Recent Advances in First‐Row‐Transition‐Metal‐Catalyzed Dehydrogenative Cou­pling of C(sp³)–H Bonds

Abstract

Transition‐metal‐catalyzed cross dehydrogenative coupling is a highly efficient tool for functionalization of C(sp3)–H bonds. In particular, the inexpensive first‐row transition metals have been demonstrated as effective catalysts in this process. This microreview summarizes recent progress in two classes of first‐row‐transition‐metal‐catalyzed dehydrogenative reactions: intramolecular cyclization for C–C bond formation, and directed site‐selective C–H functionalization. These transformations provide concise and practical approaches for preparation of various organic compounds, but so far they are underdeveloped.

Ground State and Excited State Tuning in Ferric Dipyrrin Complexes Promoted by Ancillary Ligand Exchange

“…The complexes show small to intermediate amounts of rhombicity, with values of | E / D | of 0.13 for 4 , 0.04 for 5 , and 0.07 for 6 . In all cases, the feature between g eff = 5.5–6 originates from the m s = ± 3 / 2 Kramers doublet, and all other features are m s = ± 1 / 2 state transitions. No transitions originating from the m s = ± 5 / 2 Kramers doublet are observed.…”

“…1 In many cases, high-spin states, resulting from compressed ligand fields, have been implicated as essential features for the unique reactivity observed. 2 Specifically, ancillary or spectator ligands have a pronounced influence on the electronic structure, induce orbital rearrangements, and influence bonding interactions between the metal and ligands.…”

2‐Methyltetrahydrofuran: A Green Solvent for Iron‐Catalyzed Cross‐Coupling Reactions

“…[1][2][3][4][5] Selectivem ethods for cross-coupling reactions in green, renewables olvents are essentialt or educe environmental damage. The major challenge to maintain full sustainabilityo ft he process is the identification of green and renewable solvents that can be harnessed to replace the conventional solvents for this highly attractive reaction.…”

Transforming Olefins into γ,δ‐Unsaturated Nitriles through Copper Catalysis

“…Rather than requiring functionalized halides and toxic cyanide reagents, this transformation enables olefin feedstocks to be coupled with alkyl nitriles to generate homoallylic nitriles in a single-step, using an earth-abundant metal-catalyst (Figure 1). [8] …”