Cu/nitroxyl catalysts have been identified that promote highly efficient and selective aerobic oxidative lactonization of diols under mild reaction conditions using ambient air as the oxidant. The chemo- and regioselectivity of the reaction may be tuned by changing the identity of the nitroxyl cocatalyst. A Cu/ABNO catalyst system (ABNO = 9-azabicyclo[3.3.1]nonan-N-oxyl) shows excellent reactivity with symmetrical diols and hindered unsymmetrical diols, whereas a Cu/TEMPO catalyst system (TEMPO = 2,2,6,6-tetramethyl-1-piperidinyl-N-oxyl) displays excellent chemo- and regioselectivity for the oxidation of less hindered unsymmetrical diols. These catalyst systems are compatible with all classes of alcohols (benzylic, allylic, aliphatic), mediate efficient lactonization of 1,4-, 1,5-, and some 1,6-diols, and tolerate diverse functional groups, including alkenes, heterocycles, and other heteroatom-containing groups.
As a finite-energy-bandgap alternative to graphene, semiconducting molybdenum disulfide (MoS2) has recently attracted extensive interest for energy and sensor applications. In particular for broad-spectral photodetectors, multilayer MoS2 is more appealing than its monolayer counterpart. However, little is understood regarding the physics underlying the photoresponse of multilayer MoS2. Here, we employ scanning photocurrent microscopy to identify the nature of photocurrent generated in multilayer MoS2 transistors. The generation and transport of photocurrent in multilayer MoS2 are found to differ from those in other low-dimensional materials that only contribute with either photovoltaic effect (PVE) or photothermoelectric effect (PTE). In multilayer MoS2, the PVE at the MoS2-metal interface dominates in the accumulation regime whereas the hot-carrier-assisted PTE prevails in the depletion regime. Besides, the anomalously large Seebeck coefficient observed in multilayer MoS2, which has also been reported by others, is caused by hot photo-excited carriers that are not in thermal equilibrium with the MoS2 lattice.
A series of 2-dialkylphosphino-2'-alkoxy-1,1'-binaphthyl ligands (6a-c and 8a-c) have been prepared conveniently by a lithium-initiated ring-opening reaction of dinaphthofuran, followed by selective phosphorylation. These compounds displayed a remarkable air and moisture stability, both in solid form and in solution. Application of these phosphine ligands in palladium-catalyzed C-N bond forming reactions revealed the crucial roles of the steric bulk of the substituents on the phosphorus atom governing the catalytic activity. Specifically, 2-di-tert-butylphosphino-2'-isopropoxy-1,1'-binaphthyl (8b) proved to be the most effective for the aminations of aryl halides with primary amines, while the less bulky 2-dicyclohexyl-2'-methoxy-1,1'-binaphthyl (6a) was more effective for the aminations with secondary amines. The steric and electronic effects of the ligands were analyzed to account for these observations.
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