Homoallylamines and acylated homoallylamines are some of the important structural subunits of biologically active compounds such as �-amino acids and are useful intermediates in a wide range of syntheses of alkaloids and nitrogen-containing heterocycles. Thus, the enantio- and diastereoselective synthesis of homoallylamines has become one of the major goals in the fields of medicinal chemistry and organic synthesis. Consequently, the development of a new method for the synthesis of optically active homoallylamines has been continuously attempted by organic and synthetic chemists.We have recently reported a new approach to the synthesis of the N-acyliminium ion from N,O-acetal TMS ether, which was conveniently prepared from acylcarbamate. The N,O-acetal TMS ether proved to be an excellent acyliminium ion precursor in terms of convenience of preparation, chemical stability, and functional versatility in addition to the accessible structural diversity of cyclic and acyclic N-acyliminium ions. More recently, we have reported a novel asymmetric synthetic route for �-amino acids using this methodology.Herein, we describe a highly stereoselective and efficient method for the synthesis of optically active homoallylamines through chiral auxiliary assisted diastereoselective allylation of N-acyliminium ions prepared from N,O-acetal TMS ether and the facile removal of the naphthylethyl auxiliary and its application for the total synthesis of novel tripeptide containing a �-amino acid.

Expedient synthesis of chiral homoallylamines via N,O-acetal TMS ethers and its application

245th National Meeting (2013)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.