J Org Chem. 2006 Feb 17;71(4):1537-44.

Boron trifluoride-induced, new stereospecific rearrangements of chiral epoxy ethers. Ready access to enantiopure 4-(diarylmethyl)-1,3-dioxolanes and 4,5-disubstituted tetrahydrobenzo[c]oxepin-4-ols.

Islas-González G, Benet-Buchholz J, Maestro MA, Riera A, Pericàs MA.

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Departament de Química Orgànica and Parc Científic de Barcelona, Universitat de Barcelona, 08028 Barcelona, Spain.

Abstract

Upon treatment with BF3.Et2O at low temperature, enantiopure benzyl-type ethers of arylglycidols with electron withdrawing substituents at the skeletal aryl group and electron donating substituents at the benzyl group undergo stereospecific rearrangements of Friedel-Crafts type, leading to enantiopure 4-diarylmethyl-1,3-dioxolanes (2) or to enantiopure trans-4,5 disubstituted tetrahydrobenzo[c]oxepin-4-ols (5). The course of the reactions is controlled by the substitution pattern at the benzyl ether: While benzylic systems activated toward ipso substitution afford diarylmethanes 2 through a Friedel-Crafts reaction followed by fragmentation, benzylic systems activated toward ortho attack lead to enantiopure oxepinols 5 through a 7-endo-tet ring closure of Friedel-Crafts type.

PMID:: 16468802; [PubMed - indexed for MEDLINE]

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