Chemo‐selective Rh(II)/Pd(0) Dual Catalysis: Synthesis of All‐Carbon C3‐Quaternary Allylic Oxindoles from N‐Aryl‐α‐Diazo‐β‐Keto‐Amides with Functionalized Allyl Carbonates

Chen, Ling‐Hang; Ma, Yang‐Ting; Yang, Fang; Huang, Xiaoyan; Chen, Shu‐Wei; Ji, Kegong; Chen, Zi‐Sheng

doi:10.1002/adsc.201801346

Cited by 21 publications

(16 citation statements)

References 89 publications

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“…To validate the feasibility of the above-mentioned hypothesis, our investigation was commenced with the three-component reaction of α-diazoacetophenone ( 1a ) with methanol ( 2a ) and cinnamyl methyl carbonate ( 3a ) under the redox-compatible dual metal cooperative catalysis , of Rh 2 (OAc) 4 and Pd 2 (dba) 3 in dichloromethane (DCM) at room temperature (Table ). A solution of diazo compound 1a and alcohol 2 was added slowly via a syringe pump in all these conducted reactions to ensure high yield.…”

Section: Resultsmentioning

confidence: 99%

Ternary Catalysis Enabled Three-Component Asymmetric Allylic Alkylation as a Concise Track to Chiral α,α-Disubstituted Ketones

et al. 2021

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Multicomponent reactions that involve interception of onium ylides through Aldol, Mannich, and Michael addition with corresponding bench-stable acceptors have demonstrated broad applications in synthetic chemistry. However, because of the high reactivity and transient survival of these in situ generated intermediates, the substitution-type interception process, especially the asymmetric catalytic version, remains hitherto unknown. Herein, a three-component asymmetric allylation of α-diazo carbonyl compounds with alcohols and allyl carbonates is disclosed by employing a ternary cooperative catalysis of achiral Pd-complex, Rh 2 (OAc) 4 , and chiral phosphoric acid CPA. This method represents the first example of three-component asymmetric allylic alkylation through an S N 1-type trapping process, which involves a convergent assembly of two active intermediates, Pd-allyl species, and enol derived from onium ylides, providing an expeditious access to chiral α,α-disubstituted ketones in good to high yields with high to excellent enantioselectivity. Combined experimental and computational studies have shed light on the mechanism of this novel three-component reaction, including the critical role of Xantphos ligand and the origin of enantioselectivity.

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Section: Resultsmentioning

confidence: 99%

Ternary Catalysis Enabled Three-Component Asymmetric Allylic Alkylation as a Concise Track to Chiral α,α-Disubstituted Ketones

et al. 2021

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“…Notably, migratory insertion of the allyl group of II to the carbenic carbon atom is also possible, leading to undesired 1,3‐dienes after β‐hydride elimination. Theoretically, a second transition metal co‐catalyst, such as Ru(II) [3n] and Rh(II) [3p] complexes, is not mandatory for the overall transformation to product 3 .…”

Section: Methodsmentioning

confidence: 99%

Palladium‐Catalyzed Cascade C−H Functionalization/Asymmetric Allylation Reaction of Aryl α‐Diazoamides and Allenes: Lewis Acid Makes a Difference

Ruan

Han

et al. 2022

Chemistry A European J

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A Pd‐catalyzed cascade C−H functionalization/asymmetric allylation reaction with aryl α‐diazoamides and allenes has been developed. The reaction provides an efficient approach to construct chiral 3,3‐disubstituted oxindole derivatives in high levels of yield and enantioselectivity (up to 93 % ee). Notably, the chromium complex works as Lewis acid to facilitate the formation of palladium carbene and to enhance acidity of carboxylic acid, allowing for higher stereochemical control and efficiency.

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“…Combining Ru/Rh with Pd-catalyzed AAA reaction of α-diazo derivatives. [29][30][31] Scheme 17. Pd/Cu dual catalyzed AAA reaction of amino acids and proposed mechanism.…”

Section: Enantioselective Quaternary Carbon Stereocenters Via Cooperative Catalysismentioning

confidence: 99%

“…In 2019, Chen and co‐workers utilized Rh(II)/Pd(0) dual catalytic system to obtain the chiral 3‐allyl‐3‐acetyl oxindole 17 bearing an all‐carbon quaternary center and ligand L13 was selected and exhibited good reactivity and enantioselectivity (Scheme 16b) [30] . Therefore, the decisive factor for the efficiency of this transformation is the choice of Rh(II)/Pd(0) dual catalytic system that carried out cascade intramolecular aryl C−H insertion and AAA reaction under mild conditions.…”

Section: Structure Skeletons With Single Quaternary Carbon Stereocentermentioning

confidence: 99%

Enantioselective Synthesis of Quaternary Carbon Stereocenters by Asymmetric Allylic Alkylation: A Review

Huang

et al. 2021

Chemistry An Asian Journal

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Quaternary stereocenters are of great importance to the three-dimensionality and enhanced properties of new molecules, but the synthetic challenges in creating quaternary stereocenters greatly hinder their wide use in drug discovery, organic material design, and natural product synthesis. The asymmetric allylic alkylation (AAA) of allylic substrates has proven to be a powerful methodology for enantioselective formation of structure skeletons bearing single or more quaternary carbon centers in modern asymmetric organocatalysis. AAA has certain advantages in constructing the tetrasubstituted stereocenters, including but not limited to mild reactive conditions, effective reaction rates, new functional group introduction, and carbon chains length extension. This review outlines the key considerations in the application of AAA reactions and summarizes the recent progress of AAA reactions in the enantioselective synthesis of products containing quaternary stereocenters. Meanwhile, a detailed discussion of the AAA reactions such as ligands, scope of substrates, transformations and the general reaction mechanisms is also provided. We hope this review could stimulate further advances in much broader areas, including organic synthesis, asymmetric catalysis, CÀ H activation, and symmetrical pharmaceutical chemistry.

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Chemo‐selective Rh(II)/Pd(0) Dual Catalysis: Synthesis of All‐Carbon C3‐Quaternary Allylic Oxindoles from N‐Aryl‐α‐Diazo‐β‐Keto‐Amides with Functionalized Allyl Carbonates

Cited by 21 publications

References 89 publications

Ternary Catalysis Enabled Three-Component Asymmetric Allylic Alkylation as a Concise Track to Chiral α,α-Disubstituted Ketones

Ternary Catalysis Enabled Three-Component Asymmetric Allylic Alkylation as a Concise Track to Chiral α,α-Disubstituted Ketones

Palladium‐Catalyzed Cascade C−H Functionalization/Asymmetric Allylation Reaction of Aryl α‐Diazoamides and Allenes: Lewis Acid Makes a Difference

Enantioselective Synthesis of Quaternary Carbon Stereocenters by Asymmetric Allylic Alkylation: A Review

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