Synthesis of 8,9,10,11,12,13,13a,14-octahydro-7,11; 9,13-dimethanoazonino[1,2-b]isoquinolin-5(7H)-ones and some related derivatives by photocyclization reactions of 5-methylene-4-aroyl- and -acryloyl-4- azatricyclo[4.3.1.13,8]undecanes (4-azahomoadamantanes)

Abstract

5-Methylene-4-aroyl- and -acryloyl-4-azatricyclo[4.3.1.1^3,8]undecanes (2a–h) have been prepared by acylation of 5-methyl-4-azatricyclo[4.3.1.1^3,8]undec-4-ene (1). Irradiation of 4-aroyl derivatives (2a–d) afforded 2- or 4-substituted 8,9,10,11,12,13,13a,14-octahydro-7,11; 9,13-dimethanoazonino[1,2-b]isoquinolin-5(7H)-ones (3a–d) in good yields via enamide photocyclization. DDQ oxidation of (3a–d) gave the corresponding hexahydroisoquinolin-5(7H)-ones (4a–d). Among the acryloyl derivatives, only the methacryloyl derivative (2g) afforded the enamide photocyclization product (5) in a lower yield, the other acryloyl derivatives (2e,f,h) when irradiated yielding the corresponding vinylogous amide derivatives (6a–c)via a 1,3-acyl shift.