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Enantiopure secondary alcohols are fundamental high-value synthetic building blocks. One of the most attractive ways to get access to this compound class is the catalytic hydroboration. We describe a new concept for this reaction type that allowed for exceptional catalytic turnover numbers (up to 15 400), which were increased by around 1.5-3 orders of magnitude compared to the most active catalysts previously reported. In our concept an aprotic ammonium halide moiety cooperates with an oxophilic Lewis acid within the same catalyst molecule. Control experiments reveal that both catalytic centers are essential for the observed activity. Kinetic, spectroscopic and computational studies show that the hydride transfer is rate limiting and proceeds via a concerted mechanism, in which hydride at Boron is continuously displaced by iodide, reminiscent to an S N 2 reaction. The catalyst, which is accessible in high yields in few steps, was found to be stable during catalysis, readily recyclable and could be reused 10 times still efficiently working., (© 2020 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

2H-Azirines are synthetically versatile, highly strained, three-membered heterocycles containing an imino double bond. We report their efficient Ru-catalyzed synthesis using low catalyst loadings under neutral conditions from isoxazolinone substrates, which are readily accessible from β-ketoesters. The azirines were shown to be efficient precursors for functionalized pyridine, indole, dihydropyrrole, and pyrrolidine heterocycles.