Stereoelectronic control in the solvolysis of spiroepoxidic 1-norbornyl triflates: unexpected reactivity in 3-bromomethyl derivatives

• Published in: Tetrahedron letters Vol. 52; no. 15; pp. 1762 - 1765
• Main Authors: Garcia Martinez, Antonio, Teso Vilar, Enrique, Garcia Fraile, Amelia, de la Moya Cerero, Santiago, Diaz Morillo, Cristina
• Format: Journal Article
• Language: English
• Published: OXFORD Elsevier 13.04.2011
• Subjects: Alicyclic compounds; Alicyclic compounds, terpenoids, prostaglandins, steroids; Bromine; Camphor; Cascade chemical reactions; Chemical reactivity; Chemistry; Chemistry, Organic; Derivatives; Exact sciences and technology; Heterocyclic compounds; Heterocyclic compounds with o, s, se, te hetero atom and condensed derivatives; Organic chemistry; Physical Sciences; Preparations and properties; Reactivity and mechanisms; Science & Technology; Solvolysis; Terpenoids; Tetrahedrons; Tetrahydrofuran; RATES; Stereoelectronic effects; SCOPE; Domino reactions; CAMPHORS; Rearrangements; 1-Norbornyl cations; Bromine; Endo stereoisomer; Terpenoid; Chemical rearrangement; Epimer; Furan derivatives; Solvolysis; Oxygen heterocycle; Tetrahydrofurane; Spiran; Terpene; Steric effect; Monoterpene; Cations; Electronic effect; Enantiospecificity; Chemical reactivity; Chemical synthesis; Successive reaction
• ISSN: 0040-4039; 1873-3581
• DOI: 10.1016/j.tetlet.2011.02.006

Interesting norbornane-fused tetrahydrofurans, with an additional synthetically-valuable vicinal dioxy-substitution in the norbornane skeleton, are enantiospecifically obtained in high yield from epimeric camphor-derived 3-endo-bromomethyl-substituted spiroepoxidic 1-norbornyl triflates. The process takes place via a domino reaction stereoelectronically controlled by the bromine atom. The described process has synthetic value, since it opens the way for a future enantiospecific preparation of 2,3-disubstituted tetrahydrofurans from camphor. (C) 2011 Elsevier Ltd. All rights reserved.