New Methods for 1,4-Diazo N-Heterocycle Synthesis

A compound of formula II:

• or any derivative or salt thereof, wherein
• R1 is R5—S(═O)2—, or a nitrogen protecting group selected from the group consisting of acetyl (Ac), trifluoroacetyl (TFA), trichloroacetyl (TCA), tert-butyloxycarbonyl (Boc), carbobenzyloxy (Cbz), vinyloxycarbonyl (Voc), allyloxycarbonyl (Alloc), and 9-fluorenylmethyloxycarbonyl (Fmoc);
• R2 is optionally substituted C1-C12 straight or branched alkyl, C1-C12 alkenyl, C1-C12 alkynyl, C3-C10 cycloalkyl, C3-C10 hetero cycloalkyl, wherein one or more hydrogen is optionally substituted by an optionally substituted aryl, heteroaryl, C3-C10 cycloalkyl, C3-C10 hetero cycloalkyl, F, Cl, Br, I, hydroxyl, C1-C8 alkoxyl, amino group, or NHBoc, or R2 may form a fused ring with one adjacent carbon atom next to the nitrogen that R2 is attached;
• R3 and R4 are each independently H, optionally substituted C1-C12 straight or branched alkyl, C1-C12 alkenyl, C1-C12 alkynyl, C3-C10 cycloalkyl, C3-C10 hetero cycloalkyl, or an electro withdrawing group (EWG), wherein at least one of R3 and R4 is an electro withdrawing group.
• R5 is optionally substituted C1-C12 straight or branched alkyl, C1-C12 alkenyl, C1-C12 alkynyl, C3-C10 cycloalkyl, C3-C10 hetero cycloalkyl, aryl, heteroaryl;
• R6 is H, nitro, F, Cl, Br, I, amino, cyano, C1-C4 straight, branched, or cycloalkyl, C1-C4 trifluoroalkyl, hydroxyl, C1-C4 alkoxyl, or —SH;
• R7 is H, C1-C4 straight, branched, or cycloalkyl;
• and
• X is a C2-C4 saturated carbon linker, wherein C2-C4 saturated carbon linker is optionally substituted with 4-8 hydrogen, 4-8 optionally substituted C1-C12 straight or branched alkyl, wherein one of the 4-8 optionally substituted C1-C12 straight or branched alkyl may form a fused ring with the C2-C4 saturated carbon linker or with R1, or from a spiro ring with the carbon atom on the C2-C4 saturated carbon linker that the straight or branched alkyl is attached.