Synthesis, Enantiomeric Conformations, and Stereodynamics of Aromatic ortho-Substituted Disulfones

Lacour, Jérôme; Monchaud, David; Mareda, Jiri; Favarger, France; Bernardinelli, Gérald Hugues

doi:10.1002/hlca.200390020

Scientific article

English

Synthesis, Enantiomeric Conformations, and Stereodynamics of Aromatic ortho-Substituted Disulfones

Contributors

Lacour, Jérôme

; Monchaud, David; Mareda, Jiri; Favarger, France; Bernardinelli, Gérald Hugues

Published in

Helvetica chimica acta, vol. 86, no. 1, p. 65-81

Publication date

2003

Abstract

Aromatic ortho-disulfone derivatives are readily accessible from diiodide precursors by CuI-mediated reaction with sodium sulfinate salts (DMF, 110°). The sulfonyl substituents adopt in solution and in the solid state two enantiomeric conformations (? and d) as evidenced by 31P- and 1H-NMR data of the chiral D3-symmetric tris{4,5-bis[(4-methylphenyl)sulfonyl]benzene-1,2-diolato(2-)-?O,?O}phosphate(v) anion (3a) and 1,2-bis(camphor-10-sulfonyl)-4,5-dimethoxybenzene ((=1,2-bis{{[(1S,4R)-7,7-dimethyl-2-oxobicyclo[2.2.1]hept-1-yl]methyl}sulfonyl}-4,5-dimethoxybenzene; 6c). X-Ray structure analysis of 1,2-dimethoxy-4,5-bis(methylsulfonyl)benzene (6a) and 1,2-dimethoxy-4,5-bis(4-methylphenyl)sulfonyl]benzene (6b) confirmed in the solid state the preferred chiral orientation of the sulfonyl groups. Dynamic conformational isomerism was detected for 6c in its 1H-NMR in the temperature range of 110°, the corresponding free energy being 19.8 kcalmol-1.

UNIGE affiliation entities

Faculté des sciences / Section de chimie et biochimie / Département de chimie organique

Citation (ISO format)

LACOUR, Jérôme et al. Synthesis, Enantiomeric Conformations, and Stereodynamics of Aromatic ortho-Substituted Disulfones. In: Helvetica chimica acta, 2003, vol. 86, n° 1, p. 65–81. doi: 10.1002/hlca.200390020

Article

Identifiers

PID : unige:7832
DOI : 10.1002/hlca.200390020

Journal ISSN

0018-019X

822views

0downloads

Creation

21/06/2010 10:28:00

First validation

21/06/2010 10:28:00

Update

14/03/2023 15:46:52

Status update

14/03/2023 15:46:52

Last indexation

29/10/2024 15:25:33

Synthesis, Enantiomeric Conformations, and Stereodynamics of Aromatic ortho-Substituted Disulfones

Contributors

Published in

Publication date

Abstract

UNIGE affiliation entities

Citation (ISO format)

Main files (1)

Identifiers

Journal ISSN

Technical informations

Creation

First validation

Update

Status update

Last indexation