Activation modes in biocatalytic radical cyclization reactions

Radical cyclizations are essential reactions in the biosynthesis of secondary metabolites and the chemical synthesis of societally valuable molecules. In this review, we highlight the general mechanisms utilized in biocatalytic radical cyclizations. We specifically highlight cytochrome P450 monooxygenases (P450s) involved in the biosynthesis of mycocyclosin and vancomycin, non-heme iron- and α-ketoglutarate-dependent dioxygenases (Fe/αKGDs) used in the biosynthesis of kainic acid, scopolamine, and isopenicillin N, and radical S-adenosylmethionine (SAM) enzymes that facilitate the biosynthesis of oxetanocin A, menaquinone, and F420. Beyond natural mechanisms, we also examine repurposed flavin-dependent ‘ene’-reductases (ERED) for non-natural radical cyclization. Overall, these general mechanisms underscore the opportunity for enzymes to augment and enhance the synthesis of complex molecules using radical mechanisms.

Preparation of anthranils via chemoselective oxidative radical cyclization of 3-(2-azidoaryl) substituted propargyl alcohols

In presence of K2S2O8 and HOAc, propargyl alcohols can go oxidative radical cyclizations to give a pool of anthranils. Excellent chemoselectivity was seen, and the synthesized anthranils can be employed as N-nucleophiles in various transformations.

Synthesis and characterization of piperazine-substituted dihydrofuran derivatives viaMn(OAc)3 mediated radical cyclizations

The aim of this study is to synthesize novel piperazine-containing dihydrofuran compounds (3a-n)from radical additions and cyclizations of diacyl and alkyl-acyl piperazine derivatives (1a-h) with 1,3-dicarbonyl compounds (2a-c) mediated by Mn(OAc)3 for the first time. From the reactions of 1a-c with dimedone (2a);1a, 1c, and 1d with acetylacetone (2b); and 1a with ethylacetoacetate(2c) ,the dihydrofuran-piperazine compounds 3a-c, 3d-f, and 3g were obtained in medium to high yields (31%–81%), respectively. In addition, dihydrofuran-piperazine compounds 3h-j and 3k-n were prepared at low to medium yields (20%–40%) from the reactions of 1e-g with 2a and 1e-h with 2c, respectively.

Photocatalyzed syntheses of phenanthrenes and their aza-analogues. A review

Phenanthrenes and their aza-analogues have important applications in materials science and in medicine. Aim of this review is to collect recent reports describing their synthesis, which make use of radical cyclizations promoted by a visible light-triggered photocatalytic process.

The Use of Copper and Vanadium Mineral Ores in Catalyzed Mechanochemical Carbon–carbon Bond Formations

Under mechanochemical conditions in ball mills, copper- and vanadium-containing minerals initiate atom transfer radical cyclizations and oxidative couplings, respectively. Only catalytic quantities of the minerals are required, and the reactions proceed either under neat conditions or in the presence of a minimal amount of solvent.