Synthesis of 2‐silaoxane via 1,3‐ photocycloaddition

Abstract

Irradiation of an aryl group with a silyl tethered alkene yields a tetracyclic 2-silaoxane with high regioselectivity. The multicyclic structure has been further modified to give an unstable tricyclic diol. Photocycloaddition between cyclopentene and phenylcyclopropane gave a single major cycloadduct without cyclopropyl ring opening, indicating that the putative radical intermediate involved in cycloaddition apparently has a very short lifetime if it exists at all.

11 Organic photochemistry

“…Silicon has been used in a tether for intramolecular 1,3-photocycloaddition. 13 Irradiation of 21, containing an aryl group with a silyl tethered alkene, gives the tetracyclic 2-silaoxane 22 which contains five contiguous stereocenters that are formed with regio-and stereochemical control in a single step (Scheme 11). The tethering group can be removed while maintaining the stereocenters.…”