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US 6,946,569 B2Granted
Asymmetric catalysis based on chiral phospholanes and hydroxyl phospholanes
AssigneeThe Penn State Research Foundation
InventorXumu Zhang
Life of this patent
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Abstract
Chiral phosphine ligands derived from chiral natural products including D-mannitol and tartaric acid. The ligands contain one or more 5-membered phospholane rings with multiple chiral centers, and provide high stereoselectivity in asymmetric reactions.
Claims21
A compound of formula C′, or the corresponding enantiomer:
- wherein:
- a) R and R2 is independently selected from the group consisting of:
- aryl, alkyl, alkyl aryl, aryl alkyl, chiral oxazolino which may be substituted with carboxylic acid, alkoxy, hydroxy, alkylthio, thiol, dialkylamino, or diphenylphosphino groups;
- of wherein R2 is a group having the formula:
- wherein Z is a group represented by the formula:
- b) R1 is selected from the group consisting of:
- H, alkyl, silyl, aryl, a water soluble unit, or a linked polymer chain and an inorganic support;
- and
- c)
- is selected from the group consisting of:
- —(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;
- and
- 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 group;
- and
- wherein R5 is selected from a group consisting of:
- hydrogen, C1-C8 alkyl, C1-C8 fluoroalkyl, C1-C8 perfluoroalkyl, aryl, substituted aryl, arylalkyl, ring-substituted arylalkyl, and —CR32(CR32)qX(CR32)pR1 wherein q and p are integers, the same or different, ranging from 1 to 8;
- wherein R3 is selected from the group consisting of:
- aryl, alkyl, substituted aryl, and substituted alkyl;
- and X is as defined above.
18 more elements
A catalyst comprising a compound in the form of a complex with a transition metal wherein said compound is selected from compounds represented by the formula;
- wherein:
- a) each R and R2 is independently selected from the group consisting of:
- aryl, alkyl, alkyl aryl, aryl alkyl, chiral oxazolino which may be substituted with carboxylic acid, alkoxy, hydroxy, alkylthio, thiol, dialkylamino, or diphenylphosphino groups;
- or wherein R2 is a group having the formula:
- wherein Z is a group represented by the formula:
- b) R1 is selected from the group consisting of:
- H, alkyl, silyl, aryl, a water soluble unit, a linked polymer chain and an inorganic support;
- and
- c)
- is selected from the group consisting of:
- —(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;
- and
- 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 acid group;
- and
- wherein R5 is selected from the group consisting of:
- hydrogen, C1-C8 alkyl, C1-C8 fluoroalkyl, C1-C8 perfluoroalkyl, aryl, substituted aryl, arylalkyl, ring-substituted arylalkyl, and —CR32(CR32)gX(CR32)pR1 wherein q and p are integers, the same or different, ranging from 1 to 8;
- wherein R3 is selected from the group consisting of:
- aryl, alkyl, substituted aryl, and substituted alkyl;
- and X is as defined above.
18 more elements
Dependencies are inferred from the claim text.