RESUMEN

Semiconductor quantum dots (QDs) offer many advantages as photocatalysts for synthetic photoredox catalysis, but no reports have explored the use of QDs with nickel catalysts for C-C bond formation. We show here that 5.7 nm CdS QDs are robust photocatalysts for photoredox-promoted cross-electrophile coupling (40 000 TON). These conditions can be utilized on small scale (96-well plate) or adapted to flow. NMR studies show that triethanolamine (TEOA) capped QDs are the active catalyst and that TEOA can displace native phosphonate and carboxylate ligands, demonstrating the importance of QD surface chemistry.

RESUMEN

Strong reducing agents (<-2.0 V vs saturated calomel electrode (SCE)) enable a wide array of useful organic chemistry, but suffer from a variety of limitations. Stoichiometric metallic reductants such as alkali metals and SmI2 are commonly employed for these reactions; however, considerations including expense, ease of use, safety, and waste generation limit the practicality of these methods. Recent approaches utilizing energy from multiple photons or electron-primed photoredox catalysis have accessed reduction potentials equivalent to Li0 and shown how this enables selective transformations of aryl chlorides via aryl radicals. However, in some cases, low stability of catalytic intermediates can limit turnover numbers. Herein, we report the ability of CdS nanocrystal quantum dots (QDs) to function as strong photoreductants and present evidence that a highly reducing electron is generated from two consecutive photoexcitations of CdS QDs with intermediate reductive quenching. Mechanistic experiments suggest that Auger recombination, a photophysical phenomenon known to occur in photoexcited anionic QDs, generates transient thermally excited electrons to enable the observed reductions. Using blue light-emitting diodes (LEDs) and sacrificial amine reductants, aryl chlorides and phosphate esters with reduction potentials up to -3.4 V vs SCE are photoreductively cleaved to afford hydrodefunctionalized or functionalized products. In contrast to small-molecule catalysts, QDs are stable under these conditions and turnover numbers up to 47 500 have been achieved. These conditions can also effect other challenging reductions, such as tosylate protecting group removal from amines, debenzylation of benzyl-protected alcohols, and reductive ring opening of cyclopropane carboxylic acid derivatives.

Asunto(s)

Puntos Cuánticos , Catálisis , Química Orgánica , Electrones , Puntos Cuánticos/química , Sustancias Reductoras

RESUMEN

We present a combined electrochemical, kinetic, and synthetic study with a novel and easily accessible class of titanocene catalysts for catalysis in single-electron steps. The tailoring of the electronic properties of our Cp2 TiX-catalysts that are prepared in situ from readily available Cp2 TiX2 is achieved by varying the anionic ligand X. Of the complexes investigated, Cp2 TiOMs proved to be either equal or substantially superior to the best catalysts developed earlier. The kinetic and thermodynamic properties pertinent to catalysis have been determined. They allow a mechanistic understanding of the subtle interplay of properties required for an efficient oxidative addition and reduction. Therefore, our study highlights that efficient catalysts do not require the elaborate covalent modification of the cyclopentadienyl ligands.