Visible-Light Mediated Hydrosilylative and Hydrophosphorylative Cyclizations of Enynes and Dienes
Described herein is a visible-light mediated intermolecular radical cyclization approach to access heterocycles. Heteroatom radicals, such as silicon and phosphorus atom radicals, were generated via direct hydrogen atom abstraction by the photoexcited catalyst species with hydro-silanes and phosphine oxides. The radical addition/cyclization/HAT (hydrogen atom transfer) reaction sequences of 1,6-enynes and 1,6-dienes were highly efficient delivering the desired heterocycles in good yields.
The Isomerization of Allylrhodium Intermediates in the Rhodium-Catalyzed Nucleophilic Allylation of Cyclic Imines
Allylrhodium species generated from potassium allyltrifluoroborates can undergo isomerization by 1,4-rhodium(I) migration to give more complex isomers, which then react with cyclic imines to provide products with up to three new stereochemical elements. High enantioselectivities are obtained using chiral diene-rhodium complexes. Rhodium dance: Allylrhodium species generated from potassium allyltrifluoroborates can undergo isomerization by a 1,4-rhodium(I) migration to give more complex isomers, which then react with cyclic imines to provide products with up to three new stereochemical elements. High enantioselectivities are obtained with chiral diene-rhodium complexes.
Hepburn, Hamish B.,Lam, Hon Wai
supporting information
p. 11605 - 11610
(2016/02/19)
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