Cooperativity between the Substrate and Ligand in Palladium-Catalyzed Allylic Alkylation Using 1-Aryl-1-propynes

Gupta, Aniket; Saha, Anusuya; Rahaman, Ajijur; Kumar, J. Sharath; Suresh, Eringathodi; Si, Mrinal Kanti; Bhadra, Sukalyan

doi:10.1021/acs.joc.2c00592

Cited by 2 publications

(2 citation statements)

References 35 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[25] In this regard, Bhadra et al unveiled a powerful catalyst system for the allylic alkylation of ketones, β-ketoesters and aldehydes by an alkyne. [26] The strategy is based on a unique mode of action of a mono protected amino acid ligand (MPAA). It was hypothesized that the N-acyl oxygen of an in situ formed Pd(II)À MPAA complex would abstract the α-proton of an imine, thereby improving the ease of tautomerization to the enamine form to expedite the allylic alkylation process (TS6, Scheme 20).…”

Section: α-Allylic Alkylation Reactionsmentioning

confidence: 99%

See 1 more Smart Citation

Bioinspired Functionalization of Carbonyl Compounds Enabled by Metal Chelated Bifunctional Ligands

Gupta,

Rahaman,

Bhadra

2023

Chemistry A European J

Self Cite

View full text Add to dashboard Cite

In Nature, enzymatic reactions proceed through exceptionally ordered transition states giving rise to extraordinary levels of stereoselection. In those reactions, the active site of the enzyme plays crucial roles – through one position, it holds the substrate in the proximity to the reaction epicentre that facilitates both the reactivity and stereoselectivity of the chemical process. Inspired by this natural phenomenon, synthetic chemists have designed bifunctional ligands that not only coordinate to a metal centre but also preassociate with an organic substrate, e.g. aldehyde and ketone, and exerts stereodirecting influence to accelerate the attack of the incoming reacting partner from a particular enantiotopic face. The chief goal of the current review is to give an overview of the recently developed approaches enabled by privileged bio‐inspired bifunctional ligands that not only bind to the metal catalyst but also activates carbonyl substrates via organocatalysis, thereby easing in the new bond forming step. As carbonyl a‐functionalizations are dominated by enamine and enolate chemistry, the current review primarily focusses on enamine‐ and enolate‐metal catalysis by bifunctional ligands. Thus, developments based on traditional cooperative catalysis occurring through two directly coupled but independent catalytic cycles of an organocatalyst and a metal catalyst are not covered.

show abstract

Section: α-Allylic Alkylation Reactionsmentioning

confidence: 99%

“…In this regard, Bhadra et al. unveiled a powerful catalyst system for the allylic alkylation of ketones, β‐ketoesters and aldehydes by an alkyne [26] . The strategy is based on a unique mode of action of a mono protected amino acid ligand (MPAA).…”

Section: Enamine‐metal Lewis Acid Catalysis On a Bifunctional Ligand ...mentioning

confidence: 99%

Bioinspired Functionalization of Carbonyl Compounds Enabled by Metal Chelated Bifunctional Ligands

Gupta,

Rahaman,

Bhadra

2023

Chemistry A European J

Self Cite

View full text Add to dashboard Cite

show abstract

Synthesis and Ring‐Closing Reactions of Aminocyclohexane Derivatives Bearing Unsaturated Side Chains at C2: Stereocontrolled Approaches to cis‐ and trans‐Fused Perhydro‐indoles and ‐quinolines

Xing,

He,

Song

et al. 2024

Eur J Org Chem

View full text Add to dashboard Cite

Two epimeric pairs of N‐Ts‐protected cyclohexylamines that incorporate an unsaturated side‐chain at the C2 position have been prepared. Contrary to expectations, none of these underwent clean, photochemically‐induced intramolecular hydroamination reactions to give the corresponding perhydro‐indole or ‐quinolines. However, they did participate in efficient olefin cross metathesis (OCM) reactions with methyl crotonate. Three of the four acrylates so‐formed engaged in base‐promoted and completely diastereoselective, intramolecular aza‐Michael addition (cyclisation) reactions to give the isomeric and C2‐substituted perhydro‐indoles or ‐quinolines with the structures of these being confirmed by single‐crystal X‐ray analyses. DFT calculations generated results consistent with the observed diastereoselectivities and the proposed transition states. Manipulation of the ester groups associated with the cyclization products allowed for their conversion, inter alia, into the corresponding n‐propyl residues and thus providing novel analogues of neurotoxic alkaloids such as pumiliotoxin C.

show abstract

Cooperativity between the Substrate and Ligand in Palladium-Catalyzed Allylic Alkylation Using 1-Aryl-1-propynes

Cited by 2 publications

References 35 publications

Bioinspired Functionalization of Carbonyl Compounds Enabled by Metal Chelated Bifunctional Ligands

Bioinspired Functionalization of Carbonyl Compounds Enabled by Metal Chelated Bifunctional Ligands

Synthesis and Ring‐Closing Reactions of Aminocyclohexane Derivatives Bearing Unsaturated Side Chains at C2: Stereocontrolled Approaches to cis‐ and trans‐Fused Perhydro‐indoles and ‐quinolines

Contact Info

Product

Resources

About