The selective isomerization of strained heterocyclic compounds is an important tool in organic synthesis. An unprecedented regioselective isomerization of 2,2‐disubstituted oxetanes into homoallylic alcohols is described. The use of tris(pentafluorophenyl)borane (B(C6F5)3), a commercially available Lewis acid was key to obtaining good yields and selectivities since other Lewis acids afforded mixtures of isomers and substantial polymerization. The reaction took place under exceptionally mild reaction conditions and very low catalyst loading (0.5 mol %). DFT calculations disclose the mechanistic features of the isomerization and account for the high selectivity displayed by the B(C6F5)3 catalyst. The synthetic applicability of the new reaction is demonstrated by the preparation of γ‐chiral alcohols using iridium‐catalyzed asymmetric hydrogenation.
The selective isomerization of strained heterocyclic compounds is an important tool in organic synthesis.A n unprecedented regioselective isomerization of 2,2-disubstituted oxetanes into homoallylic alcohols is described. The use of tris(pentafluorophenyl)borane (B(C 6 F 5 ) 3 ) , ac ommercially available Lewis acid was key to obtaining good yields and selectivities since other Lewis acids afforded mixtures of isomers and substantial polymerization. The reaction took place under exceptionally mild reaction conditions and very low catalyst loading (0.5 mol %). DFT calculations disclose the mechanistic features of the isomerization and account for the high selectivity displayed by the B(C 6 F 5 ) 3 catalyst. The synthetic applicability of the new reaction is demonstrated by the preparation of g-chiral alcohols using iridium-catalyzed asymmetric hydrogenation. Dr.A .C abrØ,S.R afael, Prof. X. Verdaguer,P rof. A. Riera Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.
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