ChemInform Abstract: Metalloporphyrin‐catalyzed C‐C Bond Formation

Abstract

Review: 126 refs.

Porphyrin‐Catalyzed Photochemical C–H Arylation of Heteroarenes

“…However, fully aromatic porphyrins with well‐established photophysical properties have already been used to harvest light energy for artificial photosynthesis, phototherapy, imaging, and so on . Moreover, their metal complexes proved efficient in catalyzing various reactions, for example, C–H hydroxylation, cyclopropanation, alkylation, amination, epoxidation, olefination, oxidative Mannich reaction, and oxidative amine coupling . However, in photochemistry they are mainly associated with the generation of singlet oxygen or other reactive oxygen species .…”

Ruthenium(II) and Ruthenium(III) Complexes of p-Benziporphyrin: Merging Equatorial and Axial Organometallic Coordination

“…Interestingly, an azulene moiety incorporated into the macrocycle (carbaporphyrin or carbaporphyrinogen) provides also the π-surface suitable to bind the Ru 4 (CO) 9 cluster. , The short overview can be completed by atypical ruthenocene-type complexes of N-fused porphyrins and ruthenocenoporphyrin in which a d-electron subunit has been built into a π-electron conjugation pathway . In general, the organometallic paramagnetic ruthenium­(III) porphyrins are rather rare and typically quite reactive, although with some remarkable exceptions. ,, From that perspective, a controlled and predictable formation of ruthenium­(II,III)···carbon interactions is of critical importance and opens new venues for exploration of the behavior of ruthenium porphyrins especially in the context of the extensive interest in their reactivity, − motivated by the catalytic activity of such complexes where the formation of C–H, C–C, C–N, and CO bonds has been reported. ,,− …”

Synthesis and Photophysical Properties of Porphyrin Macrorings Composed of Free-Base Porphyrins and Slipped-Cofacial Zinc Porphyrin Dimers

“…(Figure S13). A distinct change was observed at the eliminated exomethylene and methine signals of the allyl ether groups, where the multiplet signals coupled with the neighboring sp 3 -methylene and terminal exomethylene protons at 6.0−6.2 ppm in N-(Zn-Fb-Zn) 3 were simplified to appear as two triplet signals coupled with only the neighboring sp 3 methylene protons at 6.0 and 6.3 ppm in C-(Zn-Fb-Zn) 3 (Figure 5a). A metathesis reaction using the first-generation Grubbs catalyst can provide both E-and Z-olefins, and the Eolefin is preferentially formed.…”

“…Porphyrins are well-known macrocyclic dyes having intense absorption bands in the visible region and can coordinate to various metal ions to form very stable complexes, allowing their use in a wide range of applications. − In recent studies, for photochemical reactions, manganese, iron, cobalt, ruthenium, and rhodium porphyrins have been utilized as photoredox catalysts for olefin epoxidation, , CO 2 reduction, oxidation of hydrocarbons, , water oxidation, syntheses of N -acyl sulfimides and sulfoximines, and carbon–carbon σ-bond oxidation . Zinc porphyrins are used as the photosensitizer in photocatalytic CO 2 reduction, , photoinduced living polymerization, photoinduced α-functionalization of aldehydes, photooxidation of alcohols, light-driven O 2 reduction, and selective oxidation of aromatic alcohols …”