Nagoya University · Materials Science
Professor Yoshihiro Miyake's research lab specializes in transition metal-catalyzed and photoredox-mediated transformations, with a focus on developing innovative methods for C–H functionalization, C–C and C–heteroatom bond formation, and the synthesis of complex organic molecules under mild conditions. The lab pioneers the use of visible light and transition metal polypyridyl complexes as photocatalysts to generate reactive intermediates such as α-aminoalkyl radicals and silyl enol ethers, enabling selective and efficient transformations. Key research directions include the direct functionalization of sp³ C–H bonds, allylic and propargylic substitutions, and the construction of heterocyclic scaffolds via cycloaddition and radical addition processes. The work emphasizes atom-economical, step-economical, and late-stage functionalization strategies for complex molecule synthesis, particularly in medicinal chemistry and natural product synthesis.
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Synthetic use of α-aminoalkyl radicals formed by single electron oxidation of amines is quite limited. Here we demonstrate addition of α-aminoalkyl radicals to electron-deficient alkenes by visible-light-mediated electron transfer using transition metal polypyridyl complexes as photocatalysts, via a sequential redox pathway.
Abstract In sharp contrast to the well‐established transition metal‐ catalyzed allylic substitution reactions, the study of the corresponding propargylic substitution reactions has been quite limited for constructing carbon–carbon and carbon–heteroatom bonds at the propargylic position. However, during the last decade, general and useful catalytic reactions have been developed extensively. In this Review, we summarize recent advances in catalytic propargylic substitution reactions of propargylic
Visible-light-mediated addition of α-aminoalkyl radicals generated from α-silylamines to α,β-unsaturated carbonyl compounds using a photoredox catalyst is developed. We also succeeded in the isolation of a silyl enol ether as a primary product of the photochemical reaction.
Reactions of arylacetic acids bearing an amino group at the para-position in the benzene ring with alkenes in the presence of a catalytic amount of transition metal polypyridyl complexes as photocatalysts under visible light illumination proceed smoothly to give the corresponding benzylated products via oxidative decarboxylation in good to high yields.
Abstract Visible‐light‐mediated direct sp 3 CH amination of benzocyclic amines via α‐aminoalkyl radicals by using photoredox catalysts is described here. The obtained N , N ‐acetals were also successfully applied for carbon–carbon bond forming reactions with carbon nucleophiles. The procedure is suitable for a late‐stage modification of CH bonds to CC bonds.
It's complex: Ruthenium-catalyzed [3+2] cycloaddition of ethynylcyclopropanes with aldehydes and aldimines has been found to give the corresponding 2-ethynyltetrahydrofurans or -pyrrolidines in high to excellent yields. In both cases, the formation of a ruthenium allenylidene complex as a key reactive intermediate is supported by density functional theory calculations. Cp*=η5-C5Me5. As a service to our authors and readers, this journal provides supporting information supplied by the authors. Suc
Trifluoromethylation: The treatment of allylic halides with trifluoromethyltrimethylsilane in the presence of a catalytic amount of copper(I) thiophene-2-carboxylate (CuTC) gives the corresponding allylic trifluoromethylation products in good to high yields and with complete regioselectivity (see scheme). The use of THF as a solvent is crucial for obtaining good yields of product.
We have succeeded in the visible light-mediated synthetic use of α-aminoalkyl radicals derived from α-silyl secondary amines toward addition to α,β-unsaturated carbonyl compounds. The resulting γ-aminocarbonyl compounds are converted into γ-lactams and pyrroles in a one-pot process.
The functionalization of fullerene has been extensively studied and various fullerene derivatives have been synthesized. We have succeeded in the functionalization of [60]fullerene by using α-aminoalkyl radicals generated by visible-light-mediated single-electron oxidation of α-silylamines as synthetic intermediates. In these reactions, the introduction of diarylamino groups, which are useful electron donors, has been easily achieved.
An efficient method for the homocoupling of aryl halides by electron-transfer oxidation of Lipshutz cuprates (Ar2Cu(CN)Li2) with organic electron acceptors is disclosed. Thus, various types of Lipshutz cuprates are prepared by successive treatment of aryl or heteroaryl bromides with tert-butyllithium and CuCN. The electron-transfer oxidation of Lipshutz cuprates with p-benzoquinones proceeds smoothly to afford the corresponding homocoupling products in moderate to good yields. Furthermore, it ca
Reactions of propargylic halides with trifluoromethyltrimethylsilane in the presence of a catalytic amount of copper(I) thiophene-2-carboxylate (CuTC) have been found to give the corresponding trifluoromethylated products in good to high yields with a high selectivity.
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