Generation of 1,2-oxathiolium ions from (arysulfonyl)- and (arylsulfinyl)allenes in Brønsted acids. NMR and DFT study of these cations and their reactions

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Generation of 1,2-oxathiolium ions from (arysulfonyl)- and (arylsulfinyl)allenes in Brønsted acids. NMR and DFT study of these cations and their reactions. / Lozovskiy, Stanislav V.; Ivanov, Alexander Yu; Khoroshilova, Olesya V.; Vasilyev, Aleksander V.

In: Beilstein Journal of Organic Chemistry, Vol. 14, 22.11.2018, p. 2897-2906.

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

BibTeX

@article{0777899f3c7e4da7bb4887aaa6bc1dbd,

title = "Generation of 1,2-oxathiolium ions from (arysulfonyl)- and (arylsulfinyl)allenes in Br{\o}nsted acids. NMR and DFT study of these cations and their reactions",

abstract = "In strong Br{\o}nsted acids (CF3SO3H, FSO3H, D2SO4), (arysulfonyl)allenes (ArSO2-CR1=C=CR2R3) and (arylsulfinyl)allenes (ArSO-CR1=C=CR2R3) undergo cyclization into the corresponding stable 1,2-oxathiolium ions, which were studied by means of NMR and DFT calculations. Quenching of solutions of these cations with low nucleophilic media, aqueous HCl, leads to their deprotonation with a stereoselective formation of (arysulfonyl)butadienes (for instance, ArSO2-CR1=C-C(Me)=CH2, for R2 = R3 = Me, yields of 87-98%). Reactions of (arysulfonyl)allenes in the system TfOH (0.1 equiv)-HFIP (hexafluoropropan-2-ol) followed by hydrolysis give rise to allyl alcohols (ArSO2-CR1=CH-C(OH)R2R3, yields of 78-99%). Reflux of solutions of (arysulfonyl)allenes in the presence of TfOH (1 equiv) in 1,2-dichlorobenzene leads to the cyclization into thiochromene 1,1-diox-ides in high yields. Under the action of TfOH or AlX3 (X = Cl, Br) followed by hydrolysis of reaction mixtures, (arylsulfinyl)allenes give allyl alcohols (ArSO2-CR1=CH-C(OH)R2R3). Plausible reaction mechanisms have been proposed for all studied reactions.",

keywords = "(Arylsulfinyl)allenes, (Arylsulfonyl)allenes, 1,1-dioxides, 1,2-oxathiolium ions, Butadienes, Thiochromene",

author = "Lozovskiy, {Stanislav V.} and Ivanov, {Alexander Yu} and Khoroshilova, {Olesya V.} and Vasilyev, {Aleksander V.}",

year = "2018",

month = nov,

day = "22",

doi = "10.3762/bjoc.14.268",

language = "English",

volume = "14",

pages = "2897--2906",

journal = "Beilstein Journal of Organic Chemistry",

issn = "1860-5397",

publisher = "Beilstein-Institut Zur Forderung der Chemischen Wissenschaften",

}

RIS

TY - JOUR

T1 - Generation of 1,2-oxathiolium ions from (arysulfonyl)- and (arylsulfinyl)allenes in Brønsted acids. NMR and DFT study of these cations and their reactions

AU - Lozovskiy, Stanislav V.

AU - Ivanov, Alexander Yu

AU - Khoroshilova, Olesya V.

AU - Vasilyev, Aleksander V.

PY - 2018/11/22

Y1 - 2018/11/22

N2 - In strong Brønsted acids (CF3SO3H, FSO3H, D2SO4), (arysulfonyl)allenes (ArSO2-CR1=C=CR2R3) and (arylsulfinyl)allenes (ArSO-CR1=C=CR2R3) undergo cyclization into the corresponding stable 1,2-oxathiolium ions, which were studied by means of NMR and DFT calculations. Quenching of solutions of these cations with low nucleophilic media, aqueous HCl, leads to their deprotonation with a stereoselective formation of (arysulfonyl)butadienes (for instance, ArSO2-CR1=C-C(Me)=CH2, for R2 = R3 = Me, yields of 87-98%). Reactions of (arysulfonyl)allenes in the system TfOH (0.1 equiv)-HFIP (hexafluoropropan-2-ol) followed by hydrolysis give rise to allyl alcohols (ArSO2-CR1=CH-C(OH)R2R3, yields of 78-99%). Reflux of solutions of (arysulfonyl)allenes in the presence of TfOH (1 equiv) in 1,2-dichlorobenzene leads to the cyclization into thiochromene 1,1-diox-ides in high yields. Under the action of TfOH or AlX3 (X = Cl, Br) followed by hydrolysis of reaction mixtures, (arylsulfinyl)allenes give allyl alcohols (ArSO2-CR1=CH-C(OH)R2R3). Plausible reaction mechanisms have been proposed for all studied reactions.

AB - In strong Brønsted acids (CF3SO3H, FSO3H, D2SO4), (arysulfonyl)allenes (ArSO2-CR1=C=CR2R3) and (arylsulfinyl)allenes (ArSO-CR1=C=CR2R3) undergo cyclization into the corresponding stable 1,2-oxathiolium ions, which were studied by means of NMR and DFT calculations. Quenching of solutions of these cations with low nucleophilic media, aqueous HCl, leads to their deprotonation with a stereoselective formation of (arysulfonyl)butadienes (for instance, ArSO2-CR1=C-C(Me)=CH2, for R2 = R3 = Me, yields of 87-98%). Reactions of (arysulfonyl)allenes in the system TfOH (0.1 equiv)-HFIP (hexafluoropropan-2-ol) followed by hydrolysis give rise to allyl alcohols (ArSO2-CR1=CH-C(OH)R2R3, yields of 78-99%). Reflux of solutions of (arysulfonyl)allenes in the presence of TfOH (1 equiv) in 1,2-dichlorobenzene leads to the cyclization into thiochromene 1,1-diox-ides in high yields. Under the action of TfOH or AlX3 (X = Cl, Br) followed by hydrolysis of reaction mixtures, (arylsulfinyl)allenes give allyl alcohols (ArSO2-CR1=CH-C(OH)R2R3). Plausible reaction mechanisms have been proposed for all studied reactions.

KW - (Arylsulfinyl)allenes

KW - (Arylsulfonyl)allenes

KW - 1,1-dioxides

KW - 1,2-oxathiolium ions

KW - Butadienes

KW - Thiochromene

UR - http://www.scopus.com/inward/record.url?scp=85057617797&partnerID=8YFLogxK

U2 - 10.3762/bjoc.14.268

DO - 10.3762/bjoc.14.268

M3 - Article

AN - SCOPUS:85057617797

VL - 14

SP - 2897

EP - 2906

JO - Beilstein Journal of Organic Chemistry

JF - Beilstein Journal of Organic Chemistry

SN - 1860-5397

ER -

ID: 44002008