Oxidative bridgehead functionalization of (4 + 3) cycloadducts obtained from oxidopyridinium ions.

Treatment of selected (4 + 3) cycloadducts derived from oxidopyridinium ions with -iodosuccinimide (NIS) in hexafluoroisopropanol (HFIP) resulted in the formation of bridgehead ethers a net oxidative C-H activation.

Tropane Skeleta from the Intramolecular Photocycloaddition of (4+3) Cycloadducts of Oxidopyridinium Ions and Dienes.

Easily prepared cycloadducts derived from the (4+3) cycloaddition of oxidopyridinium ions with dienes reacted intramolecularly in a [2+2] cycloaddition process to afford complex polycyclic species in which the tropane skeleton was embedded.

Selectivity in the (4 + 3) Cycloaddition of Oxidopyridinium Ions.

The (4 + 3) cycloaddition of 2-trialkylsilyl-4-alkylbutadienes with an -methyloxidopyridinium ion affords cycloadducts with high regioselectivity and excellent selectivity.