Synthesis and ring opening reactions of a 2-silabicyclo[2.1.0]pentane

Abstract

Methyl 2-silabicyclo[2.1.0]pentane-1-carboxylate, obtained by a photochemical intramolecular cyclopropanation reaction of an [small alpha]-allylsilyl-[small alpha]-diazoacetate, undergoes ring opening reactions under different conditions leading to methyl 2-[diisopropyl(methoxy)silylmethyl]cyclopropane-1-carboxylate, a 1-sila-4-cyclopentene-2-carboxylate or an allyl(methoxysilyl)ketene.

Lightening Diazo Compounds?

“…Over the years of studies on light-induced reactions of diazo compounds, many C–H insertions were developed (Scheme ). ,,− Most of them are exhaustively described in previous reviews; , therefore, here we focus only on the most recent advancements.…”

Oxidative detagging of fluorous organosilanes

“…Lithiation of the starting material was achieved at À30 8C with n-butyl lithium in a 1:1 mixture of Et 2 O and THF. Subsequent addition of commercially available chloro(dimethyl)allylsilane or freshly distilled chloro(diisopropyl)allylsilane or chloro(methyl)(phenyl)allylsilane (prepared in one step from dichloro(diisopropyl)silane or dichloro(methyl)(phenyl)silane respectively [8]) led to the formation of the desired products 1b-d after stirring at room temperature typically for 4 h (entries 1-3, Table 1). Despite extending the reaction time to 16 h, 1c could not be accessed in a higher yield than 50% (Scheme 3, Table 1, entry 2).…”

Synthesis of azasilacyclopentenes and silanols via Huisgen cycloaddition-initiated C–H bond insertion cascades

“…Varying the alkyl groups at R 1 and R 2 of 74 does not significantly affect the formation of the azasilacyclopentene. Although an allyl group could potentially undergo cyclopropanation with an intermediate silyl carbene, 32a,38 only the azasilacyclopentene 75e is seen (entry 5). Cyclic substrates generally provided spiro-oxazolones (entry 6–10).…”