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.

Automated summary

Stereochemical communication was achieved in homopropargylation and homoallylation of aldehydes through the Ti-O temporary linker strategy. Propargylic and allylic alcohol derivatives were used as convenient pronucleophiles, eliminating the need for pre-fabrication of propargylation/allylation reagents. Surprisingly, 1,6-diastereoselectivity was affected by both the Grignard reagent and the reaction solvent.