Palladium-Catalyzed Direct Selanylation of Chalcogenophenes and Arenes Assisted by 2-(Methylthio)amide.

The direct and selective conversion of a C-H bond into a C-Se bond remains a significant challenge, which is even more intricate with substrates having an innate regioselectivity under several reaction conditions, such as chalcogenophenes. We overrode their selectivity toward selanylation using palladium, copper, and the 2-(methylthio)amide directing group. This chelation-assisted direct selanylation was also suitable for mono and double ortho functionalization of arenes. The mechanistic studies indicate high-valent Pd(IV) species in the catalytic cycle, a reversible C-H activation step, and Cu(II) as a sequestering agent for organoselenide byproducts.

Transition metal catalysed direct sulfanylation of unreactive C-H bonds: an overview of the last two decades.

Transition metal catalysed direct sulfanylations of unreactive C-H bonds have become a unique and straightforward synthetic strategy in late-stage C-S bond formation of relevant complex molecules. Such transformations represent a breakthrough in modern synthetic organic chemistry, as they offer unusual reactivity patterns and avoid pre-functionalization of the starting materials. Despite inherent challenges in activating/functionalizing unreactive C-H bonds, a considerable number of different transition metals have shown the ability to selectively catalyze these processes toward C-S bond formation. In this sense, this review article covers the development and mechanistic analysis of the direct sulfanylation of Csp3-H and Csp2-H bonds through transition metal catalysed reactions in the last two decades, providing an essential guide for organic chemists working on this research area.

Green Hydroselenation of Aryl Alkynes: Divinyl Selenides as a Precursor of Resveratrol.

A simple and efficient protocol to prepare divinyl selenides has been developed by the regio- and stereoselective addition of sodium selenide species to aryl alkynes. The nucleophilic species was generates in situ, from the reaction of elemental selenium with NaBH4, utilizing PEG-400 as the solvent. Several divinyl selenides were obtained in moderate to excellent yields with selectivity for the (Z,Z)-isomer by a one-step procedure that was carried out at 60 °C in short reaction times. The methodology was extended to tellurium, giving the desired divinyl tellurides in good yields. Furthermore, the Fe-catalyzed cross-coupling reaction of bis(3,5-dimethoxystyryl) selenide 3f with (4-methoxyphenyl)magnesium bromide 5 afforded resveratrol trimethyl ether 6 in 57% yield.

Silver-catalyzed direct selanylation of indoles: synthesis and mechanistic insights.

Herein we describe the Ag(i)-catalyzed direct selanylation of indoles with diorganoyl diselenides. The reaction gave 3-selanylindoles with high regioselectivity and also allowed direct access to 2-selanylindoles when the C3 position of the indole ring was blocked via a process similar to Plancher rearrangement. Experimental analyses and density functional theory calculations were carried out in order to picture the reaction mechanism. Among the pathways considered (via concerted metalation-deprotonation, Ag(iii), radical, and electrophilic aromatic substitution), our findings support a classic electrophilic aromatic substitution via Lewis adducts between Ag(i) and diorganoyl diselenides. The results also afforded new insights into the interactions between Ag(i) and diorganoyl diselenides.

Crystal structures of 3-halo-2-organochalcogenylbenzo[b]chalcogenophenes.

The structure of the title compounds 3-bromo-2-(phenyl-sulfan-yl)benzo[b]thiophene (C14H9BrS2; 1), 3-iodo-2-(phenyl-sulfan-yl)benzo[b]thio-phene (C14H9IS2; 2), 3-bromo-2-(phenyl-selan-yl)benzo[b]seleno-phene (C14H9BrSe2; 3), and 3-iodo-2-(phenyl-selan-yl)benzo[b]seleno-phene (C14H9ISe2; 4) were determined by single-crystal X-ray diffraction; all structures presented monoclinic (P21/c) symmetry. The phenyl group is distant from the halogen atom to minimize the steric hindrance repulsion for all structures. Moreover, the structures of 3 and 4 show an almost linear alignment of halogen-selenium-carbon atoms arising from the intra-molecular orbital inter-action between a lone pair of electrons on the halogen atom and the anti-bonding σ*Se-C orbital (n halogen→σ*Se-C). This inter-action leads to significant differences in the three-dimensional packing of the mol-ecules, which are assembled through π-π and C-H⋯π inter-actions. These data provide a better comprehension of the inter-molecular packing in benzo[b]chalcogenophenes, which is relevant for optoelectronic applications.

Transition metal catalysed direct selanylation of arenes and heteroarenes.

Transition metal catalysed C-H functionalization has reached an exciting level of sophistication, and, today, it represents a paradigm shift from the standard logic of synthetic chemistry. The direct conversion of C-H bonds into C-heteroatoms remains, however, a critical challenge. Nowadays, there is a great demand in general synthetic chemistry in, for example, the materials science for the development of straightforward C-Se bond formation, in order to fulfil the practical requirements. In this sense, this review summarizes recent outstanding advances in the C-Se bond formation through transition metal-catalysed direct selanylation, providing new insights into their mechanistic aspects and disclosing effective synthetic routes with high atom economy. In addition, this review intends to show the growing opportunities to construct complex chemical scaffolds containing selenium atoms.