Acyclic Remote 1,6-Stereoselection.

Stereochemical communication in homopropargylation and homoallylation of aldehydes was achieved by the Ti-O temporary linker strategy. Propargylic and allylic alcohol derivatives were employed as convenient pronucleophiles, obviating prefabrication of propargylation/allylation reagents. It was surprising that 1,6-diastereoselectivity was affected by not only the Grignard reagent but also the reaction solvent.

Nazarov cyclization of dienylaziridines: synthesis of cyclopentadienyl/hydrinedienyl/indenyl glycines.

Cyclopentadienyl, hydrinedienyl, and indenyl glycines were synthesized using dienylaziridines as Nazarov cyclization precursors for the first time. Several substrates were synthesized to demonstrate the compatibility of this reaction. Asymmetric synthesis of these amino acids was also developed to show the additional scope of this method.