Catalytic transformation of ubiquitous C–H bonds into valuable C–N bonds offers an efficient synthetic approach to construct N-functionalized molecules. Over the last few decades, transition metal catalysis has been repeatedly proven to be a powerful tool for the direct conversion of cheap hydrocarbons to synthetically versatile amino-containing compounds. This Review comprehensively highlights recent advances in intra- and intermolecular C–H amination reactions utilizing late transition metal-based catalysts. Initial discovery, mechanistic study, and additional applications were categorized on the basis of the mechanistic scaffolds and types of reactions. Reactivity and selectivity of novel systems are discussed in three sections, with each being defined by a proposed working mode.

Transition Metal-Catalyzed C–H Amination: Scope, Mechanism, and Applications

The chemistry of heavier main-group elements such as aluminium, silicon and phosphorus is very different from that of the lighter ones such as boron, carbon and nitrogen, yet discussions of this topic have been dominated by comparisons with the light elements. Philip Power's review focuses on advances in chemistry of the heavier main-group elements that reveal them as having more in common with the transition metals than the lighter members of the main groups. The concept of heavier main-group elements as 'transition metals' is supported by recent work showing that many of the new compounds react with small molecules such as H2, NH3, C2H4 and CO under mild conditions and display potential as catalysts. The last quarter of the twentieth century and the beginning decade of the twenty-first witnessed spectacular discoveries in the chemistry of the heavier main-group elements. The new compounds that were synthesized highlighted the fundamental differences between their electronic properties and those of the lighter elements to a degree that was not previously apparent. This has led to new structural and bonding insights as well as a gradually increasing realization that the chemistry of the heavier main-group elements more resembles that of transition-metal complexes than that of their lighter main-group congeners. The similarity is underlined by recent work, which has shown that many of the new compounds react with small molecules such as H2, NH3, C2H4 or CO under mild conditions and display potential for applications in catalysis.

Main-group elements as transition metals

N-heterocyclic carbene analogues with low-valent group 13 and group 14 elements: syntheses, structures, and reactivities of a new generation of multitalented ligands.

The Chemistry of β-Diketiminatometal Complexes

ConspectusOwing to the prevalence of nitrogen-containing compounds in functional materials, natural products and important pharmaceutical agents, chemists have actively searched for the development of efficient and selective methodologies allowing for the facile construction of carbon–nitrogen bonds. While metal-catalyzed C–N cross-coupling reactions have been established as one of the most general protocols for C–N bond formation, these methods require starting materials equipped with functional groups such as (hetero)aryl halides or their equivalents, thus generating stoichiometric amounts of halide salts as byproducts. To address this aspect, a transition-metal-catalyzed direct C–H amination approach has emerged as a step- and atom-economical alternative to the conventional C–N cross-coupling reactions. However, despite the significant recent advances in metal-mediated direct C–H amination reactions, most available procedures need harsh conditions requiring stoichiometric external oxidants. In this con...

Transition-metal-catalyzed C-N bond forming reactions using organic azides as the nitrogen source: a journey for the mild and versatile C-H amination.

Dioxygen activation by a neutral beta-diketiminato copper(I) ethylene complex.

beta-Diketiminato Cu(I)-lutidine complexes [RMeNN]Cu(2,4-lutidine) (R = Me (4a), (i)Pr (4b)) were prepared in high yield from Tl[RMeNN] and [CuBr(2,4-lutidine)(2)](2). Both 4a and 4b reversibly dissociate lutidine base in toluene to give [RMeNN]Cu(toluene) solvento complexes. A related base-free dicopper species [[Me(2)NN]Cu](2) (6) bridged via eta(2)-binding of opposing N-aryl rings could be isolated by the addition of Tl[Me(2)NN] to CuBr. The lutidine precursors serve as precatalysts for the aziridination of alkenes with PhI=NTs. Styrene, beta-methylstyrene, and cyclooctene gave the highest yields (59-96%) with a low olefin to PhI=NTs ratio (3:1) and 5 mol % catalyst loading.

Cu(I) beta-diketiminates for alkene aziridination: reversible Cu-arene binding and catalytic nitrene transfer from PhI=NTs.

The present invention described herein employs employs Cu(I) complexes of an electron-rich, bidentate N,N-donor ligand (P-diketiminates) that react with both heteroatomcontaining a-substituted diazomethanes and ary1diazomethanes to yield a unique metal-carbene complex stabilized by two metal fragments that selectively reacts with alkenes. These examples are the first of isolable Cu-carbene complexes that react with alkenes to give cyclopropanes. Furthermore, electron-rich, bidentate N,N-donor ligands can be designed to impart stereo- and enantio-selectivity in the cyclopropanation of alkenes with diazoalkanes.

Diketiminato cu(i) and co(i) carbene catalysts, and cyclopropanation methods using them

A Three‐Coordinate Copper(II) Amide from Reductive Cleavage of a Nitrosamine

The synthesis and structure of a novel β-diketiminato Co(I) arene adduct [Me2NN]Co(η6-toluene) (2) are described, that serves as a synthon to the reactive, “naked” 12-electron [Me2NN]Co fragment via loss of toluene in its reactions with dioxygen, organoazides, and a nitrosobenzene. Exposure of 2 to dioxygen in ether leads to {[Me2NN]Co}2(μ-O)2 (3), a rare example of a cobalt−oxo complex thermally stable at room temperature. The X-ray structure of 3 reveals a short Co−Co separation of 2.716(4) A and exhibits positional disorder for the bridging oxo groups; the predominant configuration contains oxygen atoms in square-planar sites with short Co−O distances (1.784(3) and 1.793(4) A). Reaction of 2 with organoazides N3R (R = 3,5-Me2C6H3 (Ar) or 1-adamantyl (Ad)) results in the formation of imido complexes whose structure depends on the nature of the azido substituent. The synthesis and structures of both {Me2NN]Co}2(μ-NAr)2 (4) with arylimido groups in tetrahedral bridging sites or the three-coordinate, 16-el...

[Me2NN]Co(η6-toluene): OO, NN, and ON Bond Cleavage Provides β-Diketiminato Cobalt μ-Oxo and Imido Complexes

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