Catalytic 1,2-dihydronaphthalene and E-aryl-diene synthesis via CoIII–Carbene radical and o-quinodimethane intermediates

Catalytic 1,2-dihydronaphthalene and E-aryl-diene synthesis via CoIII–Carbene radical and o-quinodimethane intermediates† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c7sc03909c

Catalytic Dibenzocyclooctene Synthesis via Cobalt(III)–Carbene Radical and ortho‐Quinodimethane Intermediates

The metalloradical activation of ortho-benzallylaryl N-tosyl hydrazones with [Co(TPP)] (TPP=tetraphenylporphyrin) as the catalyst enabled the controlled exploitation of the single-electron reactivity of the redox non-innocent carbene intermediate. This method offers a novel route to prepare eight-membered rings, using base metal catalysis to construct a series of unique dibenzocyclooctenes thro...

Nitrene Radical Intermediates in Catalytic Synthesis

Nitrene radical complexes are reactive intermediates with discrete spin density at the nitrogen-atom of the nitrene moiety. These species have become important intermediates for organic synthesis, being invoked in a broad range of C-H functionalization and aziridination reactions. Nitrene radical complexes have intriguing electronic structures, and are best described as one-electron reduced Fis...

Catalytic N-N coupling of aryl azides to yield azoarenes via trigonal bipyramid iron-nitrene intermediates.

The reactivity of the trigonal bipyramidal iron(I) complex [SiP(iPr)(3)]Fe(N(2)) ([SiP(iPr)(3)] = (2-iPr(2)PC(6)H(4))(3)Si(-)) toward organoazides has been examined. 1-Adamantylazide was found to coordinate the iron center to form stable [SiP(iPr)(3)]Fe(eta(1)-N(3)Ad). Aryl azides instead afforded unstable [SiP(iPr)(3)]Fe(N(3)Ar) species that decayed gradually to regenerate [SiP(iPr)(3)]Fe(N(2)...

Nucleoside phosphate analogues of biological interest, and their synthesis via aryl nucleoside H-phosphonates as intermediates.

This review presents a brief account of the chemistry and mechanistic aspects of aryl H-phosphonates, and selected applications of this class of compounds as intermediates in the synthesis of a wide range of biologically important analogues of nucleoside phosphates, and oligonucleotides, in which the phosphate moieties are replaced by other structurally related groups. The aryl nucleoside H-pho...