Grant

• Current Assignee: Takasago International Corporation
• Original Assignee: Takasago International Corporation
• Inventors: Tamao, Kyoko, Sayo, Noboru
• Primary Examiner(s): Wu, David W.
• Assistant Examiner(s): CHOI, LING SIU
• Application Number:
  US09/539,413
• Time in Patent Office: 929 Days
• Field of Search: 526/240, 526/274, 526/347, 526/340
• US Class Current: 526/274
• CPC Class Codes: C07C 231/18 by stereospecific synthesis
• CPC Class Codes: C07F 15/0033 Iridium compounds
• CPC Class Codes: C07F 15/004 without a metal-carbon linkage
• CPC Class Codes: C07F 15/0046 Ruthenium compounds
• CPC Class Codes: C07F 15/0053 without a metal-carbon linkage
• CPC Class Codes: C07F 15/006 Palladium compounds
• CPC Class Codes: C07F 15/0066 without a metal-carbon linkage
• CPC Class Codes: C07F 15/0073 Rhodium compounds
• CPC Class Codes: C07F 15/008 without a metal-carbon linkage
• CPC Class Codes: C07F 9/5027 Polyphosphines
• CPC Class Codes: Y02P 20/582 Recycling of unreacted starting or intermediate materials

Abstract

Disclosed are a phosphine derivative represented by formula (I):

wherein Ar represents a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group, a transition metal complex comprising the phosphine derivative or a polymer thereof as a ligand, and a process for producing an optically active amino acid compound by asymmetric hydrogenation using the transition metal complex as a catalyst.

Claims

1. An oligomer or polymer having a structural unit represented by formula (III):

wherein Ar represents a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group, and k represents an integer of 2 to 100.

3. A transition metal complex obtained by allowing a transition metal compound to react with the oligomer or polymer according to claim 1 or the copolymer according to 2.

4. A transition metal complex according to claim 3, which has a structural unit represented by formula (VI):

wherein Ar and k are as defined in claim 1 or 2;

M represents ruthenium, rhodium, iridium or palladium;

W represents an allyl group, a methallyl group, 1,5-cyclooctadiene, norbornadiene, a halogen atom, an acetoxy group or an acetylacetonato group;

Y represents a hydrogen atom, a halogen atom, ClO₄, BF₄, PF₆, BPh₄ (tetraphenylborate), OTf (trifluoromethanesulfonyloxy) or SbF₆;

Z represents a substituted or unsubstituted benzene; and

p, q, and r each represent a number of 0 to 2 provided that p, q, and r do not simultaneously represent 0.

5. A transition metal complex according to claim 3, which has a structural unit represented by formula (VI) and a structural unit represented by formula (IV) and/or a structural unit represented by formula (V):

wherein Ar, R¹, R², k, l, and m are as defined in claim 1 or 2;

M represents ruthenium, rhodium, iridium or palladium;

W represents an allyl group, a methallyl group, 1,5-cyclooctadiene, norbornadiene, a halogen atom, an acetoxy group or an acetylacetonato group;

Y represents a hydrogen atom, a halogen atom, ClO₄, BF₄, PF₆, BPh₄ (tetraphenylborate), OTf (trifluoromethanesulfonyloxy) or SbF₆;

Z represents a substituted or unsubstituted benzene; and

p, q, and r each represent a number of 0 to 2 provided that p, q, and r do not simultaneously represent 0.

2. A copolymer having a structural unit represented by formula (III) and a structural unit represented by formula (IV) and/or a structural unit represented by formula (V):

wherein Ar represents a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group;

R¹ represents a hydrogen atom, a lower alkyl group, a lower alkoxy group or a halogen atom;

R² represents a hydrogen atom or a methyl group;

k represents an integer of 2 to 100; and

l and m each represent an integer of 0 to 1000 provided that l and m do not simultaneously represent 0 and that the sum of k, l, and m ranges from 10 to 1000.

6. A process for producing an oligomer or polymer having a structural unit represented by formula (III):

wherein Ar represents a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group; and

k represents an integer of 2 to 100,

comprising solution polymerization or suspension polymerization of a phosphine derivative represented by formula (I);

wherein Ar is as defined above.

7. A process for producing a copolymer having a structural unit represented by formula (III) and a structural unit represented by formula (IV) and/or a structural unit represented by formula (V):

wherein Ar represents a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group;

R¹ represents a hydrogen atom, a lower alkyl group, a lower alkoxy group or a halogen atom;

R² represents a hydrogen atom or a methyl group;

k represents an integer of 2 to 100; and

l and m each represent an integer of 0 to 1000 provided that l and m do not simultaneously represent 0 and that the sum of k, l, and m ranges from 10 to 1000,

comprising solution copolymerization or suspension copolymerization of a phosphine derivative represented by formula (I);

wherein Ar is as defined above,

with a styrene derivative represented by formula (IVa);

wherein R¹ and R² are as defined above,

and/or divinylbenzene represented by formula (Va);

8. A process for producing a transition metal complex having a structural unit represented by formula (VI):

wherein Ar represents a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group;

M represents ruthenium, rhodium, iridium or palladium;

W represents an allyl group, a methallyl group, 1,5-cyclooctadiene, norbornadiene, a halogen atom, an acetoxy group or an acetylacetonato group;

Y represents a hydrogen atom, a halogen atom, ClO₄, BF₄, PF₆, BPh₄ (tetraphenylborate), OTf (trifluoromethanesulfonyloxy) or SbF₆;

Z represents a substituted or unsubstituted benzene;

k represents an integer of 2 to 100; and

p, q, and r each represent a number of 0 to 2 provided that p, q, and r do not simultaneously represent 0,

comprising solution polymerization or suspension polymerization of a transition metal complex represented by formula (II);

wherein Ar, M, W, Y, Z, p, q, and r are as defined above.

9. A process for producing a transition metal complex having a structural unit represented by formula (VI) and a structural unit represented by formula (IV) and/or a structural unit represented by formula (V):

wherein Ar represents a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group;

R¹ represents a hydrogen atom, a lower alkyl group, a lower alkoxy group or a halogen atom;

R² represents a hydrogen atom or a methyl group;

M represents ruthenium, rhodium, iridiumorpalladium;

W represents an allyl group, a methallyl group, 1,5-cyclooctadiene, norbornadiene, a halogen atom, an acetoxy group or an acetylacetonato group;

Y represents a hydrogen atom, a halogen atom, ClO₄, BF₄, PF₆, BPh₄ (tetraphenylborate), OTf (trifluoromethanesulfonyloxy) or SbF₆;

Z represents a substituted or unsubstituted benzene;

p, q, and r each represent a number of 0 to 2 provided that p, q, and r do not simultaneously represent 0;

k represents an integer of 2 to 100; and

l and m each represent an integer of 0 to 1000 provided that l and m do not simultaneously represent 0 and that the sum of k, l, and m ranges from 10 to 1000,

comprising solution copolymerization or suspension copolymerization of a transition metal complex represented by formula (II);

wherein Ar, M, W, Y, Z, p, q, and r are as defined above,

with a styrene derivative represented by formula (IVa);

wherein R¹ and R² are as defined above,

and/or divinylbenzene represented by formula (Va);