Catalytic Allylic Oxidation of Alkenes Using an Asymmetric Kharasch-Sosnovsky Reaction

Kharasch and Sosnovsky reported the allylic oxidation of alkenes to give racemic allylic benzoates. This could be achieved efficiently using a tert-butyl perester as the oxidant, in the presence of a copper or cobalt salt. The use of C(2)-symmetric bis(oxazoline) ligands in the presence of copper(I) triflate with cyclic olefinic substrates gave the first synthetically useful asymmetric variant. The enantioselective control was good (up to 84 % ee) although yields were variable. In all cases the facial preference of the newly formed C-O bond was the same giving an S configuration at the allylic stereocenter. Lower stereocontrol was observed for large-ring alkenes and substantially reduced enantioselectivities were found with open-chain alkenes. This reaction has been further screened using a variety bis(oxazoline) and proline-derived ligands, which give a direct correlation between the chirality of the ligand and the enantioselectivity obtained. Individual substrates were found to be extremely sensitive to both the ligand structure and copper salt used as well as the presence of additives such as zinc, hydrazine, and molecular sieves.     

Pitch shifts for complex tones with unresolved harmonics and the implications for models of pitch perception

Complex tone bursts were bandpass filtered, 22nd-30th harmonic, to produce waveforms with five regularly occurring envelope peaks ("pitch pulses") that evoked pitches associated with their repetition period. Two such tone bursts were presented sequentially and separated by an interpulse interval (IPI). When the IPI was varied, the pitch of the whole sequence was shifted by between +2% and -5%. When the IPI was greater than one period, little effect was seen. This is consistent with a pitch mechanism employing a long integration time for continuous stimuli that resets in response to temporal discontinuities of greater than about one period of the waveform. Similar pitch shifts were observed for fundamental frequencies from 100 to 250 Hz. The pitch shifts depended on the IPI duration relative to the period of the complex, not on the absolute IPI duration. The pitch shifts are inconsistent with the autocorrelation model of Meddis and O'Mard [J. Acoust. Soc. Am. 102, 1811-1820 (1997)], although a modified version of the weighted mean-interval model of Carlyon et al. [J. Acoust. Soc. Am. 112, 621-633 (2002)] was successful. The pitch shifts suggest that, when two pulses occur close together, one of the pulses is ignored on a probabilistic basis.     

Chemical sensors that incorporate click-derived triazoles

Since the advent of click chemistry in 2001, the 1,4-disubstituted triazole has become an increasingly common motif in chemical sensors. Although these click-derived triazoles are generally used as a convenient method of ligation, their prevalence in chemosensors can be attributed to their ability to bind both cations and anions. In this critical review, we present an overview of the wide range of chemosensors that contain click-derived triazoles, with a particular focus on those cases where the triazole plays a functional, rather than merely a structural, role. Examples are categorised based on method of detection and key structural features, providing a complete picture of the current state of click-based chemosensors, as well as potential future directions for sensor design. (140 references).