Catalytic asymmetric oxidative sulfenylation of β-ketocarbonyls using a chiral primary amine

Zhang, Qi; Shi, Mingying; Mi, Xueling; Luo, Sanzhong

doi:10.1039/d1qo01748a

Cited by 7 publications

(3 citation statements)

References 44 publications

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“…Luo and co-workers developed an enantioselective oxidative thiolation of β-ketocarbonyls by using a chiral primary amine catalyst C52 in combination with tert -butyl hydroperoxide (TBHP) and a catalytic amount of tetrabutylammonium iodide (TBAI) as the oxidant (Scheme 70). 355 The delocalized 2-mercaptobenzothiazole derivatives were well tolerated under the reaction conditions to provide chiral thioethers bearing S-containing quaternary stereocenters in good yields and high enantioselectivities. However, electron-deficient and electron-rich phenyl thiol were unreactive under the standard conditions.…”

Section: Organocatalytic Enantioselective C–h/heteroatom-h Cross-dehy...mentioning

confidence: 99%

Enantioselective cross-dehydrogenative coupling enabled by organocatalysis

Jiang,

Luo,

Zhao

2024

Green Chem.

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Section: Organocatalytic Enantioselective C–h/heteroatom-h Cross-dehy...mentioning

confidence: 99%

Enantioselective cross-dehydrogenative coupling enabled by organocatalysis

Jiang,

Luo,

Zhao

2024

Green Chem.

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“…The chiral primary amine catalysts could also enable C—X bond formation in the context of quaternary center constructions, and the successful examples include amination, [ 49‐50 ] fluorination, [ 51‐52 ] sulfenylation, [ 53‐54 ] hydroxylation, [ 40 ] benzoyloxylation, [ 55 ] and N,O‐ketalization. [ 56 ] The frustrated Lewis trios (FLT), a three components Lewis acid‐base system including our primary amine catalyst, bulky borane Lewis acid and another bulky achiral amine has been developed to facilitate asymmetric disulfuration that directly installs disulfide moieties.…”

Section: Bi/multi‐function Strategy: Development and Application Of C...mentioning

confidence: 99%

Bio‐inspired Small Molecular Catalysis

2022

Self Cite

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Comprehensive Summary Nature is an inspiring resource for chemists to exploit uncharted chemical spaces. Enzymes in nature are characteristic of high efficiency and exquisite stereocontrol under rather mild conditions. Not surprisingly, chemists have a long history in developing new catalysts by learning from and imitating the natural enzymes. This review summarizes our long‐standing efforts in developing bio‐inspired small molecular catalysis. These were categorized according to the employed strategies: 1) bi‐/multi‐functional strategy for the bio‐inspired chiral primary amine catalyst; 2) cofactor strategy for bio‐inspired ortho‐quinone catalyst; 3) intermediate strategy for chiral latent carbocation catalysis based on natural carbocation process. Each section includes brief introduction of the biological origin, design of catalyst, development of methodology as well as the underlying mechanistic insights. What is the most favorite and original chemistry developed in your research group? I hope it's always the next one. How do you get into this specific field? Could you please share some experiences with our readers? Nature provides many astonishing catalytic machineries for building up molecular complexity and harnessing energy in the most efficient ways. Nature's recipe for catalysis serves as a starting point to develop new catalyst for synthetic and energy chemistry. I was trained as a synthetic chemist in a physical organic group in Nankai and ICCAS, and spent part of my graduate studies doing enzymatic synthesis of oligosaccharide and its related biological applications in Ohio State University. This gave me a mixed view on organocatalysis, then under its golden stage of renaissance, not only for its synthetic potentials as a new catalytic concept, but also with an eye on its biological origin and possible impact beyond synthesis. I also benefit a lot from the physical organic chemistry training which helps to shape my research path in width and depth, in a way I never imagined and expected at the beginning of my career. How do you supervise your students? Try to inspire beyond instruct. I learned and am still learning. “因材施教” is easy to say than to do. In reality, I become bossy the way I dislike and have to instruct heavily. What is the most important personality for scientific research? Curiosity, broad reading and sufficient “free time” for daydreaming. In order to have enough time to waste, you have to work really hard at first. Who influences you mostly in your life? My Ph.D. supervisor, Prof. Jin‐Pei Cheng who teaches me a rational and quantitative view for chemistry and inspires me all the time to pursue a rational approach in research.

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“…We have made much progress in practicing SOMO catalysis with primary amine catalysts. [19][20][21][22][23][24] Despite remarkable synthetic value of these transformations, direct observation of the key SOMO radical intermediate is still quite limited. By using mass spectroscopy, Engeser and co-workers detected the enamine radical cation under chemical oxidation conditions, supporting the existence of α-imino radical-type intermediate by SET of an enamine.…”

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confidence: 99%

Direct Observation of Enamine-Derived Radicals with Time-Resolved Electron Paramagnetic Resonance

Zhang,

Cheng,

et al. 2024

Preprint

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This study presents the direct observation of α-imino radical intermediates involved in the photoredox catalytic activation of enamines using the ultrawide single sideband phase-sensitive detection time-resolved electron paramagnetic reso-nance (U-PSD TREPR) technique. Enamines have been exten-sively used in singly occupied molecular orbital (SOMO) catal-ysis. The redox properties of enamines allow for facile oxida-tion, forming α-imino radical species that participate in vari-ous coupling reactions. Despite the synthetic value of these transformations, direct observation of the key radical inter-mediates has been limited. The U-PSD TREPR technique ena-bled direct in-situ observation of transient enamine radical cation and α-imino radical intermediates for the first time. Spectroscopic characterization and kinetic analysis provided insights into the structure and reactivity of these intermedi-ates. The results demonstrated the involvement of enamine radical cations as the key intermediates in the photoredox transformations by primary aminocatalysis.

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Catalytic asymmetric oxidative sulfenylation of β-ketocarbonyls using a chiral primary amine

Abstract: Enantioselective oxidative construction of C(sp3)-S bond has been achieved by a chiral primary amine catalyst in the presence of tert-butyl hydroperoxide and a catalytic amount of tetrabutylammonium iodide. The distinctive...

Cited by 7 publications

References 44 publications

Enantioselective cross-dehydrogenative coupling enabled by organocatalysis

Enantioselective cross-dehydrogenative coupling enabled by organocatalysis

Bio‐inspired Small Molecular Catalysis

Direct Observation of Enamine-Derived Radicals with Time-Resolved Electron Paramagnetic Resonance

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