The present review is devoted to summarizing the recent advances (2015-2017) in the field of metal-catalysed group-directed C-H functionalisation In order to clearly showcase the molecular diversity that can now be accessed by means of directed C-H functionalisation, the whole is organized following the directing groups installed on a substrate Its aim is to be a comprehensive reference work, where a specific directing group can be easily found, together with the transformations which have been carried out with it Hence, the primary format of this review is schemes accompanied with a concise explanatory text, in which the directing groups are ordered in sections according to their chemical structure The schemes feature typical substrates used, the products obtained as well as the required reaction conditions Importantly, each example is commented on with respect to the most important positive features and drawbacks, on aspects such as selectivity, substrate scope, reaction conditions, directing group removal, and greenness The targeted readership are both experts in the field of C-H functionalisation chemistry (to provide a comprehensive overview of the progress made in the last years) and, even more so, all organic chemists who want to introduce the C-H functionalisation way of thinking for a design of straightforward, efficient and step-economic synthetic routes towards molecules of interest to them Accordingly, this review should be of particular interest also for scientists from industrial R&D sector Hence, the overall goal of this review is to promote the application of C-H functionalisation reactions outside the research groups dedicated to method development and establishing it as a valuable reaction archetype in contemporary R&D, comparable to the role cross-coupling reactions play to date

/pdf/a-comprehensive-overview-of-directing-groups-applied-in-543u6d0g60.pdf

A comprehensive overview of directing groups applied in metal-catalysed C-H functionalisation chemistry.

Transient Directing Groups for Transformative C–H Activation by Synergistic Metal Catalysis

Transition-metal-catalyzed activation of C–H and C–C bonds is a challenging area in synthetic organic chemistry. Among various methods to accomplish these processes, the approach using metal–organic cooperative catalytic systems is one of the most promising. In this protocol, organic molecules as well as transition metals act as catalysts to bring about reactions, which proceed with high efficiencies and selectivities. Various metal–organic cooperative catalytic systems developed for C–H and C–C bond activation reactions are discussed in this review. Also discussed are how each metal–organic cooperative catalyst affects the reaction mechanism and what kinds of substrates can be applied in each of the catalytic processes.

Metal–Organic Cooperative Catalysis in C–H and C–C Bond Activation

ConspectusThe selective oxidation of organic molecules is a fundamentally important component of modern synthetic chemistry. In the past decades, direct oxidative C–H and C–C bond functionalization has proved to be one of the most efficient and straightforward methods to synthesize complex products from simple and readily available starting materials. Among these oxidative processes, the use of molecular oxygen as a green and sustainable oxidant has attracted considerable attention because of its highly atom-economical, abundant, and environmentally friendly characteristics. The development of new protocols using molecular oxygen as an ideal oxidant is highly desirable in oxidation chemistry. More importantly, the oxygenation reaction of simple molecules using molecular oxygen as the oxygen source offers one of the most ideal processes for the construction of O-containing compounds. Aerobic oxidation and oxygenation by enzymes, such as monooxygenase, tyrosinase, and dopamine β-monooxygenase, have been obs...

Oxygenation via C–H/C–C Bond Activation with Molecular Oxygen

Atroposelective synthesis of axially chiral biaryls by palladium-catalyzed C−H olefination, using tert-leucine as an inexpensive, catalytic, and transient chiral auxiliary, has been realized. This strategy provides a highly efficient and straightforward access to a broad range of enantioenriched biaryls in good yields (up to 98 %) with excellent enantioselectivities (95 to >99 % ee). Kinetic resolution of trisubstituted biaryls bearing sterically more demanding substituents is also operative, thus furnishing the optically active olefinated products with excellent selectivity (95 to >99 % ee, s-factor up to 600).

Atroposelective Synthesis of Axially Chiral Biaryls by Palladium-Catalyzed Asymmetric C−H Olefination Enabled by a Transient Chiral Auxiliary

A catalytic hydroesterification process using HCO2Na, Ru3(CO)12 and alcohols for the preparation of ester modified polybutadienes

Well-defined recyclable Pd- and Rh-bipyridyl group-impregnated SBA-15 catalysts were prepared for C-C bond coupling reaction and selective hydrogenation reactions, respectively. These SBA-15 derived ligands for the catalysts were prepared by direct and indirect co-condensation method using bipyridyl-linked methallylsilane. This indirect method, involving methoxysilane generated from methallylsilane shows higher loading efficiency of transition metal catalysts on SBA-15 than the direct use of methallylsilane.

Recyclable Transition Metal Catalysis using Bipyridine-Functionalized SBA-15 by Co-condensation of Methallylsilane with TEOS.

A simple, one-step method for covalent bond immobilization of biomolecules on silica operated in water is described. In the approach, an NHS-ester linked methallylsilane is utilized as a bifunctional linker to couple the biomolecule to the silica surface. Weak organic acid such as acetic acid activates the silica surface enough to react with bifunctional linker without destroying activity of biomolecule.

/pdf/a-one-step-method-for-covalent-bond-immobilization-of-408tbur0et.pdf

Woo Jin Park

Papers

Metal–Organic Cooperative Catalysis in C–H and C–C Bond Activation

A catalytic hydroesterification process using HCO2Na, Ru3(CO)12 and alcohols for the preparation of ester modified polybutadienes

Recyclable Transition Metal Catalysis using Bipyridine-Functionalized SBA-15 by Co-condensation of Methallylsilane with TEOS.

A one-step method for covalent bond immobilization of biomolecules on silica operated in aqueous solution.