Site‐Selective γ‐C(sp3)−H and γ‐C(sp2)−H Arylation of Free Amino Esters Promoted by a Catalytic Transient Directing Group

Lin, Hua; Wang, Chao; Bannister, Thomas D.; Kamenecka, Theodore M.

doi:10.1002/chem.201802465

Cited by 61 publications

(54 citation statements)

References 53 publications

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“…In 2018, Kamenecka and co‐workers reported Pd‐catalyzed γ‐C(sp 3 )−H and γ‐C(sp 2 )−H arylation of free amino esters using 2‐hydroxynicotinaldehyde ( L35 ) . It was found that the re‐esterification is necessary for this reaction due to the hydrolysis of the ester (Scheme ).…”

Section: Reversible Covalent Bonding For Transition Metal‐catalyzed Cmentioning

confidence: 99%

“…In 2018, Kamenecka and co-workers reported Pd-catalyzed g-C(sp 3 )ÀHa nd g-C(sp 2 )ÀHa rylation of free amino esters using 2-hydroxynicotinaldehyde (L35). [46] It was found that the reesterification is necessary for this reactiondue to the hydrolysis of the ester (Scheme 23). Interestingly,Y oung and co-workers presented as trategy using as toichiometrica mount of dry ice to provide CO 2 as al igand to mediate g-arylationo fa liphatic amines.…”

Section: )àHf Unctionalization Of Aminesmentioning

confidence: 99%

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Transient Ligand‐Enabled Transition Metal‐Catalyzed C−H Functionalization

et al. 2019

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Transition metal‐catalyzed C−H bond functionalization is among the most efficient and powerful strategies in synthetic organic chemistry to derivatize otherwise inert sites of organic molecules for the construction of C−C and C−heteroatom bonds. However, additional steps are often required to install the directing groups to realize selective C−H bond functionalization of the substrates. These tedious steps run counter to the step‐economical nature of the C−H activation. In contrast, direct functionalization of the substrate by using transient ligands avoids the unnecessary steps for the pre‐functionalization of the substrates. This Minireview provides a short overview of the major progress made in this field for C−H functionalization at sp2 and sp3 carbon centers with different transient working modes, including covalent, hydrogen, and ionic bonds.

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Section: Reversible Covalent Bonding For Transition Metal‐catalyzed Cmentioning

confidence: 99%

Section: )àHf Unctionalization Of Aminesmentioning

confidence: 99%

Transient Ligand‐Enabled Transition Metal‐Catalyzed C−H Functionalization

et al. 2019

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“…By applying the same aldehyde as transient directing group, Kamenecka further optimized this reaction for allylic and a-aromatic amino ester substrates and the g-(sp 3 )-and g-(sp 2 )-arylated products were obtained in decent yields (Scheme 21). 36 Instead of using aldehyde directly, Bull realized that simple a-oxylacetal can be applied as the directing aldehyde precursor in the g-arylation of aliphatic amines (Scheme 21). 37 Except for above examples where aldehydes (or their precursors) function in catalytic amount under the reaction conditions, stoichiometric amount of aldehyde, such as quinoline-8-carbaldehyde cat.…”

Section: Coupling Reactionmentioning

confidence: 99%

Aldehyde catalysis – from simple aldehydes to artificial enzymes

Yuan

Liao

Jiang³

et al. 2020

RSC Adv.

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“…We also explored a glutamate ester, which gave the product with subsequent lactamization with the side chain after the arylation reaction (1ab) due to the transient nature of the DG. 43,44 A derivative of the dipeptide aspartame was also used in the reaction, in this case giving subsequent lactamization at the C-terminus (1ac). The reaction also worked on terpene-containing examples (1ad and 1ae), including a more complex cedrenecontaining cinnamylamine (1af).…”

mentioning

confidence: 99%

CO2 As A Transient Directing Group for the Oxidative Heck Coupling of Free Allylamines With Aryl Iodides

Landge¹,

Maxwell²,

Chand-Thakuri³

et al. 2020

Preprint

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Oxidative Heck couplings are a powerful method for elaborating alkene feedstocks. While selective functionalization of terminal olefins has been achieved by catalyst design, selective functionalization of internal olefins has generally required use of directing groups except in the case of Michael acceptors. Allylamine substrates have typically required protection to be suitable for these reactions, decreasing the step and atom economy of these procedures. Herein we demonstrate that the addition of CO2 (dry ice) as a transient directing group allows for the stereospecific arylation of both secondary and primary allylamines in the presence of a PdII catalyst. Notably, the product 3,3’-diarylallylamine motif is prevalent in a variety of biologically-relevant structures, and this method represents the most straightforward synthesis of these targets to date. Key features of the method are the ability to access relatively mild conditions that facilitate a broad substrate scope, as well as direct diarylation of terminal allylamine substrates. In addition, several complex and therapeutically-relevant molecules are included to demonstrate the utility of the transformation.

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Site‐Selective γ‐C(sp³)−H and γ‐C(sp²)−H Arylation of Free Amino Esters Promoted by a Catalytic Transient Directing Group

Cited by 61 publications

References 53 publications

Transient Ligand‐Enabled Transition Metal‐Catalyzed C−H Functionalization

Transient Ligand‐Enabled Transition Metal‐Catalyzed C−H Functionalization

Aldehyde catalysis – from simple aldehydes to artificial enzymes

CO2 As A Transient Directing Group for the Oxidative Heck Coupling of Free Allylamines With Aryl Iodides

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