A chiral, non-racemic vinylsulfonium salt 6 was prepared from camphorquinone in seven steps and reacted with indole-2-carboxaldehyde to give a tricyclic azido alcohol 2 in a 35% yield and 43% e.e. and a 40% recovery of the chiral sulfide.Graphic[(1R,2S,7R,8S)-exo]-6-Ethenyl-1,11,11-trimethyl-3-oxa-6-thiatricyclo[6.2.1.02,7]undecanium trifluoromethanesulfonateC15H23F3O4S2Ee=100%[α]D24=+18 (c 0.012, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (1R,2S,7R,8S)[(1R,2S,7R,8S)-exo]-3-Ethenyl-1,11,11-trimethyl-6-oxa-3-thiatricyclo[6.2.1.02,7]undecanium trifluoromethanesulfonateC15H23F3O4S2Ee=100%[α]D24=+27 (c 0.0060, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (1R,2S,7R,8S)[(1R,2S,7R,8S)-exo]-1,11,11-Trimethyl-6-oxa-3-thiatricyclo[6.2.1.02,7]undecaneC12H20OSEe=100%[α]D24=+12 (c 0.012, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (1R,2S,7R,8S)[(1R,3R,4S)-exo]-3-(2-Thioacetylethoxy)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-oneC14H22O3SEe=100%[α]D24=+61 (c 0.014, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (1R,3R,4S)[(1R,3R,4S)-exo]-3-(2-Bromoethoxy)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-oneC12H19BrO2Ee=100%[α]D24=+83 (c 0.010, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (1R,3R,4S)[(1R,2S,7R,8S)-exo]-6-(2-Bromoethyl)-1,11,11-trimethyl-3-oxa-6-thiatricyclo[6.2.1.02,7]undecanium trifluoromethanesulfonateC15H24BrF3O4S2Ee=100%[α]D24=+57 (c 0.0090, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (1R,2S,7R,8S)