Enantioselective Synthesis of Dialkylated N-Heterocycles by Palladium-Catalyzed Allylic Alkylation

The enantioselective synthesis of α-disubstituted N-heterocyclic carbonyl compounds has been accomplished using palladium-catalyzed allylic alkylation. These catalytic conditions enable access to various heterocycles, such as morpholinone, thiomorpholinone, oxazolidin-4-one, 1,2-oxazepan-3-one, 1,3-oxazinan-4-one, and structurally related lactams, all bearing fully substituted α-positions. Broad functional group tolerance was explored at the α-position in the morpholinone series. We demonstrate the utility of this method by performing various transformations on our useful products to readily access a number of enantioenriched compounds

An Efficient Protocol for the Palladium-Catalyzed Asymmetric Decarboxylative Allylic Alkylation Using Low Palladium Concentrations and a Palladium(II) Precatalyst

Enantioselective catalytic allylic alkylation for the synthesis of 2-alkyl-2-allylcycloalkanones and 3,3-disubstituted pyrrolidinones, piperidinones and piperazinones has been previously reported by our laboratory. The efficient construction of chiral all-carbon quaternary centers by allylic alkylation was previously achieved with a catalyst derived in situ from zero-valent palladium sources and chiral phosphinooxazoline (PHOX) ligands. We now report an improved reaction protocol with broad applicability among different substrate classes in industry-compatible reaction media using loadings of palladium(II) acetate as low as 0.075 mol% and the readily available chiral PHOX ligands. The novel and highly efficient procedure enables facile scale-up of the reaction in an economical and sustainable fashion

Improvement of energy resolution in time-of-flight method for high energy neutron measurement

In the time-of-flight measurement of high energy neutrons, the time resolution is often required to be as good as possible. For improvement of the energy resolution, the time-of-flight study was made by the use of Li (p, n) reaction at forward angles. Two types of detectors were tested. One was a liquid organic scintillator NE-213 5 inches (127 mm) in diameter and 127 mm thick connected with three Hamamatsu H2431 photomultipliers 2 inches (51 mm) in diameter. The other was NE-213 of the same size with a Hamamatsu R1250 127 mm in diameter. The experiment was made at pi2 beam line of 12 GeV proton synchrotron in High Energy Accelerator Research Organization (KEK). The incident proton energy was 800 MeV, and the flight path was 5 m. Two neutron detectors were set at 0 and 5 degrees, respectively. The time resolutions for prompt gamma rays were 0.5 ns for NE-213 with three H2431s and 1.0 ns for NE-213 with R1250. The energy resolutions for 800 MeV neutrons were derived from these values were 70 and 100 MeV, respectively. 12 Refs