Highly diastereoselective intramolecular Diels–Alder reaction of chiral silatrienes

New Si-chiral 2-silahexa-3,5-dienyl acrylates were prepared in six steps from dichloro(chloromethyl)methylsilane. The EtAlCl2 catalysed intramolecular Diels–Alder reaction of these compounds gave chiral 4-sila-4a,7,8,8a-tetrahydroisochroman-1-ones in good yield. Very good diastereoselectivity was observed for a silatriene bearing a methyl and a 2-methoxyphenyl substituent on the chiral silicon atom.