No abstract

The development of methods for carbon-carbon bond formation under benign conditions is an ongoing challenge for synthetic chemists. In recent years there has been considerable interest in using selective C-H activation as a direct route for generating reactive intermediates. Herein, the use of visible-light-mediated dual photoredox organocatalysis as a mild and effective method for Csp2 -H activation of aldehydes is reported, resulting in the generation of acyl radicals. These nucleophilic acyl radical species can undergo either addition to electrophilic alkenes or nickel-catalyzed cross-coupling reactions to provide a quick access to broad range of unsymmetrical ketones, which are abundantly found in many organic building blocks.

Being a handle for synthesizing quaternary carbon centers and olefins, together with ubiquitous appearance in organic building blocks makes tertiary alcohols valuable targets in synthesis. However, traditional syntheses of these alcohols have faced several challenges including the employment of functionalized reactive reagents, undesirable side reactions and decomposition of the alcohol products under harsh conditions. The paucity of synthetic approach to bulky tertiary alcohols prompts our interest to develop a benign catalytic protocol to tackle the current issues. Here, we have successfully demonstrated the use of ketyl radicals in intermolecular cross radical-radical coupling, which has opened the new door for accessing complex tertiary alcohols. On the other hand, by starting from feedstock and naturally derived chemicals without any preactivation, it would be superior to traditional methodologies in industrial context.

A practical approach towards N-glycopeptide synthesis using an auxiliary-mediated dual native chemical ligation (NCL) has been developed. The first NCL connects an N-linked glycosyl auxiliary to the thioester side chain of an N-terminal aspartate oligopeptide. This intermediate undergoes a second NCL with a C-terminal thioester oligopeptide. Mild cleavage provides the desired N-glycopeptide.

We report the synthesis and magnetic and photomagnetic behaviour of a novel valence tautomeric cobalt complex, [Co(3,5-dbbq)2(μ-bpym)] (1) (3,5-dbbq = 3,5-di-tert-butyl-1,2-benzoquinone and μ-bpym = 2,2'-bipyrimidine). The synthesis is performed by reacting Co2(CO)8 and μ-bpym in the presence of the ligand 3,5-dbbq in a mixed solvent under inert atmosphere. The magnetic behavior clearly shows the presence of electron transfer from the catecholate ligand to the cobalt center, producing valence tautomers of [Co(II)(SQ)2] with a transition temperature (T1/2) of 215 K. Photomagnetic studies, performed via both SQUID magnetometry and X-band electron paramagnetic resonance, show the clear presence of photoinduced valence tautomerism, at temperatures considerably higher than previous systems. A metastable charge distribution is observed, strengthening previous investigations on the character of mixed valence ligands. Entropy-driven valence tautomeric interconversion is observed, and drives the transition to the most stable charge distribution. The complex has the ability to coordinate and can be used as a photoswitchable building block, with the photomagnetic characterisation evidencing a metastable state lifetime of the photo-induced valence tautomeric process of ca. 2.9 × 10(4) s below 20 K. The observed yields are higher than ones in similar systems, showing that tiny changes in the molecular structures may have a huge impact.