A series of oxometallic species and metal acetylacetonates (acac) was examined as catalysts for oxidative carbonylation of styrene with benzaldehyde using t-butylhydroperoxide as the co-oxidant in warm acetonitrile. Among them, VO((acac)2 and vanadyl(IV) chloride were found to be the only catalyst class to achieve cross-coupling processes by judiciously tuning the ligand electronic attributes, leading to β-hydroxylation- and β-peroxidation-carbonylation of styrene, respectively, in a complementary manner. Mechanistic studies indicated that vanadyl-associated acyl radicals generated by t-butoxy radical-assisted, homolytic cleavage of the aldehyde C-H bond were involved in tandem processes with an exclusive syn diastereoselectivity in the case of β-methylstyrene.
High-valent chiral oxidovanadium(V) complexes derived from 3,5-substituted-N-salicylidene-L-tert-leucine were used as catalysts in asymmetric reduction of N-benzyl-βketoamides. Among six different solvents, three different alcohol additives, and two different boranes examined, the use of pinacolborane in tetrahydrofuran (THF) with a t-BuOH additive led to the best results at −20 °C. The corresponding βhydroxyamides can be furnished with yields up to 92% and an enantiomeric excess (ee) up to 99%. We have successfully extended this catalytic protocol for the synthesis of an (S)-duloxetine precursor.
Chemoselective enatiodivergent reduction of N-benzyl-α-keto amides catalyzed by chiral oxido-vanadium(V) complexes derived from reduced form of N-salicylidene L-tert Leucinate can be achieved in good yields and good to high enantioselectivities....
Directed assembly of loosely, Na-bound, oxidovanadate-centered quartets of C-symmetry from tailor-made chiral N-salicylidene-vanadyl(V) complexes, for the first time, allows for highly efficient Ba- or Hg-specific detection (by V NMR and VCD), transport (forming a unique helical capsule or a capped square planar complex, respectively), and green recovery from an aqueous phase containing 4 different alkaline earth ions or from at least 10 different metal ions of similar size and charge capacity into the CHCl layer without interference from oxa- or oxophilic ions like Mg, Ca, Cu, Cd, and Pb.
Product and Industrial Design (ID) is frequently regarded as a masculine and maledominated profession. Female Taiwanese industrial designers, similar to those in other countries, have not been as active as men in this field. However, more female students are enrolled in ID programmes in Taiwan than are male students, with the total ratio of female students reaching 61 per cent countrywide. To understand the cause of such inactivity, investigating female ID students’ career choices as they complete professional education is crucial. This study investigated the vocational maturity and career choices of female ID students in Taiwan. A questionnaire survey was conducted on 417 female ID students from 24 departments belonging to one of 23 Taiwanese universities. The results show that vocational maturity was generally positive, but a significant proportion of women intend to work outside of ID, possibly due to an overly negative view of ID as an industry. The outcome can be used to guide educators to assist female ID talents plan their career and enhance their employment opportunities.
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