Silenes in organic synthesis 1: Diastereoselectivity in the siloxysilene-diene diels-alder cycloaddition

Silylenes, Silenes, and Disilenes: Novel Silicon‐Based Reagents for Organic Synthesis?

“…[83] The chemistry of silenes is equally diverse but as yet is much less well explored. [84] As with the silylene chemistry discussed above, the general applicability of such an approach is limited by the high temperature requirements. [84] As with the silylene chemistry discussed above, the general applicability of such an approach is limited by the high temperature requirements.…”

“…The chemistry of silenes is equally diverse but as yet is much less well explored. Earlier reports have shown that simple siloxysilenes undergo thermal Diels–Alder reactions with electron rich dienes with moderate diastereoselectivity (Scheme ) 84…”

Anomalous rearrangements in the reaction of acylpolysilanes with TMSNTf2

“…In the course of an investigation of the use of silenes as reagents for novel transformations in organic synthesis we had need to generate silenes from acylpolysilanes in what is effectively a 1,3 silyl migration. 1 This is normally achieved through either thermal (T = ca. 180 °C) or photochemical initiation.…”

“…180 °C) or photochemical initiation. 1,2 Neither of these methods is compatible with the range of functionality which we wished to explore. Consequently, in order to determine whether it was possible to generate silenes through the Lewis acid promoted 1,3-silyl shift of acylpolysilanes, we investigated the reaction of benzoylpolysilane with silyl based Lewis acids (TMSOTf, TMSNTf 2 ).…”

The first intramolecular silene Diels–Alder reactions

“…Building on our earlier experience for the generation of silenes through either a thermal 1,3-silyl shift of an acyl polysilane 12 or a sila-Peterson reaction, 13a initial attempts focused on simple acyclic substrates combining silene precursor and dienyl fragments. Hepta-4,6-dienol 3 could be readily generated through a sequence involving the Claisen ortho ester rearrangement of divinyl carbinol 1 and reduction of the resultant ester 2.…”