Site-Selective Ortho/Ipso C-H Difunctionalizations of Arenes using Thianthrene as a Leaving Group.

Site-selective ortho/ipso C-H difunctionalizations of aromatic compounds were designed to afford polyfunctionalized arenes including challenging 1,2,3,4-tetrasubstituted ones (62 examples, up to 97 % yields). To ensure the excellent regioselectivity of the process while keeping high efficiency, an original strategy based on a "C-H thianthenation/Catellani-type reaction" sequence was developed starting from simple arenes. Non-prefunctionalized arenes were first regioselectively converted into the corresponding thianthrenium salts. Then, a palladium-catalyzed, norbornene (NBE)-mediated process allowed the synthesis of ipso-olefinated/ortho-alkylated polyfunctionalized arenes using a thianthrene as a leaving group (revisited Catellani reaction). Pleasingly, using a commercially available norbornene (NBE) and a unique catalytic system, synthetic challenges known for the Catellani reaction with aryl iodides were smoothly and successfully tackled with the "thianthrenium" approach. The protocol was robust (gram-scale reaction) and was widely applied to the two-fold functionalization of various arenes including bio-active compounds. Moreover, a panel of olefins and alkyl halides as coupling partners was suitable. Pleasingly, the "thianthrenium" strategy was successfully further applied to the incorporation of other groups at the ipso (CN/alkyl/H, aryl) and ortho (alkyl, aryl, amine, thiol) positions, showcasing the generality of the process.

Sequential ortho-/meta-C-H functionalizations of N-tosyl-benzamides for the synthesis of polyfunctionalized arenes.

Selective one-pot sequential ortho-/meta-C-H functionalizations provided highly desirable polyfunctionalized arenes. Starting from readily available carboxylic acid derivatives, the concomitant formation of C-O and C-halogen bonds was achieved under mild reaction conditions (12 examples, up to 75% yield). The utility of the products was illustrated with post-functionalization reactions and Metiglinid synthesis.

Ru(II)-Catalyzed Hydroarylation of in†situ Generated 3,3,3-Trifluoro-1-propyne by C-H Bond Activation: A Facile and Practical Access to ß-Trifluoromethylstyrenes.

In this study, a practical and straightforward synthesis of ß-(E)-trifluoromethylstyrenes by ruthenium-catalyzed C-H bond activation was developed. The readily available and inexpensive 2-bromo-3,3,3-trifluoropropene (BTP), a non-ozone depleting reagent, was used as a reservoir of 3,3,3-trifluoropropyne. With this approach, the monofunctionalization of a panel of heteroarenes was possible in a safe and scalable manner (23 examples, up to 87 % yield). Mechanistic investigations and density functional theory (DFT) calculations were also conducted to get a better understanding of the mechanism of this transformation. These studies suggested that 1) a cyclometallated ruthenium complex enabled the transformation, 2) this complex exhibited high efficiency in this transformation compared to the commercially available [RuCl2 (p-cymene)]2 and 3) the mechanism proceeded through a bis-cyclometallated ruthenium intermediate for the carboruthenation step.

Design and Use of Electrophilic Thiocyanating and Selenocyanating Reagents: An Interesting Trend for the Construction of SCN- and SeCN-Containing Compounds.

Organothiocyanate and organoselenocyanate compounds are of paramount importance in organic chemistry as they are key intermediates to access sulfur- and selenium-containing compounds. Therefore, among the different synthetic pathways to get SCN- and SeCN-containing molecules, original methodologies using electrophilic reagents have recently been explored. This Minireview will showcase the recent advances that have been made. In particular, the design of several electrophilic sources and their applications for the thiocyanation and the selenocyanation of various classes of compounds will be highlighted and discussed.

Ortho C-H arylation of arenes at room temperature using visible light ruthenium C-H activation.

A ruthenium-catalyzed ortho C-H arylation process is described using visible light. Using the readily available catalyst [RuCl2(p-cymene)]2, visible light irradiation was found to enable arylation of 2-aryl-pyridines at room temperature for a range of aryl bromides and iodides.