Halonium, chalconium, and pnictonium salts as noncovalent organocatalysts: a computational study on relative catalytic activity

Standard

Halonium, chalconium, and pnictonium salts as noncovalent organocatalysts: a computational study on relative catalytic activity. / Болотин, Дмитрий Сергеевич ; Новиков, Александр Сергеевич.

In: Organic & biomolecular chemistry, Vol. 20, No. 38, 09.09.2022, p. 7632-7639.

Research output: Contribution to journal › Article › peer-review

BibTeX

@article{1b0d4e07c9d9492d804f7989800b97dd,

title = "Halonium, chalconium, and pnictonium salts as noncovalent organocatalysts: a computational study on relative catalytic activity",

abstract = "This theoretical study sheds light on the relative catalytic activity of pnictonium, chalconium, and halonium salts in reactions involving elimination of chloride and electrophilic activation of a carbonyl group. DFT calculations indicate that for cationic aromatic onium salts, values of the electrostatic potential on heteroatom σ-holes gradually increase from pnictogen- to halogen-containing species. The higher values of the potential on the halogen atoms of halonium salts result in the overall higher catalytic activity of these species, but in the case of pnictonium and chalconium cations, weak interactions from the side groups provide an additional stabilization effect on the reaction transition states. Based upon quantum-chemical calculations, the catalytic activity of phosphonium(V) and arsenonium(V) salts is expected to be too low to obtain effective noncovalent organocatalytic compounds, whereas stibonium(V), telluronium(IV) and iodonium(III) salts exhibit higher potential in application as noncovalent organocatalysts.",

author = "Болотин, {Дмитрий Сергеевич} and Новиков, {Александр Сергеевич}",

note = "Publisher Copyright: {\textcopyright} 2022 The Royal Society of Chemistry.",

year = "2022",

month = sep,

day = "9",

doi = "10.1039/d2ob01415g",

language = "English",

volume = "20",

pages = "7632--7639",

journal = "Organic and Biomolecular Chemistry",

issn = "1477-0520",

publisher = "Royal Society of Chemistry",

number = "38",

}

RIS

TY - JOUR

T1 - Halonium, chalconium, and pnictonium salts as noncovalent organocatalysts: a computational study on relative catalytic activity

AU - Болотин, Дмитрий Сергеевич

AU - Новиков, Александр Сергеевич

PY - 2022/9/9

Y1 - 2022/9/9

N2 - This theoretical study sheds light on the relative catalytic activity of pnictonium, chalconium, and halonium salts in reactions involving elimination of chloride and electrophilic activation of a carbonyl group. DFT calculations indicate that for cationic aromatic onium salts, values of the electrostatic potential on heteroatom σ-holes gradually increase from pnictogen- to halogen-containing species. The higher values of the potential on the halogen atoms of halonium salts result in the overall higher catalytic activity of these species, but in the case of pnictonium and chalconium cations, weak interactions from the side groups provide an additional stabilization effect on the reaction transition states. Based upon quantum-chemical calculations, the catalytic activity of phosphonium(V) and arsenonium(V) salts is expected to be too low to obtain effective noncovalent organocatalytic compounds, whereas stibonium(V), telluronium(IV) and iodonium(III) salts exhibit higher potential in application as noncovalent organocatalysts.

AB - This theoretical study sheds light on the relative catalytic activity of pnictonium, chalconium, and halonium salts in reactions involving elimination of chloride and electrophilic activation of a carbonyl group. DFT calculations indicate that for cationic aromatic onium salts, values of the electrostatic potential on heteroatom σ-holes gradually increase from pnictogen- to halogen-containing species. The higher values of the potential on the halogen atoms of halonium salts result in the overall higher catalytic activity of these species, but in the case of pnictonium and chalconium cations, weak interactions from the side groups provide an additional stabilization effect on the reaction transition states. Based upon quantum-chemical calculations, the catalytic activity of phosphonium(V) and arsenonium(V) salts is expected to be too low to obtain effective noncovalent organocatalytic compounds, whereas stibonium(V), telluronium(IV) and iodonium(III) salts exhibit higher potential in application as noncovalent organocatalysts.

UR - https://www.mendeley.com/catalogue/d392c122-a4db-3ac5-8037-5221177cb8c4/

UR - http://www.scopus.com/inward/record.url?scp=85139573020&partnerID=8YFLogxK

U2 - 10.1039/d2ob01415g

DO - 10.1039/d2ob01415g

M3 - Article

VL - 20

SP - 7632

EP - 7639

JO - Organic and Biomolecular Chemistry

JF - Organic and Biomolecular Chemistry

SN - 1477-0520

IS - 38

ER -

ID: 98808832