Chiral Primary Amine/Palladium Dual Catalysis for Asymmetric Allylic Alkylation of β‐Ketocarbonyl Compounds with Allylic Alcohols

Zhou, Han; Zhang, Long; Xu, Changming; Luo, Sanzhong

doi:10.1002/ange.201505946

Cited by 44 publications

(7 citation statements)

References 67 publications

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“…The presence of stoichiometric amount of amine/TfOH would facilitate the hydropalladation process, hence the formation of addition product 4a in this instance. In accordance with our previous studies, [61][62][63][64] a steric model could be proposed to account for the observed stereoselectivity. 64 Bulkiness from the protonated amino moiety and the space-demanding palladium intermediate (II or V) both contribute to the stereocontrol.…”

Section: Investigation Of Mechanismsupporting

confidence: 88%

Catalytic Asymmetric Addition and Telomerization of Butadiene with Enamine Intermediates

et al. 2022

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We report herein tunable asymmetric addition and telomerization of butadiene by synergistic chiral primary amine/achiral palladium catalysis. A selection of different achiral phosphine ligand in concert with the chiral primary amine-TfOH conjugates enables both chemo-and enantioselective control of the coupling with butadiene. Bidentate DPEPhos ligand led to 1,4-addition adduct whereas monodentate (p-Tol) 3 P ligand gave telomerization product. A range of α-branched β-ketoesters and aldehydes could be applied to afford allylation or telomerization products bearing all-carbon quaternary centers in high efficiency and good chemo-, regioand stereoselectivities.

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Section: Investigation Of Mechanismsupporting

confidence: 88%

Catalytic Asymmetric Addition and Telomerization of Butadiene with Enamine Intermediates

et al. 2022

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“…In the last decade, great efforts have been conducted on this important transformation in order to replace the traditionally employed alcohol derivatives (such as carbonates, acetates, phosphates…) as substrates, for the more readily available and environmentally friendly allylic alcohols . However, despite the enormous progresses already accomplished in the area, the asymmetric allylic alkylation reaction, also known as asymmetric Tsuji‐Trost reaction, of 1,3‐dicarbonyl compounds, employing such substrates is still undeveloped and, to the best of our knowledge, there are only a handful of works reported in the literature on this respect being, most of them, catalyzed by expensive transition‐metal based catalytic systems . In addition, even scarcer is the use of unsymmetrical 1,3‐dicarbonyl compounds, such as β ‐keto esters, which would render two consecutive all‐carbon stereocenters, as nucleophiles…”

Section: Methodsmentioning

confidence: 99%

Copper‐Catalyzed Asymmetric Allylic Alkylation of β‐Keto Esters with Allylic Alcohols

Trillo

Baeza

2017

Adv Synth Catal

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The asymmetric allylic alkylation reaction of b-keto esters catalyzed by copper complex tBuBOX-Cu(OTf) 2 employing allylic alcohols as environmentally friendly electrophilic partner, is herein described. This new protocol renders in general the corresponding allylic products with two consecutive all-carbon stereocenters in good both yields and enantioselectivities and with low to modest diastereoselection. The regioselectivity of the process seems to be governed by the formation of the most stable olefin according to the results obtained when non-symmetrically substituted alcohols were employed. The scope, limitations and mechanistic aspects of the process are also discussed.

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“…[ 29‐33 ] These catalysts also work effectively in concert with other catalytic systems including photoredox, electrochemical, metal catalysis as well as another organocatalysts, thus significantly expanding their catalytic spaces. [ 34‐41 ]…”

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

confidence: 99%

Bio‐inspired Small Molecular Catalysis

2022

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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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Chiral Primary Amine/Palladium Dual Catalysis for Asymmetric Allylic Alkylation of β‐Ketocarbonyl Compounds with Allylic Alcohols

Cited by 44 publications

References 67 publications

Catalytic Asymmetric Addition and Telomerization of Butadiene with Enamine Intermediates

Catalytic Asymmetric Addition and Telomerization of Butadiene with Enamine Intermediates

Copper‐Catalyzed Asymmetric Allylic Alkylation of β‐Keto Esters with Allylic Alcohols

Bio‐inspired Small Molecular Catalysis

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