There is, I think, something ethereal about i —the square root of minus one. I remember first hearing about it at school. It seemed an odd beast at that time—an intruder hovering on the edge of reality.

Usually familiarity dulls this sense of the bizarre, but in the case of i it was the reverse: over the years the sense of its surreal nature intensified. It seemed that it was impossible to write mathematics that described the real world in …

I and i

8.4.5. Nitromercuration Reactions 3878 9. Hydroamination of Alkenes and Alkynes under Microwave Irradiation 3878 * To whom correspondence should be addressed. Phone: +49 241 8

Hydroamination: direct addition of amines to alkenes and alkynes.

C–H activation has surfaced as an increasingly powerful tool for molecular sciences, with notable applications to material sciences, crop protection, drug discovery, and pharmaceutical industries, among others. Despite major advances, the vast majority of these C–H functionalizations required precious 4d or 5d transition metal catalysts. Given the cost-effective and sustainable nature of earth-abundant first row transition metals, the development of less toxic, inexpensive 3d metal catalysts for C–H activation has gained considerable recent momentum as a significantly more environmentally-benign and economically-attractive alternative. Herein, we provide a comprehensive overview on first row transition metal catalysts for C–H activation until summer 2018.

3d Transition Metals for C-H Activation.

Transition-metal-catalyzed C-H activation has recently emerged as a powerful tool for the functionalization of organic molecules. While many efforts have focused on the functionalization of arenes and heteroarenes by this strategy in the past two decades, much less research has been devoted to the activation of non-acidic C-H bonds of alkyl groups. This Minireview highlights recent work in this area, with a particular emphasis on synthetically useful methods.

/pdf/functionalization-of-organic-molecules-by-transition-metal-2i1323mmoy.pdf

Functionalization of Organic Molecules by Transition‐Metal‐Catalyzed C(sp3) ? H Activation

Catalytic additions of ammonia or primary and secondary amines to non-activated alkenes and alkynes are called hydroaminations. These reactions of fundamental simplicity represent the most atom efficient processes for the formation of amines, enamines and imines, which are important bulk and fine chemicals or building blocks in organic synthesis. Consequently, the development of corresponding hydroamination reactions has received much attention and great progress has been achieved in the case of catalytic hydroaminations of alkynes over the past four years. To illustrate this progress, this tutorial review will mostly focus on recent developments in the field of intermolecular hydroamination of alkynes that appeared in the literature between the end of 2002 and October 31, 2006.

/pdf/the-catalytic-hydroamination-of-alkynes-14hsqkjxwh.pdf

The catalytic hydroamination of alkynes

https://onlinelibrary.wiley.com/doi/pdf/10.1002/anie.200990199

Chiral Neutral Zirconium Amidate Complexes for the Asymmetric Hydroamination of Alkenes

Intramolecular hydroamination of unactived olefins with Ti(NMe2)4 as a precatalyst.

Transition metal-catalysed C–H activation has emerged as an increasingly powerful platform for molecular syntheses, enabling applications to natural product syntheses, late-stage modification, pharmaceutical industries and material sciences, among others. This Primer summarizes representative best practices for the experimental set-up and data deposition for C–H activation, as well as discussing key developments including recent advances in asymmetric, photoinduced and electrocatalytic C–H activation. Likewise, strategies for applications of C–H activation towards the assembly of structurally complex (bio)polymers and drugs in academia and industry are discussed. In addition, current limitations in C–H activation and possible approaches for overcoming these shortcomings are reviewed. This Primer provides an overview of the best practices for C–H activation as well as key advances in asymmetric, photoinduced and electrocatalytic-mediated catalysis for this synthetic platform. An overview of how C–H activation facilitates the synthesis of molecules such as structurally complex (bio)polymers and drugs is provided along with the current challenges and priorities for the next decade.

Laurel L. Schafer

Papers

Chiral Neutral Zirconium Amidate Complexes for the Asymmetric Hydroamination of Alkenes

Intramolecular hydroamination of unactived olefins with Ti(NMe2)4 as a precatalyst.

C–H activation

Tantalum–Amidate Complexes for the Hydroaminoalkylation of Secondary Amines: Enhanced Substrate Scope and Enantioselective Chiral Amine Synthesis

Scandium-Catalyzed Intramolecular Hydroamination. Development of a Highly Active Cationic Catalyst