Rhodium‐Catalyzed Reaction of Silacyclobutanes with Unactivated Alkynes to Afford Silacyclohexenes

Abstract

Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

Rhodium‐Catalyzed Intermolecular Silylation of Csp−H by Silacyclobutanes

“…The unexpected result of 2 d suggested that the silyl protecting group might take a role in the reaction, of which we have no understanding at this point. The bulkiness of TIPS, which shields the C≡C bond, [21] as well as the inductive electron‐donation effect from silyl group [21] are probably the reasons for the observed direct silylation, which is utterly different than the [4+2] cycloaddition under very similar conditions reported by Song and co‐workers [17i] . In addition, we also attempted the enantioselective variants of this reaction by using chiral BINAP ligands.…”

Enantioselective Construction of Six- and Seven-Membered Triorgano-Substituted Silicon-Stereogenic Heterocycles

“…To the best of our knowledge, only Shintani, Hayashi, Nozaki et al and Song have succeeded in forming six-membered tetraorgano-substituted silicon-stereogenic silanes (Fig. 1b) [36][37][38][39][40] , while the construction of Si-chirality on six-and seven-membered triorgano-substituted monohydrosilanes via asymmetric catalysis is still unknown to date, which is presumably due to a lack of general and e cient synthetic methods. Given the increasing demand for the synthesis of novel functional-materials-oriented silicon-bridged biaryls, construction of six-or seven-membered monohydrosilanes in a chiral version is highly attractive.…”

Synthesis of silacyclopent-2-en-4-ols via intramolecular [2 + 2] photocycloaddition of benzoyl(allyl)silanes

“…16 Due to their high ring strain and Lewis acidity, SCBs are often used as precursors to other organosilicon compounds through ring opening/expansion reactions catalysed by transition metals. 16,17 Even though ring expansion of SCBs can also provide silacyclopentanes under specific conditions, the most direct method for their synthesis consists in the addition of metal treated 1,3-butadienes to dichlorosilanes. 18,19 The synthesis of silacyclopentenes through palladium-catalysed silylene-1,3-diene [4 + 1] cycloaddition 20 allows flexibility on substitution of the cyclopentene core.…”