Redox Dehydration Coupling Catalysts and Methods Related Thereto

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.

What we claim: 
     
         1 . A method of catalyzing a coupling reaction comprising mixing
 a) a compound comprising a hydroxy group,   b) a PR 3 , wherein PR 3  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 . The method of  claim 1 , wherein mixing includes a CuI 2 (NMI) 4 . 
     
     
         3 . The method of  claim 1 , wherein the catalytic heterocycle has the following formula: 
       
         
           
           
               
               
           
         
         or salts thereof wherein, 
         Y is N, CH, or C—R 5 ; 
         Z is N or CH, 
         D is S or Se, or Te; 
         W is C═O, S═O, SO 2 , P═O, PO 2  CH 2 , or CR a   2 ; 
         R a  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; 
         R 1  is alkyl or hydrogen; 
         R 2  is alkyl or hydrogen; or R 1  and R 2  come together to form a carbocyclyl; 
         R 4  is selected from alkyl, alkenyl, alkanoyl, cyano, dialkylamino, carbocyclyl, aryl, and heterocyclyl wherein R 4  is optionally substituted with one or more, the same or different, R 40  or R 41 ; 
         R 40  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 R 40  is optionally substituted with one or more, the same or different, R 41 ; 
         R 41  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; 
         R 5  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 R 5  is optionally substituted with one or more, the same or different, R 50 ; 
         R 50  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. 
       
     
     
         4 . The method of  claim 1 , wherein the catalytic heterocycle has the following formula: 
       
         
           
           
               
               
           
         
         or salts wherein, 
         Y is N, CH, or C—R 5 ; 
         Z is N or CH, 
         D is S or Se, or Te; 
         W is C═O, S═O, SO 2 , P═O, PO 2 , CH 2 , or CR a   2 ; 
         R a  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; 
         R 1  is hydrogen or alkyl; 
         R 2  is hydrogen or alkyl; or R 1  and R 2  come together to form a carbocyclyl; 
         R 3  is hydrogen or alkyl; 
         R 4  is hydrogen or alkyl, or R 3  and R 4  come together to form a heterocyclyl; 
         R 5  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 R 5  is optionally substituted with one or more, the same or different, R 50 ; 
         R 50  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. 
       
     
     
         5 . The method of  claim 4 , wherein the compound is 5-nitro-2-(2-(pyridin-2-yl)propan-2-yl)benzo[d]isothiazol-3(2H)-one. 
     
     
         6 . The method of  claim 1 , wherein the catalytic heterocycle has the following formula: 
       
         
           
           
               
               
           
         
         or salts wherein, 
         Y is N, CH, or C—R 5 ; 
         Z is N or CH, 
         D is S or Se, or Te; 
         W is C═O, S═O, SO 2 , P═O, PO 2 , CH 2 , or CR a   2 ; 
         R a  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; 
         R 1 , R 2 , R 3 , R 4 , and R 7  are each individually and independently hydrogen or alkyl; 
         R 6  is hydrogen or alkyl; or R 6  and R 7  come together to form a heterocyclyl, or R 4  and R 6  come together to form a heterocyclyl; 
         R 5  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 R 5  is optionally substituted with one or more, the same or different, R 50 ; 
       
       R 50  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. 
     
     
         7 . The method of  claim 6 , wherein the compound is 2-(2-(dimethylamino)ethyl)-5-nitrobenzo[d]isothiazol-3(2H)-one 
     
     
         8 . The method of  claim 1 , wherein the catalytic molecule has the following formula: 
       
         
           
           
               
               
           
         
         or salts thereof wherein, 
         Y is N, CH, or C—R 5 ; 
         Z is N or CH, 
         D is Se or Te; 
         W is C═O, S═O, SO 2 , P═O, PO 2 , CH 2 , or CR a   2 ; 
         R a  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; 
         R 1  is hydrogen or alkyl; 
         R 4  is selected from alkyl, alkenyl, alkanoyl, cyano, dialkylamino, carbocyclyl, aryl, and heterocyclyl wherein R 4  is optionally substituted with one or more, the same or different, R 40  or R 41 ; 
         R 40  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 R 40  is optionally substituted with one or more, the same or different, R 41 ; 
         R 41  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; 
         R 5  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 R 5  is optionally substituted with one or more, the same or different, R 50 ; 
         R 50  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 . The method of  claim 1 , wherein the catalytic molecule has the following formula: 
       
         
           
           
               
               
           
         
         or salts thereof wherein, 
         Y is N, CH, or C—R 5 ; 
         Z is N or CH, 
         D is S or Se, or Te; 
         W is C═O, S═O, SO 2 , P═O, PO 2 , CH 2 , or CR a   2 ; 
         R a  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; 
         R 1 , R 2 , R 3 , R 4 , and R 7  each individually and independently alkyl or hydrogen; 
         R 6  is alkyl or hydrogen; or R 6  and R 7  come together to form a heterocyclyl; or R 6  and R 4  come together to form a heterocyclyl; 
         R 5  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 R 5  is optionally substituted with one or more, the same or different, R 50 ; 
       
       R 50  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 . The method of  claim 9  wherein the compound is selected from 6,6′-diselanediylbis(N-(2-(dimethylamino)ethyl)-3-nitrobenzamide) and 6,6′-diselanediylbis(N-(2-(dimethylamino)ethyl)-N-methyl-3-nitrobenzamide) or salts thereof. 
     
     
         11 . The method of  claim 1 , wherein the catalytic molecule has the following formula: 
       
         
           
           
               
               
           
         
         or salts thereof wherein, 
         Y is N, CH, or C—R 5 ; 
         Z is N or CH, 
         D is S or Se, or Te; 
         W is C═O, S═O, SO 2 , P═O, PO 2 , CH 2 , or CR a   2 ; 
         R a  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; 
         R 1 , R 2 , R 3 , and R 4 , each individually and independently, are alkyl or hydrogen; 
         R 6  is alkyl or hydrogen; or R 6  and R 4  come together to form a heterocyclyl; 
         R 5  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 R 5  is optionally substituted with one or more, the same or different, R 50 ; 
         R 50  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 . 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, SO 2 , P═O, PO 2 , CH 2 , or CR a   2 ; 
         m is 0, 1, 2, 3, or 4; 
         R a  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; 
         R 1  is alkyl; 
         R 2  is alkyl; or R 1  and R 2  come together to form a carbocyclyl; 
         R 4  is selected from alkyl, alkenyl, alkanoyl, cyano, dialkylamino, carbocyclyl, aryl, and heterocyclyl wherein R 4  is optionally substituted with one or more, the same or different, R 40  or R 41 ; 
         R 40  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 R 40  is optionally substituted with one or more, the same or different, R 41 ; 
         R 41  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; 
         R 5  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 R 5  is optionally substituted with one or more, the same or different, R 50 ; 
         R 50  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. 
       
     
     
         13 . A compound having the following formula: 
       
         
           
           
               
               
           
         
         or salts wherein, 
         Y is N, CH, or C—R 5 ; 
         Z is N or CH, 
         D is S or Se, or Te; 
         W is C═O, S═O, SO 2 , P═O, PO 2 , CH 2 , or CR a   2 ; 
         R a  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; 
         R 1  is hydrogen or alkyl; 
         R 2  is hydrogen or alkyl; or R 1  and R 2  come together to form a carbocyclyl; 
         R 3  is hydrogen or alkyl; 
         R 4  is hydrogen or alkyl, or R 3  and R 4  come together to form a heterocyclyl; 
         R 5  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 R 5  is optionally substituted with one or more, the same or different, R 50 ; 
         R 50  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. 
       
     
     
         14 . A compound having the following formula: 
       
         
           
           
               
               
           
         
         or salts wherein, 
         Y is N, CH, or C—R 5 ; 
         Z is N or CH, 
         D is S or Se, or Te; 
         W is C═O, S═O, SO 2 , P═O, PO 2 , CH 2 , or CR a   2 ; 
         R a  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; 
         R 1  is hydrogen or alkyl; 
         R 2  is hydrogen or alkyl; or R 1  and R 2  come together to form a carbocyclyl; 
         R 3  is hydrogen or alkyl; 
         R 4  is hydrogen or alkyl, or R 3  and R 4  come together to form a heterocyclyl; 
         R 6  is hydrogen or alkyl; 
         R 7  is hydrogen or alkyl, or R 6  and R 7  come together to form a heterocyclyl, or R4 and R7 come together to form a heterocyclyl; 
         R 5  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 R 5  is optionally substituted with one or more, the same or different, R 50 ; 
       
       R 50  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. 
     
     
         15 . A compound having the following formula: 
       
         
           
           
               
               
           
         
         or salts thereof wherein, 
         Y is N, CH, or C—R 5 ; 
         Z is N or CH, 
         D is S or Se, or Te; 
         W is C═O, S═O, SO 2 , P═O, PO 2  CH 2 , or CR a   2 ; 
         R a  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; 
         R 1 , R 2 , R 3 , R 4 , and R 7  each individually and independently alkyl or hydrogen; 
         R 6  is alkyl or hydrogen; or R 6  and R 7  come together to form a heterocyclyl; or R 6  and R 4  come together to form a heterocyclyl; 
         R 5  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 R 5  is optionally substituted with one or more, the same or different, R 50 ; 
       
       R 50  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.