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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-b

Mechanistic investigations on the Cp*Rh(III)-catalyzed direct C-H amination reaction led us to reveal the new utility of 1,4,2-dioxazol-5-one and its derivatives as highly efficient amino sources. Stepwise analysis on the C-N bond-forming process showed that competitive binding of rhodium metal center to amidating reagent or substrate is closely related to the reaction efficiency. In this line, 1,4,2-dioxazol-5-ones were observed to have a strong affinity to the cationic Rh(III) giving rise to d

Guiding nitrenes away from a migration Nitrogen conventionally shares its electrons in three bonds with one or more partners. A singly bonded nitrogen, or nitrene, is exceptionally reactive and can insert itself into normally inert C–H bonds. If the nitrene forms next to a carbonyl center, though, it tends to react with the C–C bond on the other side instead. Hong et al. used theory to guide the design of an iridium catalyst that inhibits this rearrangement, steering the nitrene toward C–H inser

Calibration between color camera and 3D Light Detection And Ranging (LIDAR) equipment is an essential process for data fusion. The goal of this paper is to improve the calibration accuracy between a camera and a 3D LIDAR. In particular, we are interested in calibrating a low resolution 3D LIDAR with a relatively small number of vertical sensors. Our goal is achieved by employing a new methodology for the calibration board, which exploits 2D-3D correspondences. The 3D corresponding points are est

The mechanism of the Ir(III)- and Rh(III)-mediated C-N coupling reaction, which is the key step for catalytic C-H amidation, was investigated in an integrated experimental and computational study. Novel amidating agents containing a 1,4,2-dioxazole moiety allowed for designing a stoichiometric version of the catalytic C-N coupling reaction and giving access to reaction intermediates that reveal details about each step of the reaction. Both DFT and kinetic studies strongly point to a mechanism wh

High Resolution Image Download MS PowerPoint Slide The practical aspects of Cp*Rh(III)-catalyzed direct C–H amidation with 1,4,2-dioxazol-5-ones were investigated on the operational safety, use of green solvent, and scalability. Differential scanning calorimeter (DSC) measurement showed that 3-phenyl-1,4,2-dioxazol-5-one is thermally stable while benzoyl azide, a conventionally employed precursor of acyl nitrene, rapidly decomposes to isocyanate. It was confirmed that the replacement of acyl azi

Engineering site-selectivity is highly desirable especially in C-H functionalization reactions. We report a new catalyst platform that is highly selective for the amidation of benzylic C-H bonds controlled by π-π interactions in the secondary coordination sphere. Mechanistic understanding of the previously developed iridium catalysts that showed poor regioselectivity gave rise to the recognition that the π-cloud of an aromatic fragment on the substrate can act as a formal directing group through

Delineating complex ligand effects on enantioselectivity is a longstanding challenge in asymmetric catalysis. With α-amino acid ligands, the essential difficulty lies in accurately describing integrated perturbations induced by simultaneous variation about the α side chain and N protecting group of the ligand, which hampers an intuitive understanding of the structure–enantioselectivity relationships. To deconvolute such complexity in chiral amino acid enabled enantioselective C–H functionalizati

Abstract A four‐coordinate cobalt–imido complex, ( t Bu mPNP)Co=NMes ( t Bu mPNP=modified PNP pincer ligand) has been synthesized from addition of 2,4,6‐trimethylphenylazide (Mes–N 3 ) to the corresponding dinitrogen complex. The solid‐state structure determined by X‐ray diffraction established a rare, idealized planar geometry with a Co=N bond distance of 1.716(2) Å. Magnetic measurements revealed an S =1 ground state with CAS‐SCF calculations supporting radical character on the imide nitrogen.

A conceptual theory for analyzing and understanding oxidative addition reactions that form the cornerstone of many transition metal mediated catalytic cycles that activate C-C and C-H bonds, for example, was developed. The cleavage of the σ- or π-bond in the organic substrate can be envisioned to follow a closed or an open shell formalism, which is matched by a corresponding electronic structure at the metal center of the catalyst. Whereas the assignment of one or the other mechanistic scenario

Here, we report a highly chemo-, diastereo-, and enantioselective allyl-allyl coupling between branched allyl alcohols and α-silyl-substituted allylboronate esters, catalyzed by a chiral iridium complex. The α-silyl-substituted allylboronate esters can be chemoselectively coupled with allyl electrophiles, affording a diverse set of enantioenriched (E)-1-boryl-substituted 1,5-dienes in good yields, with excellent stereoselectivity. By permuting the chiral iridium catalysts and the substrates, we