TY - JOUR

T1 - Diaryliodoniums as Hybrid Hydrogen- and Halogen-Bond-Donating Organocatalysts for the Groebke−Blackburn−Bienaymé Reaction

AU - Ильин, Михаил Вячеславович

AU - Сысоева, Александра Александровна

AU - Новиков, Александр Сергеевич

AU - Болотин, Дмитрий Сергеевич

N1 - Publisher Copyright: © 2022 The Authors. Published by American Chemical Society.

PY - 2022/4/1

Y1 - 2022/4/1

N2 - Dibenziodolium and diphenyliodonium triflates display high catalytic activity for the multicomponent reaction that leads to a series of imidazopyridines. Density functional theory (DFT) calculations indicate that both the salts can play the role of hybrid hydrogen- and halogen-bond-donating organocatalysts, which electrophilically activate the carbonyl and imine groups during the reaction process. The ortho-H atoms in the vicinal position to the I atom play a dual role: forming additional noncovalent bonds with the ligated substrate and increasing the maximum electrostatic potential on the σ-hole at the iodine atom owing to the effects of polarization. Dibenziodolium triflate exhibits higher catalytic activity, and the results obtained from 1H nuclear magnetic resonance (NMR) titrations, in conjunction with those from DFT calculations, indicate that this could be explained in terms of the additional energy required for the rotation of the phenyl ring in the diphenyliodonium cation during ligation of the substrate.

AB - Dibenziodolium and diphenyliodonium triflates display high catalytic activity for the multicomponent reaction that leads to a series of imidazopyridines. Density functional theory (DFT) calculations indicate that both the salts can play the role of hybrid hydrogen- and halogen-bond-donating organocatalysts, which electrophilically activate the carbonyl and imine groups during the reaction process. The ortho-H atoms in the vicinal position to the I atom play a dual role: forming additional noncovalent bonds with the ligated substrate and increasing the maximum electrostatic potential on the σ-hole at the iodine atom owing to the effects of polarization. Dibenziodolium triflate exhibits higher catalytic activity, and the results obtained from 1H nuclear magnetic resonance (NMR) titrations, in conjunction with those from DFT calculations, indicate that this could be explained in terms of the additional energy required for the rotation of the phenyl ring in the diphenyliodonium cation during ligation of the substrate.

UR - http://www.scopus.com/inward/record.url?scp=85125278280&partnerID=8YFLogxK

UR - https://www.mendeley.com/catalogue/36801873-3ab3-34b4-8fd2-885ffeef32ac/

U2 - 10.1021/acs.joc.1c02885

DO - 10.1021/acs.joc.1c02885

M3 - Article

VL - 87

SP - 4569

EP - 4579

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

SN - 0022-3263

IS - 7

ER -