The CoII complex of a D2‐symmetric chiral porphyrin ([Co(D2‐Por*)], see scheme) is a highly effective catalyst for the enantioselective aziridination of alkenes with fluoroaryl azides. The reaction can be performed at RT with low catalyst loading, and the olefin is the limiting reagent. Furthermore, the reaction is tolerant toward different combinations of aromatic olefins and fluoroaryl azides.

The Co(II) complex of the D2h-symmetric amidoporphyrin 3,5-DitBu-IbuPhyrin, [Co(P1)], has proven to be an effective metalloradical catalyst for intermolecular amination of C(sp2)–H bonds of aldehydes with fluoroaryl azides. The [Co(P1)]-catalyzed process can employ aldehydes as the limiting reagents and operate under neutral and non-oxidative conditions, generating nitrogen gas as the only byproduct. The metalloradical aldehydic C–H amination is suitable for different combinations of aldehydes and fluoroaryl azides, producing the corresponding N-fluoroaryl amides in good to excellent yields. A series of mechanistic studies support a stepwise radical mechanism for the Co(II)-catalyzed intermolecular C–H amination.

The synthesis of meso,meso‐linked fluoroalkylporphyrin arrays has been accomplished, in excellent yields, by the simple treatment of a CHCl3 solution of zincated 5‐fluoroalkyl‐10,20‐diarylporphyrins (where fluoroalkyl = CF3, ClC2F4, n‐ClC4F8, n‐C6F13, etc.) with iodine(III) reagents such as PhI(O–CO–CF3)2 (PIFA, also named as bis(trifluoroacetoxy)iodo]benzene) or PhI(OAc)2 (PIDA). For nonfluorinated zincated 5‐substituted‐10–20‐diarylporphyrins (where substituent = phenyl, 4‐methoxyphenyl, 4‐methylphenyl, etc.) the similar coupling reactions also proceed fast and quantitatively. Moreover, various 15‐unsubstituted metalloporphyrins can also be coupled in high yields. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)