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Synthesis
DOI: 10.1055/a-2714-8611
Paper

A computational study of C–H bond abstraction in β-Amino Alcohols: O side activation over N-side via boronate adduct formation

Authors

  • Nil Sanosa

    1   Departamento de Química, Instituto de Investigación Química de la Universidad de La Rioja (IQUR), Universidad de la Rioja, Logroño, Spain (Ringgold ID: RIN16764)

  • Adrián Gómez Suárez

    2   Organic Chemistry, Bergische Universitat Wuppertal, Wuppertal, Germany (Ringgold ID: RIN26603)

  • Ignacio Funes-Ardoiz 

    3   Chemistry, Instituto de Investigación Química de la Universidad de La Rioja (IQUR), Universidad de la Rioja, Logrono, Spain (Ringgold ID: RIN16764)

Supported by: Agencia Estatal de Investigación PID2021-126075NB-I00,RYC2022-035776-I
Supported by: Fundación Banco Santander Contratos Predoctorales 2023
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Abstract A Density Functional Theory (DFT) study was performed to evaluate the reaction mechanism underlying the chemoselective C–H abstraction in β-amino alcohols under a photoredox-catalyzed platform. Our results support a three-step mechanism based on the formation of a highly activated tetracoordinated boronate adduct followed by a selective hydrogen atom transfer (HAT) and a Giese-type radical addition, which together generate the experimentally observed γ-oxo-δ-amino esters. We demonstrated that α-hydroxy C–H bonds are more readily activated towards the HAT step than the α-amino C–H bond. This enhanced chemoselectivity arises from the tetracoordinated boronate adduct, which increases the hydridic character of the α-hydroxy H atom and lowers the bond dissociation energy (BDE) of the C–H bond.



Publication History

Received: 31 July 2025

Accepted after revision: 01 October 2025

Accepted Manuscript online:
01 October 2025

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