Stereochemistry of cyclic ether formation—II
1973; Elsevier BV; Volume: 29; Issue: 22 Linguagem: Inglês
10.1016/s0040-4020(01)93532-x
ISSN1464-5416
AutoresM. LJ. MIHAILOVIC, S.Lj. Gojković, Stanimir Konstantinović,
Tópico(s)Chemical Synthesis and Reactions
ResumoThe mechanism and stereochemistry of δ-C atom functionalisation in the reactions of secondary straight-chain aliphatic alcohols with lead tetraacetate, ceric ammonium nitrate, and heavy metal (Pb4+, Hg2+, Ag+) salts (AcO)−1, O2−, CO32−-halogen (I2, Br2, Cl2) combinations are discussed. By demonstrating the intermediacy of 5-bromo-2-hexanol, it was confirmed that the dark silver oxidebromine induced cyclisation of 2-hexanol (and alcohols in general) involves (as the other hypohalite reactions) intramolecular 1,5-hydrogen abstraction by alkoxy radicals and formation of δ-bromohydrins. A novel and simple procedure for obtaining tetrahydrofurans from alcohols by way of the hypochlorite reaction, using silver or mercuric salts and chlorine, is described.
Referência(s)