Rearrangement of Linalool, Geraniol, and Nerol and their derivatives
Author
dc.contributor.author
Cori Moully, Osvaldo
Author
dc.contributor.author
Chayet Timmiling, Liliana
Author
dc.contributor.author
Perez Roepke, Luz Maria
Author
dc.contributor.author
Bunton, Clifford A.
Author
dc.contributor.author
Hachey, David
Admission date
dc.date.accessioned
2018-12-20T14:37:55Z
Available date
dc.date.available
2018-12-20T14:37:55Z
Publication date
dc.date.issued
1986
Cita de ítem
dc.identifier.citation
J. Org. Chem. 1986, 51, 1310-1316
Identifier
dc.identifier.issn
15206904
Identifier
dc.identifier.issn
00223263
Identifier
dc.identifier.other
10.1021/jo00358a028
Identifier
dc.identifier.uri
https://repositorio.uchile.cl/handle/2250/156744
Abstract
dc.description.abstract
Acid-catalyzed conversion of linalool into geraniol, nerol, and a-terpineol is slower than the corresponding reactions of geraniol and nerol, because the tertiary linalyl carbocation reverts to linalool rather than going forward to rearranged products. The linalyl carbocation does not lose its stereochemical identity, and oxygen exchange of linalool is faster than rearrangement or cyclization. Solvolyses of linalyl esters and chloride are faster than those of the geranyl and neryl derivatives. These solvolyses are different from acid heterolysis of linalool in that there is extensive racemization of linalool, but cyclization to a-terpineol goes with considerable retention of configuration. Participation by the 6,7-double bond controls the stereochemistry of linalool heterolysis and solvolysis of linalyl esters, but it does not markedly affect the reaction rates