The Enantioselective Intermolecular Saegusa Allylation

Liu, Ji; Laguna, Edward M.; Mangadan, Arun Raj Kizhakkayil; Kang, Kyoungmin; Aponick, Aaron

doi:10.1021/acscatal.1c04546

Cited by 3 publications

(3 citation statements)

References 46 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In 2021, Aponick and co-workers reported an enantioselective approach toward the intermolecular Saegusa allylation . The decarboxylative coupling takes place between cyclic β-ketoacids and allyl carbonates leading to α-allylated ketones bearing quaternary stereocenters in the presence of the palladium catalyst.…”

Section: Reaction Classificationmentioning

confidence: 99%

“…In 2021, Aponick and co-workers reported an enantioselective approach toward the intermolecular Saegusa allylation. 69 The decarboxylative coupling takes place between cyclic β-ketoacids and allyl carbonates leading to α-allylated ketones bearing quaternary stereocenters in the presence of the palladium catalyst. The reaction exhibits high yield and enantioselectivity for the formation of 5-, 6-, and 7-membered cyclic ketones bearing differently substituted α-allylated quaternary centers (Scheme 83).…”

Section: Generation Of Nucleophiles Via Decarboxylationmentioning

confidence: 99%

See 1 more Smart Citation

Carboxylic Acids as Building Blocks in Catalytic Asymmetric Reactions

Majumdar

2022

ACS Catal.

View full text Add to dashboard Cite

Catalytic asymmetric transformation is a powerful strategy for the introduction of chirality to synthesize diverse nonracemic molecular entities. Chiral molecules play a significant role in the pharmaceutical area, as 50% of current drugs that are in use and 80% of the developing drugs are chiral. Asymmetric catalysis has been explored tremendously by synthetic organic chemists, and still continuous efforts are being directed toward advanced discoveries. The role of carboxylic acids as building blocks in catalytic asymmetric reactions is an emerging area. Carboxylic acids are known for their robustness and thus low reactivity. They are widely available, yet quite challenging substrates for catalytic asymmetric synthesis. The catalyst required for this kind of transformation must withstand acidic as well as oxidizing conditions. Catalyst and reaction design are required to break the glass ceiling of low reactivity of the acid substrates to ensure the useful transformation becomes successful. At the same time, high stereoselectivity needs to be achieved with complete control. Because of these challenges, carboxylic acids are highly intriguing substrates in the asymmetric catalysis research area, and more interesting methods are developing. There have been many important advancements in the last three decades. These literature reports show that carboxylic acids can act as both C- and O-nucleophiles. Furthermore, they can also be employed as electrophiles in asymmetric reactions under catalytic conditions. Brilliant application of catalyst and reaction designs made these transformations possible. This review article summarizes all these important developments on the use of carboxylic acids as building blocks in asymmetric catalysis.

show abstract

Section: Reaction Classificationmentioning

confidence: 99%

Section: Generation Of Nucleophiles Via Decarboxylationmentioning

confidence: 99%

Carboxylic Acids as Building Blocks in Catalytic Asymmetric Reactions

Majumdar

2022

ACS Catal.

View full text Add to dashboard Cite

show abstract

“…In these substrates, the allyl electrophile is attached to the enolate precursor. Only a handful of intermolecular protocols for Pd-catalyzed AAA have been disclosed (Scheme B) . In 2004, the Stoltz group demonstrated that silyl enol ethers and diallyl carbonates were suitable coupling partners for Pd-catalyzed AAA in the presence of a specialized fluoride source .…”

mentioning

confidence: 99%

Pd/Rh Dual Catalysis: Tandem Isomerization–Allylation to Access α-Quaternary Carbonyl Compounds

et al. 2022

View full text Add to dashboard Cite

A dual metal approach enables the use of unsymmetrical diallyl carbonates as viable enolate precursors for allylic alkylation reactions, allowing facile access to various α-quaternary allylated aldehydes and ketones. This methodology features a regioselective Pd-catalyzed decarboxylative oxidative addition, forming an electrophilic Pd π-allyl species and releasing an allylic alkoxide, which undergoes a Rh-catalyzed isomerization to an enolate in situ. Recombination of the Pd π-allyl species and Rhenolate nucleophile then affords the α-quaternary carbonyl compound.

show abstract

Pd-Catalyzed Intermolecular Asymmetric Allylic Alkylation Using β-Keto Acids as Enolate Precursors

2022

Synfacts

View full text Add to dashboard Cite

The Enantioselective Intermolecular Saegusa Allylation

Cited by 3 publications

References 46 publications

Carboxylic Acids as Building Blocks in Catalytic Asymmetric Reactions

Carboxylic Acids as Building Blocks in Catalytic Asymmetric Reactions

Pd/Rh Dual Catalysis: Tandem Isomerization–Allylation to Access α-Quaternary Carbonyl Compounds

Pd-Catalyzed Intermolecular Asymmetric Allylic Alkylation Using β-Keto Acids as Enolate Precursors

Contact Info

Product

Resources

About