REGIOSELECTIVE ELECTROPHILIC ADDITIONS TO 2-OXYGENATED-7-OXABICYCLOHEPT-5-ENES: A SIMPLE ENTRY INTO THE 4,7-DIOXATRICYCLO3,6>OCTANE SKELATON

Article abstract of DOI:10.1016/S0040-4020(01)89091-8

The regio- and stereoselectivity of the reaction between PhSeCl and PhSCl and a number of 7-oxabicyclo<2.2.1>hept-5-enes bearing an oxygenated substituent on C-2 is discussed.In most cases, both electrophiles react with complete regio- and stereoselectivity to provide 5-endo-chloro-6-exo-benzeneselenenyl (benzenesulfenyl) derivatives. 7-Oxanorbornen-2-endo-ols behave differently with both electrophiles.Thus, while PhSeCl produces 5-endo-chloro-6-exo-benzeneselenenyl adducts and small amounts of 4,7-dioxatricyclo<3.2.1.0^3,6>octane derivatives, PhSCl affords a good yield of 5-exo-methyl-2-exo-phenylsulfenyl-4,7-dioxatricyclo>3.2.1.o^3,6>octane.