Vinylsilanes were directly prepared from the corresponding vinyl triflates under magnesium-promoted reductive conditions in THF with no transition metal catalyst, and gem-bis-silylated compounds were obtained in NMP. Investigation of the redox potential of starting materials and products suggested that reductive coupling reactions of vinyl triflates might be controlled by the reduction potential. A variety of gem-bis-silylated compounds and 3-silyladipic acid esters were easily synthesized in only two steps from vinyl triflates in high yields.

Chiral N,N-4-(dimethylamino)pyridine (DMAP) derivatives, which can be readily prepared by the Ugi multicomponent reaction in a one-pot manner, have been efficiently applied to the enantioselective Steglich rearrangement of oxindole derivatives to give the desired products bearing a quaternary carbon center in high yield (>98% yield) and with high enantioselectivity (up to 99:1 er).

Accessible Chiral N,N-4-(Dimethylamino)pyridine Derivatives. -The rearrangement of O-acylated oxidoles proceeds smoothly in the presence of chiral pyridine catalysts (I) to give oxindole derivatives in excellent yields with enantioselectivities up to 98%. -(MANDAI*, H.; FUJIWARA, T.; NODA, K.; FUJII, K.; MITSUDO, K.; KORENAGA, T.; SUGA, S.; Org. Lett. 17 (2015) 18, 4436-4439, http://dx.doi.org/10.1021/acs.orglett.5b02089 ; Grad. Sch. Nat. Sci. Technol., Okayama Univ. Sci., Okayama 700, Japan; Eng.) -Mais 05-134