Designed Chiral Acyl Radical Equivalents. Preparation and Cyclizations of Disymmetrically Substituted 1,3-Dioxabicyclo[4.4.0]decan-2-yl Radicals.
The diastereoselectivity of 5-exo-trigonal cyclizations of 2-(4-penten-1-yl)-1,3-dioxolan-2-yl and 2-(4-penten-1-yl)-1,3-dioxan-2-yl radicals is investigated. When dioxolanes or dioxanes derived from C(2) symmetrically substituted diols are employed the diastereoselectivity is poor. In the dioxanyl series this is a consequence of the cyclization occurring through a twist-boat conformer. Disymmetrically substituted dioxanyl radicals, derived from the alcohols 21 and 41, are, however, constrained to chairlike conformations and accordingly give rise to highly diastereoselective cyclizations. Conditions are described for the hydrolysis of the resulting spiroacetals and for determination of the ee of the resulting 2-methylcyclopentanones.
Stien
D.
D
LCMO, Associé au CNRS, Faculté des Sciences Saint-Jérôme, Av. Normandie-Niemen, 13397 Marseille Cedex 20, France, and Department of Chemistry, University of Illinois at Chicago, 845 West Taylor Street, Chicago, Illinois 60607-7061.
Samy
R.
R
Nouguier
R.
R
Crich
D.
D
Bertrand
M. P.
MP