Process for Producing Optically Pure beta-Lactones from Aldehydes and Compositions Produced Thereby
AssigneeThe University of Toledo
InventorYun-Ming Lin
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Abstract
Bi-functional cobalt-containing catalysts useful for making stereo specific compounds and compositions, along with methods of making, and uses thereof in the syntheses of optically pure β-lactones from aldehydes and ketene are described. Precursors, intermediates, compositions, and particular features of the use if the compositions, such as high enantiomeric selectivity, high yield and low mole percent of catalyst useful are provided.
Claims46
A catalyst compound represented by the structure (10A):
- wherein one or more R moieties are:
- H, or branched or unbranched alkyl or aryl groups.
(canceled)
A catalyst compound represented by the structure (10):
-6. (canceled)
A method for making a β-lactone (12), represented by Scheme 4:
- wherein (11) is selected from:
- aromatic aldehydes and aliphatic aldehydes, and wherein the β-lactone (12) has an enantiomeric excess (ee) greater than or equal to about 70%;
- and R represents independently for each occurrence H, alkyl and aryl.
-12. (canceled)
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(canceled)
A process enantioselectively producing a β-lactone compound, the method comprising:
- enantioselectively converting ketene into an ammonium enolate using a Lewis acid-Lewis base bi-functional catalyst, and
- delivering the ammonium enolate into an aldehyde in the presence of the bi-functional catalyst under conditions sufficient to produce β-lactone compound;
- and
- wherein the enantioselective conversion of the aldehyde produces the β-lactone compound in an enantiomeric excess (ee) of at least about 90%.
-19. (canceled)
A method for making a substantially optically pure hydroxamate aldol represented by the Scheme 6:
- wherein in R is selected from:
- BnOCH2CH2—;
- BnOCH2—;
- CH3(CH2)4CH2—;
- CH3(CH2)9CH2—;
- PhCH2CH2—;
- PhCH2—;
- 2-Chlorophenyl-;
- 2-Fluorophenyl-;
- 3-Chlorophenyl-;
- 3-Fluorophenyl-;
- 4-Nitrophenyl-;
- or, 4-Cyanophenyl-;
- and
- wherein the hydroxamate aldol has a yield of at least 95% and an enantiomeric excess (ee) greater than about 98%.
-22. (canceled)
Use of one or more β-lactone (12) compounds as a substantially optically pure chiral compound for forming at least one of:
- β-lactams, and β-amino acids.
A compound of the Formula I
- wherein one of X1 through X4 is alkoxy, alkyl, or a linker and the remaining three are hydrogen;
- Y is alkyl, alkenyl, or alkynyl;
- and R1 through R4 are alkyl (C3-10) or silyl.
(canceled)
A composition of matter comprising Formula I,
- wherein one of X1 through X4 is O-methyl or vinyl and the remaining three are hydrogen;
- Y is vinyl;
- and R1 through R4 are isopropyl or t-butyl;
- and wherein the composition further comprises at least one counterion selected from the group consisting of:
- SbF6- and BF4-.
(canceled)
A composition of matter comprising Formula I,
- wherein X1, X2 and X4 are hydrogen;
- X3 is O-methyl;
- Y is vinyl;
- R1 through R4 are each t-butyl;
- and wherein the composition further comprises at least one SbF6− counterion.
-33. (canceled)
A stereoisomer as depicted in a figure selected from the group consisting of:
- FIG. 10A1;
- FIG. 10A2;
- FIG. 11A1;
- FIG. 11A2;
- FIG. 12A1;
- FIG. 12A2;
- FIG. 13A1;
- FIG. 13A2.
-43. (canceled)
-54. (canceled)
A compound of the Formula II
- wherein one of X1 through X4 are alkyl and the remaining three are hydrogen;
- Y is hydrogen, alkoxy, alkyl, or a linker;
- Y is alkyl, alkenyl, or alkynyl;
- and R1 through R4 are alkyl (C3-10) or silyl.
(canceled)
A method to make a compound of Formula H
- wherein one of X1 through X4 is alkoxy, alkyl, or a linker and the remaining three are hydrogen;
- Y is alkyl, alkenyl, or alkynyl;
- and R1 through R4 are alkyl (C3-10) or silyl;
- or
- wherein one of X1 through X4 is O-methyl or vinyl and the remaining three are hydrogen;
- Y is vinyl;
- and R1 through R4 are isopropyl or t-butyl;
- or
- wherein X1, X2 and X4 are hydrogen;
- X3 is O-methyl;
- Y is vinyl;
- R1 through R4 are each t-butyl;
- or
- wherein one of X1 through X4 are alkyl and the remaining three are hydrogen;
- Y is hydrogen, alkoxy, alkyl, or a linker;
- Y is alkyl, alkenyl, or alkynyl;
- and R1 through R4 are alkyl (C3-10) or silyl;
- or
- wherein one of X1, X2, and X4 is alkoxy and the other two are hydrogen;
- X3 is hydrogen;
- Y is alkyl (C3-10);
- and R1 through R4 are alkyl (C3-10) or silyl;
- or
- wherein X1, X2 and X4 are each hydrogen;
- X3 is vinyl;
- Y is vinyl;
- and R1 through R4 are isopropyl or t-butyl.
- comprising:
- dissolving an anhydrous cobalt salt in a solution of salen ligand.
(canceled)
A method to make a compound of Formula II
- wherein one of X1 through X4 is alkoxy, alkyl, or a linker and the remaining three are hydrogen;
- Y is alkyl, alkenyl, or alkynyl;
- and R1 through R4 are alkyl (C3-10) or silyl;
- or
- wherein one of X1 through X4 is O-methyl or vinyl and the remaining three are hydrogen;
- Y is vinyl;
- and R1 through R4 are isopropyl or t-butyl;
- or
- wherein X1, X2 and X4 are hydrogen;
- X3 is O-methyl;
- Y is vinyl;
- R1 through R4 are each t-butyl;
- or
- wherein one of X1 through X4 are alkyl and the remaining three are hydrogen;
- Y is hydrogen, alkoxy, alkyl, or a linker;
- Y is alkyl, alkenyl, or alkynyl;
- and R1 through R4 are alkyl (C3-10) or silyl;
- or
- wherein one of X1, X2, and X4 is alkoxy and the other two are hydrogen;
- X3 is hydrogen;
- Y is alkyl (C3-10);
- and R1 through R4 are alkyl (C3-10) or silyl;
- or
- wherein X1, X2 and X4 are each hydrogen;
- X3 is vinyl;
- Y is vinyl;
- and R1 through R4 are isopropyl or t-butyl,
- comprising:
- a.) dissolving salen ligand in solvent;
- b.) degassing the solution of step a.)
- c.) dissolving cobalt salt in the solution of step b.)
- d.) removing the solvent of step a.) so as to produce a concentrated solution;
- and
- e.) adding degassed pentane to the concentrated solution of step d.) so as to precipitate a compound of Formula II.
-91. (canceled)
-95. (canceled)
A method to make a compound of Formula II
- wherein one of X1 through X4 is alkoxy, alkyl, or a linker and the remaining three are hydrogen;
- Y is alkyl, alkenyl, or alkynyl;
- and 121 through R4 are alkyl (C3-10) or silyl;
- or
- wherein one of X1 through X4 is O-methyl or vinyl and the remaining three are hydrogen;
- Y is vinyl;
- and R1 through R4 are isopropyl or t-butyl;
- or
- wherein X1, X2 and X4 are hydrogen;
- X3 is O-methyl;
- Y is vinyl;
- R1 through R4 are each t-butyl;
- or
- wherein one of X1 through X4 are alkyl and the remaining three are hydrogen;
- Y is hydrogen, alkoxy, alkyl, or a linker;
- Y is alkyl, alkenyl, or alkynyl;
- and R1 through R4 are alkyl (C3-10) or silyl;
- or
- wherein one of X1, X2, and X4 is alkoxy and the other two are hydrogen;
- X3 is hydrogen;
- Y is alkyl (C3-10);
- and R1 through R4 are alkyl (C3-10) or silyl;
- or
- wherein X1, X2 and X4 are each hydrogen;
- X3 is vinyl;
- Y is vinyl;
- and R1 through R4 are isopropyl or t-butyl,
- comprising:
- a.) synthesizing a salen ligand from diamine and quinine,
- b.) complexing the salen ligand from step a.) with cobalt.
-129. (canceled)
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-134. (canceled)
Dependencies are inferred from the claim text.