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

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

Transition-metal-catalyzed cross-coupling reactions have been well-established as indispensable tools in modern organic synthesis. One of the major research goals in cross-coupling area is expanding the scope of the coupling partners. In the past decade, diazo compounds (or their precursors N-tosylhydrazones) have emerged as nucleophilic cross-coupling partners in C–C single bond or C═C double bond formations in transition-metal-catalyzed reactions. This type of coupling reaction involves the following general steps. First, the organometallic species is generated by various processes, including oxidative addition, transmetalation, cyclization, C–C bond cleavage, and C–H bond activation. Subsequently, the organometallic species reacts with the diazo substrate to generate metal carbene intermediate, which undergoes rapid migratory insertion to form a C–C bond. The new organometallic species generated from migratory insertion may undergo various transformations. This type of carbene-based coupling has proven...

Transition-Metal-Catalyzed Cross-Couplings through Carbene Migratory Insertion

The present review offers an overview of nonclassical (e.g., with no pre- or in situ activation of a carboxylic acid partner) approaches for the construction of amide bonds. The review aims to comprehensively discuss relevant work, which was mainly done in the field in the last 20 years. Organization of the data follows a subdivision according to substrate classes: catalytic direct formation of amides from carboxylic and amines (section 2); the use of carboxylic acid surrogates (section 3); and the use of amine surrogates (section 4). The ligation strategies (NCL, Staudinger, KAHA, KATs, etc.) that could involve both carboxylic acid and amine surrogates are treated separately in section 5.

Nonclassical Routes for Amide Bond Formation

The transition-metal-catalyzed addition of C–H bonds to carbonyls, imines, and related polarized π bonds has emerged as a particularly efficient and powerful approach for the construction of an incredibly diverse array of heteroatom-substituted products. Readily available and stable inputs are typically employed, and reactions often proceed with very high functional group compatibility and without the production of waste byproducts. Additionally, many transition-metal-catalyzed C–H bond additions to polarized π bonds occur within cascade reaction sequences to provide rapid access to a diverse array of different heterocyclic as well as carbocyclic products. This review highlights the diversity of transformations that have been achieved, catalysts that have been used, and types of products that have been prepared through the transition-metal-catalyzed addition of C–H bonds to carbonyls, imines, and related polarized π bonds.

Transition-Metal-Catalyzed C–H Bond Addition to Carbonyls, Imines, and Related Polarized π Bonds

"Comprehensive Heterocyclic Chemistry" was published in 1984 and is now available on CD-ROM.

Comprehensive heterocyclic chemistry on CD-ROM

http://orgmedichem.skku.edu/erp/erpmenus/professor_thesis/upLoadFiles/KIS-OL.pdf

Rh(III)-Catalyzed Direct Coupling of Azobenzenes with α-Diazo Esters: Facile Synthesis of Cinnolin-3(2H)-ones.

The rhodium(III)-catalyzed direct allylation of indolines with allylic carbonates at room temperature is described. These transformations provide the facile and efficient construction of C7-allylated indolic scaffold.

/pdf/mild-rh-iii-catalyzed-c7-allylation-of-indolines-with-ebscoqgfdu.pdf

Mild Rh(III)-Catalyzed C7-Allylation of Indolines with Allylic Carbonates

Cross-Coupling of Acrylamides and Maleimides under Rhodium Catalysis: Controlled Olefin Migration.

The rhodium(III)-catalyzed site-selective C–H alkylation of various N-heterocycles, such as indolines, carbazoles, and pyrroles with readily available allylic alcohols is described. This protocol allows the generation of a heterocyclic scaffold containing a β-aryl carbonyl moiety, which is known to be a crucial structural unit of biologically active compounds.

Rhodium-Catalyzed C-H Alkylation of Indolines with Allylic Alcohols: Direct Access to β-Aryl Carbonyl Compounds.

Herb extracts commercially used in Asia were screened for their estrogenic activity with a recombinant yeast system with both a human estrogen receptor (ER) expression plasmid and a reporter plasmid. Pueraria lobata (flower) had the highest estrogenic relative potency (RP, 17-estradiol = 1.00) (7.8e-3) (RP for + control), followed by Amomum xanthioides (1.3e-3), Glycyrrhiza uralensis, Zingiber officinale, Rheum palmatum, Curcuma aromatica, Eriobotrya japonica, Sophora flavescens, Anemarrhena asphodeloides, Polygonum multiflorum and Pueraria lobata (root) (9.5e-4-1.0e-4), and Prunus persica, Lycoppus lucidus and Adenophora stricta (9.0e-5-8.0e-5). In the antiproliferative assay, five human cancer cell lines representing different tissues (breast, lung and ovary) were used. Eriobotrya japonica showed strong cytotoxicity in ER-negative breast cancer (MDA-MB-231), cervix epitheloid (HeLa) and lung (A549) carcinoma cell lines.

Joa Sub Oh

Papers

Rh(III)-Catalyzed Direct Coupling of Azobenzenes with α-Diazo Esters: Facile Synthesis of Cinnolin-3(2H)-ones.

Mild Rh(III)-Catalyzed C7-Allylation of Indolines with Allylic Carbonates

Cross-Coupling of Acrylamides and Maleimides under Rhodium Catalysis: Controlled Olefin Migration.

Rhodium-Catalyzed C-H Alkylation of Indolines with Allylic Alcohols: Direct Access to β-Aryl Carbonyl Compounds.

Evaluation of oriental medicinal herbs for estrogenic and antiproliferative activities