While elucidating the inhibitory mechanism of a hydrolytic enzyme by aldehyde-containing natural product,we discovered a reaction involving a rapid 6π-azaelectrocyclization of azatrienes generated from aldehyde with ...While elucidating the inhibitory mechanism of a hydrolytic enzyme by aldehyde-containing natural product,we discovered a reaction involving a rapid 6π-azaelectrocyclization of azatrienes generated from aldehyde with lysine residues.The electrocyclic reaction of the 1-azatriene system,a cyclization precursor,exhibited a significant substituent effect.Asymmetric chiral piperidine synthesis and a one-pot library synthesis of pyridines on solid-supports were applied to synthesize pyridine/indole alkaloid-type natural product.Additionally,we developed lysine-based labeling and engineering of biomolecules and living cells based on the rapid 6π-azaelectrocyclization.Both labels and oligosaccharide structures were introduced efficiently and selectively into surface lysines under the mild conditions;notable effects of N-glycans on proteins and living cells were visualized for the first time by PET and noninvasive fluorescence imaging.展开更多
基金supported by Grants-in-Aid for Scientific Research No.19681024 and 19651095 from the Japan Society for the Promotion of ScienceGrant-in-Aid for Science Research on Priority Areas 16073222 from the Ministry of Education,Culture,Sports,Science and Technology(MEXT)+2 种基金Molecular Imaging Research Program from MEXT,Matching Fund Subsidy for a Private University,Collaborative Development of Innovative Seeds from Japan Science and Technology Agency(JST)New Energy and Industrial Technology Development Organization(NEDO,project ID:07A01014a)a Research Grants from Yamada Science Foundation
文摘While elucidating the inhibitory mechanism of a hydrolytic enzyme by aldehyde-containing natural product,we discovered a reaction involving a rapid 6π-azaelectrocyclization of azatrienes generated from aldehyde with lysine residues.The electrocyclic reaction of the 1-azatriene system,a cyclization precursor,exhibited a significant substituent effect.Asymmetric chiral piperidine synthesis and a one-pot library synthesis of pyridines on solid-supports were applied to synthesize pyridine/indole alkaloid-type natural product.Additionally,we developed lysine-based labeling and engineering of biomolecules and living cells based on the rapid 6π-azaelectrocyclization.Both labels and oligosaccharide structures were introduced efficiently and selectively into surface lysines under the mild conditions;notable effects of N-glycans on proteins and living cells were visualized for the first time by PET and noninvasive fluorescence imaging.
