Csp2–H functionalization of phenols: an effective access route to valuable materials via Csp2–C bond formation

Brufani, Giulia; Di Erasmo, Benedetta; Li, Chao-Jun; Vaccaro, Luigi

doi:10.1039/d4sc00687a

Cited by 4 publications

(1 citation statement)

References 262 publications

(471 reference statements)

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“…However, it would be highly desirable to use unprotected phenols directly and avoid the extra steps involved in the installation of directing groups onto the substrate. In the context of C–H functionalization of arenes, carbene transfer reactions catalyzed by transition metals have proven to be highly efficient . With free phenols, most of the metals predominantly yield the O–H inserted product and not the C–H one .…”

Section: Introductionmentioning

confidence: 99%

Cesium and Phenoxide Interaction Enabled by Rh Overrides the Innate Solvent-Mediated Chemoselectivity

Gogoi,

Jindal

2024

ACS Catal.

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DLPNO-CCSD(T) calculations are carried out to understand the distinctive chemoselectivity in a Rh(II)-catalyzed carbene insertion into a C(sp 2 )−H bond in unprotected phenols without preinstalled directing groups. As per the conventional rules of solvation and a separated ion pair in polar aprotic solvents like acetonitrile, the reaction should have resulted in an O−H insertion. However, our calculations reveal a transition state model that helps in overriding the innate chemoselectivity in acetonitrile. It involves an explicit participation of the added Cs 2 CO 3 base, where the interaction between the phenoxide oxygen and Cs cation, but not as a metal-bound Cs phenoxide, is crucial for controlling the chemoselectivity. Our study will be helpful in developing further reactions with a broad catalyst, substrate, and solvent scope.

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Section: Introductionmentioning

confidence: 99%

Cesium and Phenoxide Interaction Enabled by Rh Overrides the Innate Solvent-Mediated Chemoselectivity

Gogoi,

Jindal

2024

ACS Catal.

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Late-Stage Radical C–H Alkylamination of Tyrosine Compounds and Phenol-Containing Drugs

Andrade-Sampedro,

Correa

2024

Org. Lett.

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A modular site-selective iron-catalyzed radical amination of a number of phenol-containing biomolecules such as tyrosine-containing peptides, estrogens, and other phenol-based pharmaceuticals has been developed. The method features the use of the cost-efficient combination of FeBr 3 as catalyst along with triflic acid as Brønsted acid, thereby enabling the predictable appendance of morpholine and related heterocycles at the ortho C−H bond of phenols in a late-stage fashion.

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Biocatalytic Formal Asymmetric para-Aminoethylation of Unprotected Phenols to Chiral Amines

Zhang,

Deng,

Han

et al. 2024

ACS Catal.

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Enantiomerically pure amines are vital for the development of biologically active compounds in medicine and agriculture. While aminoalkylation of phenols is well-established for creating nitrogen-containing frameworks, the regio-and stereoselective paraaminoethylation of unprotected phenols is underexplored. To fill this gap, we propose a one-pot cascade biocatalysis system for the asymmetric para-aminoethylation of unprotected phenols into chiral amines, using simple pyruvate, NH 4 Cl, and D/L-alanine as starting materials. Utilizing a modular cascade approach, we successfully performed asymmetric paraaminoethylation of unprotected phenols through a sequential process of vinylation and hydroamination, achieving good conversions (51.0−72.0%) and >99% ee for both enantiomers of amines. Additionally, biobased p-hydroxycinnamic acid and L-tyrosine and their derivatives were converted into chiral amines with moderate to good conversions (39.4−87%) and >99% ee through integrating decarboxylation/hydroamination and deamination-decarboxylation/hydroamination. This cascade marks a successful de novo biosynthesis method for the formal asymmetric para-aminoethylation of unprotected phenols.

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Csp²–H functionalization of phenols: an effective access route to valuable materials via Csp²–C bond formation

Abstract: Simple phenols are crucial in the chemical value chain. Efforts aim to enhance their molecular complexity, with direct functionalization of Csp2–H as a key technique, facilitating economical and atomic construction of new Csp2–C bonds.

Cited by 4 publications

References 262 publications

Cesium and Phenoxide Interaction Enabled by Rh Overrides the Innate Solvent-Mediated Chemoselectivity

Cesium and Phenoxide Interaction Enabled by Rh Overrides the Innate Solvent-Mediated Chemoselectivity

Late-Stage Radical C–H Alkylamination of Tyrosine Compounds and Phenol-Containing Drugs

Biocatalytic Formal Asymmetric para-Aminoethylation of Unprotected Phenols to Chiral Amines

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