Catalytic Intramolecular Hydrofunctionalization of Unactivated Alkenes and Alkynes
JOURNAL OF SYNTHETIC ORGANIC CHEMISTRY JAPAN(2022)
摘要
Catalytic intramolecular hydrofunctionalizations of acyclic alkenes and alkynes are desired methods for the construction of pharmaceutically important heterocycles with 100% atom efficiencies. Although electrophilic activation of alkenes and alkynes in the presence of Lewis basic hydroxy and amino groups can cause the reactions, those of monoalkyl - and 1,2 - dialkyl- substituted alkenes and alkynes called unactivated alkenes and alkynes are difficult owing to their inherent reactivity. Herein, we introduce several transition metal - free novel catalytic systems for the intramolecular hydrofunctionalization of such unactivated alkenes and alkynes; iodine- silane catalytic system for the hydroalkoxylation of unactivated alkenes, Bronsted acid -silane and iodinesilane catalytic systems for the hydrofunctionalization/reduction of unactivated alkynes, and boron catalytic systems for double hydrofunctionalization reactions of unactivated alkynes. A novel active species, iodophenylsilane(PhSiH2I)efficiently catalyzes the intramolecular hydroalkoxylation of unactivated alkenes in the iodine -silane catalytic system. A super strong Bronsted acid catalyst can activate unactivated alkynes in the presence of silane to cause the hydrofunctionalization/ reduction. Tris(pentafluorophenyl)borane [B(C6F5)(3)] chemoselectively activates unactivated alkynes in the presence of allylsilane to cause the intramolecular hydrofunctionalization/hydroallylation. In addition, tris(pentafluorophenyl)borane hydrate[B(C6F5)(3)center dot nH(2)O]reacts with trimethylsilylcyanide to form H+[NCB(C6F (5))(3)](-), which catalyzes the intramolecular hydroalkoxylation/ hydrocyanation of unactivated alkynes. These catalytic methods enable the rapid construction of multiply -substituted oxygen - or nitrogen- containing heterocycles.
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关键词
hydroalkoxylation, hydroamination, unactivated alkenes, unactivated alkynes, electrophilic activation, iodine, silane, Bronsted acid catalyst, boron catalyst
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