Premium
Enantioselective Visible‐Light‐Induced Radical‐Addition Reactions to 3‐Alkylidene Indolin‐2‐ones
Author(s) -
Lenhart Dominik,
Bauer Andreas,
Pöthig Alexander,
Bach Thorsten
Publication year - 2016
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201600600
Subject(s) - enantioselective synthesis , diastereomer , chemistry , catalysis , substituent , trimethylsilyl , photochemistry , amine gas treating , chirality (physics) , yield (engineering) , substrate (aquarium) , silylation , organic chemistry , materials science , physics , chiral symmetry breaking , oceanography , quantum mechanics , geology , nambu–jona lasinio model , metallurgy , quark
The title compounds underwent a facile and high‐yielding addition reaction (19 examples, 66–99 % yield) with various N ‐(trimethylsilyl)methyl‐substituted amines upon irradiation with visible light and catalysis by a metal complex. If the alkylidene substituent is non‐symmetric and if the reaction is performed in the presence of a chiral hydrogen‐bonding template, products are obtained with significant enantioselectivity (58–72 % ee ) as a mixture of diastereoisomers. Mechanistic studies suggest a closed catalytic cycle for the photoactive metal complex. However, the silyl transfer from the amine occurs not only to the product, but also to the substrate, and interferes with the desired chirality transfer.