An unexpected stereoselective anomeric substitution with carbamates promoted by HNTf2 is described here. Our experiments suggest that the observed diastereoselectivity is a result of thermodynamic equilibration of protonated N-acyl aminals.

We have discovered thiazepine moiety-controlled regioselective skeletal rearrangements of 7-oxanorbornadiene derivatives (2, 7 and 12) with high regioselectivity and/or diastereoselectivity in the presence of Brønsted acid.

A cascade silver(I)-catalyzed hydroamination/Michael addition sequence has been developed to deliver highly substituted bicyclic guanidines. This transformation gives rise to geometrically and constitutionally stable ene-guanidines and generates a remote stereocenter with moderate to high diastereoselectivity.

A "green" and practical intramolecular pinacol coupling reaction promoted by InCl 3/Al catalysts in aqueous media has been developed. Under mild conditions, a novel class of polysubstituted cyclopentane-1,2-diols have been obtained with excellent diastereoselectivity.

The addition of dimethylaluminium alkoxyacetylides to Ellman's sulfinylimines is described. The reaction proceeds with excellent diastereoselectivity and high yield to produce oxygenated propargylamines in one step starting from simple dichloroenol ethers.

The geometry of the double bond in oxazolidinone-substituted ene carbamates controls the mode selectivity (ene reaction versus [2+2] cycloaddition) of singlet oxygen through stereoelectronic effects, whereas the chiral auxiliary provides high diastereoselectivity through steric shielding.

The well-defined conformation of an N,N'-diarylurea allows a chiral sulfinyl substituent to influence diastereoselectivity in the formation of new stereogenic centres up to 14 bond lengths away.

Thermolysis of the 3,5-hexadienyl acrylates (a) proceeds via the transition state E in which the connecting chain adopts a boatlike conformation due to a preference for maintaining ester overlap to afford the products b with good diastereoselectivity.

The N-heterocyclic carbene-catalyzed [4 + 2] cyclization of ketenes and 3-aroylcoumarins has been developed to give the corresponding dihydrocoumarin-fused multisubstituted dihydropyranones in high yield with good diastereoselectivity and high enantioselectivity.

The nature of the 7-substituent has a remarkable effect on the diastereoselectivity of the oxidative rearrangement of indole-2-carboxamides derived from (S)-2-methoxymethylpyrrolidine into chiral 3,3-disubstituted oxindoles.