Patent EA-001377-B1 (EA)
Title: Chiral bisphosphines compounds, complexes based thereon and process for forming same
Inventor: PYE PHILIIP
IPC: C07F9/655
Filed: 1997-06-10
Abstract: 1. Chiral bisphosphines of formula   wherein R is C1-4 alkyl, C3-6 cycloalkyl, or aryl unsubstituted or substituted with -F, -CH3, -CF3 or CH3O-; and X<1> and X<2> link the two R2P-substituted benzenes and independently form a 2 to 4 membered link consisting of 2 to 4 carbon atoms and up to one unsubstituted or substituted heteroatom selected from O, S, SO, SO2 or   2. The compound of claim 1, wherein the number of atoms in the X<1> link is the same as the number of atoms in the X<2> link. 3. The compound of claim 2, of the formula   4. The compound of claim 3, of the formula    5. A complex (BISPHOS) M->Ln,  wherein n is an integer and is 0, 1, 2, 3 or 4; M is Rh, Ir, Ru or Pd; L is a ligand reversibly coordinated for replacement by substrate; BISPHOS is a compound of the formulae   wherein R is C1-4 alkyl, C3-6 cycloalkyl, or aryl unsubstituted or substituted with -F, -CH3, -CF3 or CH3O-; and X<1> and X<2> link the two R2P-substituted benzenes and independently form a 2 to 4 membered link consisting of 2 to 4 carbon atoms and up to one unsubstituted or substituted heteroatom selected from O, S, SO, SO2 or   6. The complex of claim 5, wherein the ligand is (a) norbornadiene; (b) C1-4OH; (c) NR<1>R<2>R<3>, and R<1> and R<2> and R<3> are independently H, C1-4 alkyl, C3-7cycloalkyl, aryl, pyridyl, or tetrahydrofuryl; or (d) a diene of the formula   wherein m is an integer and is 1, 2, 3 or 4; n is an integer and is 0,1,2,3 or 4; and R<4>, R<5>, R<6> and R<7> are independently H, C1-4 alkyl; (e) ether, of the formula R<1>OR<2>, or a cyclic ether of the formula    wherein p is an integer and is 2, 3, 4 or 5; (f) bis-ether, of the formula   wherein m is defined as above; (g) bis-alcohol of the formula HO-(CR<8>R<9>)p-OH wherein p is defined as above; and R<8> and R<9> are independently H, C1-4 alkyl or aryl; or (h) ethylene.  7. The complex of claim 5 or 6, wherein the number of atoms in the X<1> link of BISPHOS is the same as the number of atoms in the X<2> link of BISPHOS. 8. The complex of claim 7, wherein M is Rh or Ir, n is 1 and L is cyclooctadiene. 9. The complex of claim 5 or 6, of the structure   10. The complex of claim 5 or 6, of the structure   11. The complex of claim 10, of the structure   wherein M is Rh or Ir. 12. The complex of claim 9, of the structure    wherein M is Rh or Ir. 13. The complex of claim 5 or 6, of the structure   wherein M is Rh or Ir. 14. The complex of claim 5, of the structure   wherein R<10> is CF3 or CH3. 15. The complex of claim 5, of the structure   16. A partly or completely enantiomerically pure compound of the formula   17. A process for forming a chiral bisphosphine compound (S)-40 or (R)-40   wherein R is C1-4 alkyl, C3-6 cycloalkyl, or aryl unsubstituted or substituted with -F, -CH3, -CF3 or CH3O-; comprising the steps of (a) treating a racemic phosphinyl compound 41   with a resolving agent to afford chiral (S)-41 or (R)-41; and (b) reducing the chiral (S)-41 or (R)-41. 18. The process of claim 17, wherein the resolving agent is dibenzoyl-L-tartaric acid and each R is phenyl.