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US 2018/0318818 A1Published application
Redox Dehydration Coupling Catalysts and Methods Related Thereto
AssigneeEmory University
InventorsSteven Lanny Liebeskind, Pavan Kumar Reddy Gangireddy, Srirama Murthy Akondi
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Abstract
This disclosure relates to synthetic coupling methods using catalytic molecules. In certain embodiments, the catalytic molecules comprise heterocyclic thiolamide, S-acylthiosalicylamide, disulfide, selenium containing heterocycle, diselenide compound, ditelluride compound or tellurium containing heterocycle. Catalytic molecules disclosed herein are useful as catalysts in the transformation of hydroxy group containing compounds to amides, esters, ketones, and other carbon to heteroatom or carbon to carbon transformations.
Claims15
A method of catalyzing a coupling reaction comprising mixing
- a) a compound comprising a hydroxy group,
- b) a PR3, wherein PR3 is a trisubsituted phosphite, phosphine or a phosphorus containing five member heterocycle,
- c) a nucleophile, and
- d) a catalytic molecule or catalytic heterocycle comprising two bonded heteroatoms wherein one heteroatom is a nitrogen and the second heteroatom is not nitrogen,
- under conditions such that a compound is formed comprising the nucleophile in place of the hydroxy group.
2 more elements
A compound having the following formula:
- or salts thereof wherein,
- A is an aryl or heteroaryl ring;
- D is sulfur, selenium, or tellurium;
- W is C═O, S═O, SO2, P═O, PO2, CH2, or CRa2;
- m is 0, 1, 2, 3, or 4;
- Ra is selected from alkyl, alkenyl, alkanoyl, halogen, nitro, cyano, hydroxy, amino, mercapto, formyl, carboxy, carbamoyl, alkoxy, alkylthio, alkylamino, dialkylamino, alkylsulfinyl, alkylsulfonyl, arylsulfonyl, carbocyclyl, aryl, and heterocyclyl;
- R1 is alkyl;
- R2 is alkyl;
- or R1 and R2 come together to form a carbocyclyl;
- R4 is selected from alkyl, alkenyl, alkanoyl, cyano, dialkylamino, carbocyclyl, aryl, and heterocyclyl wherein R4 is optionally substituted with one or more, the same or different, R40 or R41;
- R40 is selected from alkyl, alkenyl, alkanoyl, halogen, nitro, cyano, hydroxy, amino, mercapto, formyl, carboxy, carbamoyl, alkoxy, alkylthio, alkylamino, dialkylamino, alkylsulfinyl, alkylsulfonyl, arylsulfonyl, carbocyclyl, aryl, and heterocyclyl wherein R40 is optionally substituted with one or more, the same or different, R41;
- R41 is selected from halogen, nitro, cyano, hydroxy, trifluoromethoxy, trifluoromethyl, amino, formyl, carboxy, carbamoyl, mercapto, sulfamoyl, methyl, ethyl, propyl, tert-butyl, methoxy, ethoxy, acetyl, acetoxy, methylamino, ethylamino, dimethylamino, diethylamino, N-methyl-N-ethylamino, acetylamino, N-methylcarbamoyl, N-ethylcarbamoyl, N,N-dimethylcarbamoyl, N,N-diethylcarbamoyl, N-methyl-N-ethylcarbamoyl, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, mesyl, ethylsulfonyl.methoxycarbonyl, ethoxycarbonyl, N-methylsulfamoyl, N-ethylsulfamoyl, N,N-dimethylsulfamoyl, N,N-diethylsulfamoyl, N-methyl-N-ethylsulfamoyl, carbocyclyl, aryl, and heterocyclyl;
- R5 is at each occurrence individually selected from alkyl, alkenyl, alkanoyl, halogen, nitro, suflonate, cyano, hydroxy, amino, mercapto, formyl, carboxy, sulfoxy, carbamoyl, alkoxy, alkylthio, alkylamino, dialkylamino, alkylsulfinyl, alkylsulfonyl, arylsulfonyl, carbocyclyl, aryl, and heterocyclyl wherein R5 is optionally substituted with one or more, the same or different, R50;
- R50 is selected from halogen, nitro, cyano, hydroxy, trifluoromethoxy, trifluoromethyl, amino, formyl, carboxy, carbamoyl, mercapto, sulfamoyl, methyl, ethyl, propyl, tert-butyl, methoxy, ethoxy, acetyl, acetoxy, methylamino, ethylamino, dimethylamino, diethylamino, N-methyl-N-ethylamino, acetylamino, N-methylcarbamoyl, N-ethylcarbamoyl, N,N-dimethylcarbamoyl, N,N-diethylcarbamoyl, N-methyl-N-ethylcarbamoyl, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, mesyl, ethylsulfonyl.methoxycarbonyl, ethoxycarbonyl, N-methylsulfamoyl, N-ethylsulfamoyl, N,N-dimethylsulfamoyl, N,N-diethylsulfamoyl, N-methyl-N-ethylsulfamoyl, carbocyclyl, aryl, and heterocyclyl.
11 more elements
A compound having the following formula:
- or salts wherein,
- Y is N, CH, or C—R5;
- Z is N or CH,
- D is S or Se, or Te;
- W is C═O, S═O, SO2, P═O, PO2, CH2, or CRa2;
- Ra is selected from alkyl, alkenyl, alkanoyl, halogen, nitro, cyano, hydroxy, amino, mercapto, formyl, carboxy, carbamoyl, alkoxy, alkylthio, alkylamino, dialkylamino, alkylsulfinyl, alkylsulfonyl, arylsulfonyl, carbocyclyl, aryl, and heterocyclyl;
- R1 is hydrogen or alkyl;
- R2 is hydrogen or alkyl;
- or R1 and R2 come together to form a carbocyclyl;
- R3 is hydrogen or alkyl;
- R4 is hydrogen or alkyl, or R3 and R4 come together to form a heterocyclyl;
- R5 is selected from alkyl, alkenyl, alkanoyl, halogen, nitro, cyano, hydroxy, amino, mercapto, formyl, carboxy, carbamoyl, alkoxy, alkylthio, alkylamino, dialkylamino, alkylsulfinyl, alkylsulfonyl, arylsulfonyl, carbocyclyl, aryl, and heterocyclyl wherein R5 is optionally substituted with one or more, the same or different, R50;
- R50 is selected from halogen, nitro, cyano, hydroxy, trifluoromethoxy, trifluoromethyl, amino, formyl, carboxy, carbamoyl, mercapto, sulfamoyl, methyl, ethyl, propyl, tert-butyl, methoxy, ethoxy, acetyl, acetoxy, methylamino, ethylamino, dimethylamino, diethylamino, N-methyl-N-ethylamino, acetylamino, N-methylcarbamoyl, N-ethylcarbamoyl, N,N-dimethylcarbamoyl, N,N-diethylcarbamoyl, N-methyl-N-ethylcarbamoyl, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, mesyl, ethylsulfonyl.methoxycarbonyl, ethoxycarbonyl, N-methylsulfamoyl, N-ethylsulfamoyl, N,N-dimethylsulfamoyl, N,N-diethylsulfamoyl, N-methyl-N-ethylsulfamoyl, carbocyclyl, aryl, and heterocyclyl.
10 more elements
A compound having the following formula:
- or salts wherein,
- Y is N, CH, or C—R5;
- Z is N or CH,
- D is S or Se, or Te;
- W is C═O, S═O, SO2, P═O, PO2, CH2, or CRa2;
- Ra is selected from alkyl, alkenyl, alkanoyl, halogen, nitro, cyano, hydroxy, amino, mercapto, formyl, carboxy, carbamoyl, alkoxy, alkylthio, alkylamino, dialkylamino, alkylsulfinyl, alkylsulfonyl, arylsulfonyl, carbocyclyl, aryl, and heterocyclyl;
- R1 is hydrogen or alkyl;
- R2 is hydrogen or alkyl;
- or R1 and R2 come together to form a carbocyclyl;
- R3 is hydrogen or alkyl;
- R4 is hydrogen or alkyl, or R3 and R4 come together to form a heterocyclyl;
- R6 is hydrogen or alkyl;
- R7 is hydrogen or alkyl, or R6 and R7 come together to form a heterocyclyl, or R4 and R7 come together to form a heterocyclyl;
- R5 is selected from alkyl, alkenyl, alkanoyl, halogen, nitro, cyano, hydroxy, amino, mercapto, formyl, carboxy, carbamoyl, alkoxy, alkylthio, alkylamino, dialkylamino, alkylsulfinyl, alkylsulfonyl, arylsulfonyl, carbocyclyl, aryl, and heterocyclyl wherein R5 is optionally substituted with one or more, the same or different, R50;
- R50 is selected from halogen, nitro, cyano, hydroxy, trifluoromethoxy, trifluoromethyl, amino, formyl, carboxy, carbamoyl, mercapto, sulfamoyl, methyl, ethyl, propyl, tert-butyl, methoxy, ethoxy, acetyl, acetoxy, methylamino, ethylamino, dimethylamino, diethylamino, N-methyl-N-ethylamino, acetylamino, N-methylcarbamoyl, N-ethylcarbamoyl, N,N-dimethylcarbamoyl, N,N-diethylcarbamoyl, N-methyl-N-ethylcarbamoyl, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, mesyl, ethylsulfonyl.methoxycarbonyl, ethoxycarbonyl, N-methylsulfamoyl, N-ethylsulfamoyl, N,N-dimethylsulfamoyl, N,N-diethylsulfamoyl, N-methyl-N-ethylsulfamoyl, carbocyclyl, aryl, and heterocyclyl.
12 more elements
A compound having the following formula:
- or salts thereof wherein,
- Y is N, CH, or C—R5;
- Z is N or CH,
- D is S or Se, or Te;
- W is C═O, S═O, SO2, P═O, PO2 CH2, or CRa2;
- Ra is selected from alkyl, alkenyl, alkanoyl, halogen, nitro, cyano, hydroxy, amino, mercapto, formyl, carboxy, carbamoyl, alkoxy, alkylthio, alkylamino, dialkylamino, alkylsulfinyl, alkylsulfonyl, arylsulfonyl, carbocyclyl, aryl, and heterocyclyl;
- R1, R2, R3, R4, and R7 each individually and independently alkyl or hydrogen;
- R6 is alkyl or hydrogen;
- or R6 and R7 come together to form a heterocyclyl;
- or R6 and R4 come together to form a heterocyclyl;
- R5 is selected from alkyl, alkenyl, alkanoyl, halogen, nitro, cyano, hydroxy, amino, mercapto, formyl, carboxy, carbamoyl, alkoxy, alkylthio, alkylamino, dialkylamino, alkylsulfinyl, alkylsulfonyl, arylsulfonyl, carbocyclyl, aryl, and heterocyclyl wherein R5 is optionally substituted with one or more, the same or different, R50;
- R50 is selected from halogen, nitro, cyano, hydroxy, trifluoromethoxy, trifluoromethyl, amino, formyl, carboxy, carbamoyl, mercapto, sulfamoyl, methyl, ethyl, propyl, tert-butyl, methoxy, ethoxy, acetyl, acetoxy, methylamino, ethylamino, dimethylamino, diethylamino, N-methyl-N-ethylamino, acetylamino, N-methylcarbamoyl, N-ethylcarbamoyl, N,N-dimethylcarbamoyl, N,N-diethylcarbamoyl, N-methyl-N-ethylcarbamoyl, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, mesyl, ethylsulfonyl.methoxycarbonyl, ethoxycarbonyl, N-methylsulfamoyl, N-ethylsulfamoyl, N,N-dimethylsulfamoyl, N,N-diethylsulfamoyl, N-methyl-N-ethylsulfamoyl, carbocyclyl, aryl, and heterocyclyl.
9 more elements
Dependencies are inferred from the claim text.