Dirhodium catalyst compositions and synthetic processes related thereto
This disclosure relates to compositions comprising dirhodium catalysts and uses related thereto, e.g., in enantioselective transformations of donor/acceptor carbenoids. In certain embodiments, the dirhodium catalyst comprises a cyclopropyl ring substituted with a carboxylic acid ligand. In certain embodiments, the disclosure relates to compositions comprising a compound of the following formula, or salts thereof wherein, R 1 , R 2 , and R 3 are defined herein.
1. A dirhodium catalyst with a carboxylic acid ligand covalently bonded to a cyclopropyl ring substituted with a carbocyclyl, aryl, or heterocyclyl.
2. A composition comprising a compound of the following formula,
or salts thereof wherein,
R 1 is carbocyclyl, aryl, or heterocyclyl wherein R 1 is optionally substituted with one or more, the same or different, R 4 ;
R 2 is hydrogen, alkyl, halogen, cyano, hydroxy, amino, mercapto, formyl, carboxy, carbamoyl, alkoxy, alkanoyl, alkylthio, alkylamino, (alkyl) 2 amino, alkylsulfinyl, alkylsulfonyl, arylsulfonyl, carbocyclyl, aryl, or heterocyclyl, wherein R 2 is optionally substituted with one or more, the same or different, R 4 ;
R 3 is hydrogen, alkyl, halogen, cyano, hydroxy, amino, mercapto, formyl, carboxy, carbamoyl, alkoxy, alkanoyl, alkylthio, alkylamino, (alkyl) 2 amino, alkylsulfinyl, alkylsulfonyl, arylsulfonyl, carbocyclyl, aryl, or heterocyclyl, wherein R 3 is optionally substituted with one or more, the same or different, R 4 ;
R 4 is alkyl, halogen, cyano, hydroxy, amino, mercapto, formyl, carboxy, carbamoyl, alkoxy, alkanoyl, alkylthio, alkylamino, (alkyl) 2 amino, alkylsulfinyl, alkylsulfonyl, arylsulfonyl, carbocyclyl, aryl, or heterocyclyl, wherein R 4 is optionally substituted with one or more, the same or different, R 5 ;
R 5 is alkyl, halogen, cyano, hydroxy, amino, mercapto, formyl, carboxy, carbamoyl, alkoxy, alkanoyl, alkylthio, alkylamino, (alkyl) 2 amino, alkylsulfinyl, alkylsulfonyl, arylsulfonyl, carbocyclyl, aryl, or heterocyclyl, wherein R 5 is optionally substituted with one or more, the same or different, R 6 ; and
R 6 is halogen, nitro, cyano, hydroxy, trifluoromethoxy, trifluoromethyl, amino, formyl, carboxy, carbamoyl, mercapto, sulfamoyl, methyl, ethyl, 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, or heterocyclyl.
3. The composition of, claim 2 , wherein R 1 is an aryl or an aromatic heterocyclyl.
4. The composition of claim 2 , wherein R 1 is a phenyl optionally substituted with one or more R 4 .
5. The composition of claim 2 , wherein R 1 is a phenyl optionally substituted with one or more halogen, alkyl, or alkoxy.
6. The composition of claim 2 , wherein R 2 is carbocyclyl, aryl, or heterocyclyl.
7. The composition of claim 2 , wherein R 2 is an aryl or an aromatic heterocyclyl.
8. The composition of claim 2 , wherein R 2 is a phenyl optionally substituted with one or more R 4 .
9. The composition of claim 2 , wherein R 2 is a phenyl optionally substituted with one or more halogen, alkyl, or alkoxy.
10. The composition of claim 2 , wherein R 3 is carbocyclyl, aryl, or heterocyclyl.
11. The composition of claim 2 , wherein R 3 is an aryl or an aromatic heterocyclyl.
12. The composition of claim 2 , wherein R 3 is a phenyl optionally substituted with one or more R 4 .
13. The composition of claim 2 , wherein R 3 is a phenyl optionally substituted with one or more halogen, alkyl, or alkoxy.
14. The composition of claim 2 , wherein R 3 is a phenyl substituted with a halogen.
15. The composition of claim 2 , wherein R 3 is a phenyl substituted with a halogen in the ortho or para position.
16. A composition comprising a compound,
wherein X is an electron withdrawing group.
17. The composition of claim 16 , wherein X is a halogen.
18. A composition comprising a compound
19. A method of making a synthetic compound comprising mixing
a) a diazo compound,
b) a compound with a carbon hydrogen bond, and
c) a compound comprising a compound as in claim 2 ,
under conditions such that a synthetic compound is formed comprising a carbon to carbon bond between the diazo compound and the compound with a carbon hydrogen bond.
20. A method of making a synthetic compound comprising mixing
a) a diazo compound,
b) a compound with a nitrogen hydrogen bond, and
c) a compound comprising a compound as in claim 1 ,
under conditions such that a synthetic compound is formed comprising a carbon to nitrogen bond between the diazo compound and the compound with a nitrogen hydrogen bond.