Direct Enantioselective α‐Allylation of Unfunctionalized Cyclic Ketones with Alkynes through Pd‐Amine Cooperative Catalysis

Lee, Jin Tu Danence; Zhao, Yu

doi:10.1002/chem.201802273

Cited by 28 publications

(16 citation statements)

References 84 publications

(26 reference statements)

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“…The direct addition of enols/enolates to unactivated unsaturated hydrocarbons (hydroalkylation) with catalysis by transition-metal hydrides (MH) has been attracting increasing attention as an atomeconomical strategy for the C-C bond formation. Elegant progress on asymmetric variants of these reactions has recently been made [20][21][22][23][24][25][26][27][28][29][30][31][32][33][34][35][36][37][38][39] .…”

mentioning

confidence: 99%

Direct access to spirocycles by Pd/WingPhos-catalyzed enantioselective cycloaddition of 1,3-enynes

Wang

Luo

et al. 2021

Nat Commun

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Spirocycles play an important role in drug discovery and development. The direct, catalytic, and enantioselective synthesis of spirocycles from readily available starting materials and in an atom economic manner remains a highly sought-after task in organic synthesis. Herein, an enantioselective Pd-hydride-catalyzed cycloaddition method for the synthesis of spirocyclic compounds directly from two classes of commonly available starting materials, 1,3-enynes and cyclic carbon−hydrogen (C−H) bonds, is reported. The reactions employ a chiral Pd/WingPhos catalyst to both suppress the formation of bis-allenyl by-products and control the stereoselectivity. 1,3-Enynes are used as dielectrophilic four-carbon units in the cycloaddition reactions, which also enables an enyne substrate-directed enantioselectivity switch with good levels of stereocontrol. The present spirocycle synthesis tolerates a broad range of functional groups of 1,3-enyne substrates, including alcohols, esters, nitriles, halides, and olefins. A variety of diverse cyclic nucleophiles, including pharmaceutically important heterocycles and carbocycles, can be flexibly incorporated with spiro scaffolds.

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mentioning

confidence: 99%

Direct access to spirocycles by Pd/WingPhos-catalyzed enantioselective cycloaddition of 1,3-enynes

Wang

Luo

et al. 2021

Nat Commun

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“…Moreover, numerous valuable molecules have been reported by the functionalization of α ‐C(sp 3 )−H bonds as key intermediates in medicinal chemistry besides pharmaceutical synthesis as well. Although, to date, several techniques for C−C sigmabonds activation have been developed and advanced to higher‐level using transition‐metal catalyzed reactions but due to high cost and also from the environmental perspective, the researcher turned their attention to develop metal‐free as well as eco‐friendly procedures [117–124] . In this direction, Liu et al .…”

Section: Functionalization Of C−h Bondsmentioning

confidence: 99%

Applications of Oxone® in Organic Synthesis: An Emerging Green Reagent of Modern Era

2022

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Presently, the major cornerstone of the research community is to develop green as well as sustainable protocols involving inexpensive catalysts and/or reagents without the usage of hazardous solvents under globally friendlier conditions in order to shelter both mankind and environment. Therefore, needless to say, there is always a supreme need to surrogate the older, costlier and unsafe strategies with the novel economically inexpensive and environmental benign ones. To this context, in recent past, oxone® (triple salt), a very cheap oxidizing agent having the chemical formula 2KHSO5 ⋅ KHSO4 ⋅ K2SO4 and enwrapped with the unique characteristics like easy handling, non‐toxic, safe, eco‐friendly, non‐polluting, stable, and nicely soluble in water, in addition to its utility for large‐scale synthesis etc. Bearing the importance of this versatile reagent in mind, we envisioned to update the recent advances made in this direction. Consequently, in this particular review article, the developments made in the arena of oxone chemistry covering from 2013 to 2020 have been revealed as no report appeared in the literature after a wonderful Chem. Rev. published by the group of Hussain in 2013. Herein, a comprehensive detail of a variety of oxidative transformations along with the complete plausible mechanistic steps have been exposed. For sure, present review would be a very helpful tool to the scientific community not only working in the area of organic synthesis but also to the researchers working in other branches of science and technologies as well.

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“…In 2018, Zhao and co‐workers disclosed the first direct catalytic enantioselective α ‐allylation of unfunctionalized cyclic ketones with internal alkynes as the allyl metal precursor (Scheme 8). [40] This transformation uses commercially available Pd, chiral secondary amine catalysts, and a chiral bisphosphine ligand. A chiral Pd complex containing the ( S )‐DIFLUORPHOS ligand ( L2 ) catalyzes the isomerization of alkynes to an electrophilic allylpalladium species.…”

Section: Combining Aminocatalysis and Transition Metal Catalysismentioning

confidence: 99%

Combined Power of Organo‐ and Transition Metal Catalysis in Organic Synthesis

et al. 2022

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The combination of organocatalysis with transition metal catalysis is an emerging research area for the scientific community. Various unprecedented transformations that are otherwise inaccessible by individual catalytic systems can be achieved with good efficiency and stereocontrolled manner by this dual-catalytic strategy. This Review presents a detailed discussion on the recent advances in dual catalytic systems combining organocatalysis and transition metal catalysis, covering the literature of the last five years. A wide variety of combinations of transition metals with organocatalysts including aminocatalysts, such as secondary amines and more recent primary amines, Brønsted acid catalysts, especially phosphoric acids based on the chiral BINOL scaffold and N-heterocyclic carbene catalysts, are discussed. Considering the great contribution of this domain to organic synthesis, the present and future potential of this new and exciting research field is highlighted.

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Direct Enantioselective α‐Allylation of Unfunctionalized Cyclic Ketones with Alkynes through Pd‐Amine Cooperative Catalysis

Cited by 28 publications

References 84 publications

Direct access to spirocycles by Pd/WingPhos-catalyzed enantioselective cycloaddition of 1,3-enynes

Direct access to spirocycles by Pd/WingPhos-catalyzed enantioselective cycloaddition of 1,3-enynes

Applications of Oxone® in Organic Synthesis: An Emerging Green Reagent of Modern Era

Combined Power of Organo‐ and Transition Metal Catalysis in Organic Synthesis

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