Synthesis of Allenes by Hydroalkylation of 1,3-Enynes with Ketones Enabled by Cooperative Catalysis

Eaton, Maxwell; Dai, Yuping; Wang, Ziyong; Li, Bo; Lamine, Walid; Miqueu, Karinne; Liu, Shih-Yuan

doi:10.1021/jacs.3c08151

Cited by 4 publications

(2 citation statements)

References 74 publications

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Section: Introductionmentioning

confidence: 99%

“…Recently, it has been discovered that low-valent Pd(0)/phosphine complexes can facilitate direct nucleophilic addition reactions of unactivated 1,3-diynes, 1,3-enynes to electrophiles via an “outer-sphere” oxidative addition process (Scheme D). − In their seminal work, Yamamoto and co-workers reported the catalytic electrophilic hydroalkoxylation of 1,3-diynes by Pd(PPh 3 ) 4 . The Liu group and the Tsukamoto group discovered that the nucleophilic attack of 1,3-enynes toward boronic reagents or proton could be promoted by Pd(0) catalysts. More recently, the Chen group disclosed for the first time that the Pd(0)/chiral phosphine complex can serve as a π-Lewis base to raise the highest occupied molecular orbital (HOMO) energy of 1,3-dienes via η 2 coordination, thus facilitating asymmetric vinylogous transformations with electrophiles (Scheme D) .…”

Section: Introductionmentioning

confidence: 99%

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Enantioselective Cross-[4 + 2]-Cycloaddition/Decarboxylation of 2-Pyrones by Cooperative Catalysis of the Pd(0)/NHC Complex and Chiral Phosphoric Acid

Xu,

Xie,

et al. 2024

J. Am. Chem. Soc.

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Here, we describe a cooperative Pd(0)/chiral phosphoric acid catalytic system that allows us to realize the first chemo-, regio-, and enantioselective sequential cross-[4 + 2]-cycloaddition/ decarboxylation reaction between 2-pyrones and unactivated acyclic 1,3-dienes. The key to the success of this transformation is the utilization of an achiral N-heterocyclic carbene (NHC) as the ligand and a newly developed chiral phosphoric acid as the cocatalyst. Experimental investigations and computational studies support the idea that the Pd(0)/NHC complex acts as a π-Lewis base to increase the nucleophilicity of 1,3-dienes via η 2 coordination, while the chiral phosphoric acid simultaneously increases the electrophilicity of 2-pyrones by hydrogen bonding. By this synergistic catalysis, the sequential cross-[4 + 2]-cycloaddition and decarboxylation reaction proceeds efficiently, enabling the preparation of a wide range of chiral vinyl-substituted 1,3-cyclohexadienes in good yields and enantioselectivities. The synthetic utility of this reaction is demonstrated by synthetic transformations of the product to various valuable chiral six-membered carbocycles.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Enantioselective Cross-[4 + 2]-Cycloaddition/Decarboxylation of 2-Pyrones by Cooperative Catalysis of the Pd(0)/NHC Complex and Chiral Phosphoric Acid

Xu,

Xie,

et al. 2024

J. Am. Chem. Soc.

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Chemodivergent Tandem Hydroalkylation and Hydroalkenoxylation of Conjugated Enynes

Xie,

2024

ACS Catal.

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Palladium(0) π-Lewis Base Catalysis: Concept and Development

Chen,

Ouyang,

et al. 2024

J. Am. Chem. Soc.

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The development of a new catalytic strategy plays a vital role in modern organic chemistry since it permits bond formation in an unprecedented and more efficient manner. Although the application of preformed metal complexes as π-baseactivated reagents have enabled diverse transformations elegantly, the concept and strategy by directly utilizing transition metals as efficient π-Lewis base catalysts remain underdeveloped, especially in the field of asymmetric catalysis. Here, we outline our perspective on the discovery of palladium(0) as an efficient π-Lewis base catalyst, which is capable of increasing the highest occupied molecular orbital (HOMO) energy of both electron-neutral and electron-deficient 1,3-dienes and 1,3-enynes upon flexible η 2complexes formed in situ and resultant π-backdonation. Thus, fruitful carbon−carbon-forming reactions with diverse electrophiles can be achieved enantioselectively in a vinylogous addition pattern, which is conceptually different from the classical oxidative cyclization mechanism. Emphasis will be given to the concept and mechanism elucidation, catalytic features, and reaction design together with perspective on the further development of this emerging field.

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Synthesis of Allenes by Hydroalkylation of 1,3-Enynes with Ketones Enabled by Cooperative Catalysis

Cited by 4 publications

References 74 publications

Enantioselective Cross-[4 + 2]-Cycloaddition/Decarboxylation of 2-Pyrones by Cooperative Catalysis of the Pd(0)/NHC Complex and Chiral Phosphoric Acid

Enantioselective Cross-[4 + 2]-Cycloaddition/Decarboxylation of 2-Pyrones by Cooperative Catalysis of the Pd(0)/NHC Complex and Chiral Phosphoric Acid

Chemodivergent Tandem Hydroalkylation and Hydroalkenoxylation of Conjugated Enynes

Palladium(0) π-Lewis Base Catalysis: Concept and Development

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