Nonracemic Homopropargylic Alcohols via Asymmetric Allenylboration with the Robust and Versatile 10-TMS-9-borabicyclo[3.3.2]decanes

摘要

The asymmetric allenylboration of representative aldehydes with the stable,storable 1 is reported.Easily and efficiently prepared in either enantiomeric form from the air-stable crystalline 4 through simple Grignard procedures,1 gives 6 cleanly.The latter is easily isolated in high yield and ee with predictable stereochemistry.The procedure also regenerates 4 for its direct conversion back to 1 and facilitates the efficient recovery of the pseudoephedrine.The net process is the synthetic equivalent of the asymmetric addition of allenylmagnesium bromide to aldehydes.