Green Synthesis and Catalysis, Journal Year: 2022, Volume and Issue: 3(3), P. 212 - 218
Published: June 22, 2022
Language: Английский
Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(12), P. 6944 - 6952
Published: March 15, 2023
Enantioselective metallaphotoredox catalysis, which combines photoredox catalysis and asymmetric transition-metal has become an effective approach to achieve stereoconvergence under mild conditions. Although many impressive synthetic approaches have been developed access central chirality, the construction of axial chirality by still remains underexplored. Herein, we report two visible light-induced cobalt-catalyzed reductive couplings biaryl dialdehydes synthesize axially chiral aldehydes (60 examples, up 98% yield, >19:1 dr, >99% ee). This protocol shows good functional group tolerance, broad substrate scope, excellent diastereo- enantioselectivity.
Language: Английский
Citations
80
Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(14), P. 7983 - 7991
Published: March 28, 2023
Conjugate addition is among the most important synthetic protocols for constructing carbon skeletons and widely used to synthesize natural products drugs. However, asymmetric catalysis studies have mainly focused on stereogenic centers arising from conjugate alkenes. Here, we report first photoinduced cobalt-catalyzed dynamic kinetic reductive reaction that enables formation of heterobiaryls with axial chirality (45 examples, up 91% yield 97% ee). This method features mild conditions, good functional-group tolerance, excellent enantiomeric control. Significantly, large amounts metal waste precious catalysts can be avoided under these conditions. Migration chiral arylcobalt species into alkene might rate-determining step based studies.
Language: Английский
Citations
62
Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(7)
Published: Jan. 2, 2024
Chromium-catalyzed enantioselective Nozaki-Hiyama-Kishi (NHK) reaction represents one of the most powerful approaches for formation chiral carbon-heteroatom bond. However, construction sterically encumbered tetrasubstituted stereocenter through NHK still posts a significant challenge. Herein, we disclose cobalt-catalyzed aza-NHK ketimine with alkenyl halide to provide convenient synthetic approach manufacture enantioenriched α-vinylic amino acid. This protocol exhibits excellent functional group tolerance 99 % ee in cases. Additionally, this asymmetric reductive method is also applicable aldimine access trisubstituted stereogenic centers.
Language: Английский
Citations
18
Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(28), P. 18892 - 18898
Published: July 5, 2024
Herein, we designed a reaction for the desymmetrization-addition of cyclopropenes to imines by leveraging synergy between photoredox and asymmetric cobalt catalysis. This protocol facilitated synthesis series chiral functionalized cyclopropanes with high yield, enantioselectivity, diastereoselectivity (44 examples, up 93% yield >99% ee). A possible mechanism involving cyclopropene desymmetrization Co-H species imine addition Co-alkyl was proposed. study provides novel route important extends frontier metallaphotoredox
Language: Английский
Citations
17
ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 1147 - 1157
Published: Jan. 3, 2025
This study describes a photoredox/cobalt dual-catalyzed asymmetric Grignard-type addition reaction, enabling the synthesis of axially chiral hexatomic (six–six) N-heterobiaryls bearing extra secondary alcohol unit via an efficient dynamic kinetic transformation racemic N-heterobiaryl triflate substrates. The conversion facilitated both photoredox and classical reductive reaction conditions exhibits good functional group tolerance, broad substrate scope, satisfactory stereoselectivity. Furthermore, control experiments density theory calculations provide preliminary mechanistic insights.
Language: Английский
Citations
4
European Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 26(1)
Published: Dec. 9, 2022
Abstract Dual catalysis is one of the most powerful strategies for development chemical reactions in organic synthesis. This strategy can be divided into cooperative catalysis, relay and sequential according to actual mode operation communication between catalysts. In recent years, such has been applied a large number studies since it advantages of: 1) increasing reactivity enabling challenging transformations; 2) offering way controlling stereoselectivity asymmetric reactions, which traditional catalytic systems; 3) catalyze stereodivergent synthesis molecules bearing or more stereocenters from same starting materials. Perspective, intends introduce reader EurJOC special collection on Catalysis , aims summarize different categories dual demonstrate their benefits constructing new bonds selective manner. Finally, current challenges trends will also presented.
Language: Английский
Citations
57
Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(50), P. 23001 - 23009
Published: Dec. 8, 2022
A new regio- and stereoselective reductive coupling of alkynes crotononitrile has been developed via visible light organophotoredox cobalt dual catalysis. variety enantioenriched homoallylic nitriles bearing a stereodefined trisubstituted alkene have easily synthesized with good to excellent (up >20:1 rr), stereo- (>20:1 E/Z), enantioselectivity 98% ee) control under mild conditions. The corresponding nitrile products were smoothly converted into various chiral building blocks. Remarkably, simple organic base together water utilized as hydrogen sources in this photoinduced reaction.
Language: Английский
Citations
40
Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 62(3)
Published: Nov. 17, 2022
Abstract Due to its mild reaction conditions and unique chemoselectivity, hydrogen atom transfer (HAT) hydrogenation represents an indispensable method for the synthesis of complex molecules. Its analog using deuterium, deuterium (DAT) deuteration, is expected enable access deuterium‐labeled compounds. However, DAT deuteration has been scarcely studied synthetic purposes, a that possesses favorable characteristics HAT hydrogenations remained elusive. Herein, we report protocol photocatalytic electron‐deficient alkenes. In contrast previous this tolerates variety synthetically useful functional groups including haloarenes. The late‐stage also allows deuterated amino acids as well donepezil‐ d 2 . Thus, work demonstrates potential chemistry become alternative choice preparing deuterium‐containing
Language: Английский
Citations
39
Nature Chemistry, Journal Year: 2023, Volume and Issue: 16(3), P. 398 - 407
Published: Dec. 11, 2023
Language: Английский
Citations
31
Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(24)
Published: April 12, 2023
Catalytic metal hydride hydrogen atom transfer (MHAT) reactions have proven to be a powerful method for alkene functionalization. This work reports the discovery of Co-porphines as highly efficient MHAT catalysts with loading only 0.01 mol % unprecedented chemoselective allene functionalization under photoirradiation. Moreover, newly developed bimetallic strategy by combination photo Co-MHAT and Ti catalysis enabled successful carbonyl allylation wide range amino, oxy, thio, aryl, alkyl-allenes providing expedient access valuable β-functionalized homoallylic alcohols in over 100 examples exceptional regio- diastereoselectivity. Mechanism studies DFT calculations supported that selectively transferring atoms from cobalt allenes generating allyl radicals is key step catalytic cycle.
Language: Английский
Citations
27