Asymmetric catalysis based on chiral phospholanes and hydroxyl phospholanes

A compound of the following formula or its corresponding enantiomer:

• 54
• wherein:
• A) R is each C1-C8 alkyl, C1-C8 alkyl aryl;
• aryl C1-C8 alkyl, aryl, each of which may be substituted with carboxylic acid, alkoxy, hydroxy, C1-C8 alkylthio, thiol, dialkylamino, or diphenylphosphino, or chiral oxazoline;
• and
• B) R1 is each H, C1-C8 alkyl, silane, aryl, a water soluble unit, or a linked polymer chain or linked inorganic support;
• and
• C)R2 is either R, H, or a symmetrical bidentate structure having the formula
• 55
• wherein
• 56
• is
• i) —(CH2)n— where n is an integer from 1 to 8;
• or
• ii) —(CH2)nX(CH2)m— where n and m are the same or different integers from 1 to 8, and X is O, S, NR4, PR4, AsR4, SbR4, divalent aryl, divalent fused aryl, divalent 5-membered heterocyclic ring, or divalent fused heterocyclic ring, where R4 is C1-C8 alkyl, aryl, substituted aryl, or substituted C1-C8 alkyl;
• or
• iii) 1,2-divalent phenyl, 2,2′-divalent 1,1′biphenyl, 2,2′-divalent, 1,1′ binapthyl, or ferrocene, each of which may be substituted independently with C1-C8 alkyl or aryl, F, Cl, Br, I, COOR5, SO3R5, PO3R52, OR5, SR5, NR52, PR52, AsR52, SbR52, nitro, vinyl, substituted vinyl, alkynyl wherein R5 is H, C1-C8 alkyl, substituted C1-C8 alkyl, C1-C8 fluoroalkyl, C1-C8 perfluoroalkyl, aryl or substituted aryl;
• and
• wherein Z is a compound selected from the group of compounds having the following formula and their corresponding enantiomers:
• 57

A compound selected from the group of compounds of the following formula:

• 63
• wherein
• A) R is C1-C8 alkyl, C1-C8 alkyl aryl, aryl C1-C8 alkyl, or aryl, each of which may be substituted with carboxylic acid, alkoxy, hydroxy, alkylthio, thiol, dialkylamino, diphenylphosphino or chiral oxazoline;
• and
• B) R1 is H, C1-C8 alkyl, silane, aryl, a water soluble unit, or a linked polymer chain, or linked inorganic support;
• and
• C)R2 is either R, H, or a symmetrical bidentate structure having the following formula:
• 64
• wherein
• 65
• is
• i) —(CH2)n— where n is an integer from 1 to 8;
• or
• ii) —(CH2)nX(CH2)m— where n and m are the same or different integers from 1 to 8, and X is O, S, NR4, PR4, AsR4, SbR4, divalent aryl, divalent fused aryl, divalent 5-membered heterocyclic ring, or divalent fused heterocyclic ring, where R4 is C1-C8 alkyl, aryl, substituted aryl, or substituted alkyl;
• or
• iii) 1,2-divalent phenyl, 2,2′-divalent 1,1′-biphenyl, 2,2′-divalent, 1,1′-binapthyl, or ferrocene, each of which may be substituted independently with C1-C8 alkyl or aryl, F, Cl, Br, I, COOR5, SO3R5, PO3R52, OR5, SR5, NR52, PR52, AsR52, SbR52, nitro, vinyl, substituted vinyl, alkynyl wherein R5 is H, C1-C8 alkyl, substituted C1-C8 alkyl, C1-C8 fluoroalkyl, C1-C8 perfluoroalkyl, aryl or substituted aryl;
• and
• wherein Z is a compound selected from the group of compounds having the following formula:
• 66

A process for preparing a compound of formula A, represented by the formula:

• 84
• said process comprising:
• reacting a compound of formula B* with a phosphine to form compound B:
• 85
• and thereafter
• reacting compound B with an acid to form compound A;
• wherein the phosphine is
• 86
• ;
• A) R is aryl, C1-C8 alkyl, C1-C8 alkyl aryl, or aryl C1-C8 alkyl, which may be substituted with carboxylic acid, alkoxy, hydroxy, C1-C8 alkylthio, thiol, dialkylamino, diphenylphosphino, or chiral oxazolino groups;
• B) the ring component
• 87
• represents a protected diol, a crown ether linkage, or
• —O—(CH2CH2)n—O— wherein n is an integer ranging from 1 to 8 and the methylene groups are optionally substituted by alkyl or linked to a polymer;
• and
• C)
• 88
• may be:
• —(CH2)n— where n is an integer ranging from 1 to 8;
• —(CH2)n—X—(CH2)n— wherein n, m are each integers, the same or different, ranging from 1 to 8;
• or
• 1,2-divalent phenyl, 2,2′-divalent 1,1′ biphenyl or 2,2′-divalent 1,2′binapthyl or ferrocene, each of which may be substituted with aryl or substituted aryl, or alkyl having 1-8 carbon atoms, heteroatom groups such as F, Cl, Br, I, COOR5, SO3R5, PO3R52, OR5, SR5, NR52, PR52, AsR52, or SbR52,
• wherein the substitution on 1,2-divalent phenyl, the ferrocene or biaryl bridge can be independently halogen, C1-C8 alkyl, alkoxyl, aryl, aryloxy, nitro, amino, vinyl, substituted vinyl, alkynyl, or sulfonic acids;
• and R5 is hydrogen, C1-C8 alkyl, C1-C8 fluoroalkyl, or C1-C8 perfluoro, aryl;
• substituted aryl;
• aryl C1-C8 alkyl;
• ring-substituted arylalkyl;
• or CR32(CR32)qX(CR32)pR1 wherein q and p are integers, the same or different, ranging from 1 to 8;
• X is O, S, NR4, PR4, AsR4, SbR4, divalent aryl, divalent fused aryl, divalent 5-membered ring heterocyclic group, or divalent fused heterocyclic group, wherein R3 and R4 are aryl, C1-C8 alkyl, substituted aryl and substituted alkyl groups.

A process comprising subjecting a substrate to an asymmetric reaction in the presence of a catalyst comprising a chiral ligand represented by the formula A, A′, B, B′, C, C′, D, or D′, or the corresponding enantiomer:

• 93
• wherein:
• a) R and R2 are independently aryl, alkyl, alkyl aryl, aryl alkyl, or chiral oxazolino which may be substituted with carboxylic acid, alkoxy, hydroxy, alkylthio, thiol, dialkylamino, or diphenylphosphino groups;
• b) R1 can be H, alkyl, silane, aryl, a water soluble unit, or a linked polymer chain or inorganic support;
• c) the ring component
• 94
• represents a protected diol, a crown ether linkage, —O-alkyl-O— wherein the alkyl group is linked to a polymer, or —O—(CH2CH2—O)n— wherein n is an integer ranging from 1 to 8 and the methylene groups are optionally substituted by C1-C8 alkyl;
• and
• d)
• 95
• may be:
• —(CH2)n— where n is an integer ranging from 1 to 8;
• —(CH2)nX(CH2)m— wherein n and m are each integers, the same or different, ranging from 1 to 8, and X is O, S, NR4, PR4, AsR4, SbR4, divalent aryl, divalent fused aryl, divalent 5-membered ring heterocyclic group, or divalent fused heterocyclic group, wherein R4 is aryl, alkyl, substituted aryl, or substituted alkyl;
• or
• 1,2-divalent phenyl, 2,2′-divalent 1,1′biphenyl or 2,2′-divalent 1,2′binapthyl or ferrocene, each of which may be substituted with aryl, C1-C8 alkyl, F, Cl, Br, I, COOR5, SO3R5, PO3R52, OR5, SR5, NR52, PR52, AsR52, or SbR52, wherein:
• the substitution on 1,2-divalent phenyl, the ferrocene or biaryl bridge can be independently halogen, alkyl, alkoxyl, aryl, aryloxy, nitro, amino, vinyl, substituted vinyl, alkynyl, or sulfonic acids;
• and
• R5 is hydrogen, C1-C8 alkyl, C1-C8 fluoroalkyl, or C1-C8 perfluoroalkyl, aryl;
• substituted aryl;
• arylalkyl;
• ring-substituted arylalkyl;
• or —CR32(CR32)qX(CR32)pR1 wherein q and p are integers, the same or different, ranging from 1 to 8;
• R3 is aryl, alkyl, substituted aryl, or substituted alkyl;
• and X is as defined above;
• wherein said asymmetric reaction is a hydrogenation, hydride transfer, hydrosilylation, hydroboration, hydrovinylation, olefin metathesis, hydroformylation, hydrocarboxylation, allylic alkylation, cyclopropanation, Diels-Alder, Aldol, Heck [m+n] cycloaddition, or Michael addition reaction.