TY - JOUR

T1 - Chalcogen- and Halogen-Bond-Donating Cyanoborohydrides Provide Imine Hydrogenation

AU - Ильин, Михаил Вячеславович

AU - Сафинская, Яна Валерьевна

AU - Полонников, Денис Алексеевич

AU - Новиков, Александр Сергеевич

AU - Болотин, Дмитрий Сергеевич

N1 - Export Date: 11 March 2024 CODEN: JOCEA Адрес для корреспонденции: Bolotin, D.S.; Institute of Chemistry, Universitetskaya Nab. 7/9, Russian Federation; эл. почта: d.s.bolotin@spbu.ru Сведения о финансировании: Russian Science Foundation, RSF, 23-73-10003 Текст о финансировании 1: This study was supported by the Russian Science Foundation (grant 23-73-10003). The physicochemical studies were performed at the Center for Magnetic Resonance and Center for Chemical Analysis and Materials Research, Center for X-ray Diffraction Studies (all at Saint Petersburg State University). Пристатейные ссылки: Aleksiev, M., Garcia Mancheno, O., Enantioselective dearomatization reactions of heteroarenes by anion-binding organocatalysis (2023) Chem. 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PY - 2024/2/19

Y1 - 2024/2/19

N2 - Sulfonium, selenonium, telluronium, and iodonium cyanoborohydrides have been synthesized, isolated, and fully characterized by various methods, including single-crystal X-ray diffraction (XRD) analysis. The quantum theory of atoms in molecules’ analysis based on the XRD data indicated that the hydride···σ-hole short contacts observed in the crystal structures of each compound have a purely noncovalent nature. The telluronium and iodonium cyanoborohydrides provide a significantly higher rate of the model reaction of imine hydrogenation compared with sodium and tetrabutylammonium cyanoborohydrides. Based on the NMR and high-resolution electrospray ionization mass spectrometry data indicating that the reaction progress is accompanied by the cation reduction, a mechanism involving intermediate formation of elusive onium hydrides has been proposed as an alternative to conventional electrophilic activation of the imine moiety by its ligation to the cation’s σ-hole. © 2024 American Chemical Society

AB - Sulfonium, selenonium, telluronium, and iodonium cyanoborohydrides have been synthesized, isolated, and fully characterized by various methods, including single-crystal X-ray diffraction (XRD) analysis. The quantum theory of atoms in molecules’ analysis based on the XRD data indicated that the hydride···σ-hole short contacts observed in the crystal structures of each compound have a purely noncovalent nature. The telluronium and iodonium cyanoborohydrides provide a significantly higher rate of the model reaction of imine hydrogenation compared with sodium and tetrabutylammonium cyanoborohydrides. Based on the NMR and high-resolution electrospray ionization mass spectrometry data indicating that the reaction progress is accompanied by the cation reduction, a mechanism involving intermediate formation of elusive onium hydrides has been proposed as an alternative to conventional electrophilic activation of the imine moiety by its ligation to the cation’s σ-hole. © 2024 American Chemical Society

KW - Crystal atomic structure

KW - Electrospray ionization

KW - Hydrides

KW - Mass spectrometry

KW - Positive ions

KW - Quantum theory

KW - Reaction intermediates

KW - Single crystals

KW - Sodium compounds

KW - X ray diffraction analysis

KW - Atoms-in-molecules analysis

KW - Chalcogens

KW - Crystals structures

KW - Halogen bonds

KW - Iodonium

KW - Quantum Theory of Atoms in Molecules

KW - Short contacts

KW - Single crystal X-ray diffraction analysis

KW - Synthesised

KW - X-ray diffraction data

KW - Hydrogenation

UR - https://www.mendeley.com/catalogue/0c0dab88-a2bf-34fa-b2a1-572ee621c85f/

U2 - 10.1021/acs.joc.3c02282

DO - 10.1021/acs.joc.3c02282

M3 - статья

VL - 89

SP - 2916

EP - 2925

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

SN - 0022-3263

IS - 5

ER -