Asymmetric hydrogenation of quinazolinium salts was catalysed by halogen-bridged dinuclear iridium complexes bearing chiral diphosphine ligands, yielding tetrahydroquinazoline and 3,4-dihydroquinazoline with high enantioselectivity. A derivative of chiral dihydroquinazoline was used as a chiral NHC ligand.
TMPMgCl·LiCl and TMPZnCl·LiCl allow facile magnesiation and zincation, respectively, of the 1,4-dithiin scaffold, producing polyfunctionalized 1,4-dithiins. A subsequent metalation of these S-heterocycles can also be achieved with the same TMP bases, leading to 2,3-disubstituted-1,4-dithiins. The Mg- and Zn-TMP bases allow as well the successful metalation of 1,4,5,8-tetrathianaphthalene and 1,4,5,6,9,10-hexathiaanthracene.
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