Gem-disubstituted pyrrolidines, piperazines, and diazepanes, and compositions and methods of making the same

A compound of formula (III) or formula (IV):

• wherein, as valence and stability permit,
• R21 is —C(O)aryl or —C(O)heteroaryl, each optionally substituted with alkoxy, alkyl, or haloalkyl;
• R22 is —C(O)OR22a, —C(O)aryl, or —C(O)heteroaryl, wherein each of aryl and heteroaryl are optionally substituted with alkoxy, alkyl, or haloalkyl;
• R22a is C1-6 alkyl, C6-10 aryl, or C5-9 heteroaryl, wherein each of aryl and heteroaryl are optionally substituted with alkoxy, alkyl, or haloalkyl;
• R23 is H, halogen, alkynyl, alkenyl, or C1-6 alkyl, each optionally substituted with OH, cyano, alkoxy, aryloxy, acyl, alkoxycarbonyl, halogen, aryl, or —NHC(O)OR23a;
• R23a is C1-6 alkyl, (C6-10 aryl)alkyl, or (C5-9 heteroaryl)alkyl;
• R24 is H or halogen;
• and
• p is 1,
• or
• a compound of formula (E):
• or a salt thereof,
• wherein, as valence and stability permit,
• R23 is halogen, alkynyl, alkenyl, or C1-6 alkyl, each optionally substituted with halogen, OH, cyano, alkoxy, aryloxy, alkoxycarbonyl, or —NHC(O)OR23a;
• R23a is C1-6 alkyl;
• and
• R24 is H.