Synthesis and hydrolysis of optically active naphthyl-phenyl-bis(acyloxy) spiro-λ4-sulfane: Absolute configurations of spiro-λ4-sulfanes, related sulfonium salts and naphthyl phenyl sulfoxides determined by CD spectroscopy using exciton chirality and empirical rules

Jeno Varga, J. Rábai, Ferenc Ruff, Árpád Kucsman, E. Vass, M. Hollósi, D. Szabó

Research output: Contribution to journalArticle

1 Citation (Scopus)

Abstract

(S)-(+)- and (R)-(-)-enantiomers of naphthyl-phenyl-bis(acyloxy)spiro- λ4-sulfane 2 were prepared from the precursors (R)-(-)- and (S)-(+)-naphthyl phenyl sulfoxide dicarboxylic acid 2a with acetic anhydride. The hydrolysis of spiro-λ4-sulfane (R)-(-)-2 in acidic and basic solutions gave as major products sulfoxide (S)-(+)-2a and (R)-(-)-2a, respectively. The selectivity of the reactions was interpreted with the different reactivities of the ortho and peri neighboring carboxylic groups of the sulfoxide 2a, and with the different ability of the five and six-membered rings to be cleaved in spiro-λ4-sulfane 2. The absolute configurations of the enantiomeric spiro-λ4-sulfanes 2 and sulfoxides 2a were determined by CD spectroscopy. Exciton coupling was observed in the spectrum of spiro-λ4-sulfane 2 between the benzene 1La and naphthalene 1Bb transitions, which results in a negative couplet for (R)-(-)-2. Exciton coupling can be expected only for the 1Bb transitions of the S-phenyl and S-naphthyl rings of the sulfoxides, which define a positive couplet for (S)-(+)-2a. Empirical rules were found to be valid for the determination of configuration of spiro-λ4-sulfanes and related sulfonium compound derivatives with a trigonal bipyramidal structure, and for that of naphthyl-phenyl-sulfoxides. Both spiro-λ4-sulfanes and sulfoxides should be viewed from the side of the lone pair; the axial substituents in the former case and the downwards oriented S=O bond in the latter case are placed in a vertical plane. Rings and substituents in the upper-right and lower-left sectors define positive exciton couplets, while the opposite case is characterized by negative exciton-coupled circular dichroism (EC-CD).

Original languageEnglish
Pages (from-to)3745-3753
Number of pages9
JournalTetrahedron Asymmetry
Volume14
Issue number23
DOIs
Publication statusPublished - Nov 28 2003

Fingerprint

sulfoxide
Chirality
Sulfoxides
chirality
Excitons
hydrolysis
Hydrolysis
Spectrum Analysis
Salts
excitons
Spectroscopy
salts
synthesis
configurations
Sulfonium Compounds
spectroscopy
rings
Dicarboxylic Acids
Enantiomers
dicarboxylic acids

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry
  • Materials Chemistry
  • Drug Discovery

Cite this

@article{f002d52649144c8c93d2240dde4c27d0,
title = "Synthesis and hydrolysis of optically active naphthyl-phenyl-bis(acyloxy) spiro-λ4-sulfane: Absolute configurations of spiro-λ4-sulfanes, related sulfonium salts and naphthyl phenyl sulfoxides determined by CD spectroscopy using exciton chirality and empirical rules",
abstract = "(S)-(+)- and (R)-(-)-enantiomers of naphthyl-phenyl-bis(acyloxy)spiro- λ4-sulfane 2 were prepared from the precursors (R)-(-)- and (S)-(+)-naphthyl phenyl sulfoxide dicarboxylic acid 2a with acetic anhydride. The hydrolysis of spiro-λ4-sulfane (R)-(-)-2 in acidic and basic solutions gave as major products sulfoxide (S)-(+)-2a and (R)-(-)-2a, respectively. The selectivity of the reactions was interpreted with the different reactivities of the ortho and peri neighboring carboxylic groups of the sulfoxide 2a, and with the different ability of the five and six-membered rings to be cleaved in spiro-λ4-sulfane 2. The absolute configurations of the enantiomeric spiro-λ4-sulfanes 2 and sulfoxides 2a were determined by CD spectroscopy. Exciton coupling was observed in the spectrum of spiro-λ4-sulfane 2 between the benzene 1La and naphthalene 1Bb transitions, which results in a negative couplet for (R)-(-)-2. Exciton coupling can be expected only for the 1Bb transitions of the S-phenyl and S-naphthyl rings of the sulfoxides, which define a positive couplet for (S)-(+)-2a. Empirical rules were found to be valid for the determination of configuration of spiro-λ4-sulfanes and related sulfonium compound derivatives with a trigonal bipyramidal structure, and for that of naphthyl-phenyl-sulfoxides. Both spiro-λ4-sulfanes and sulfoxides should be viewed from the side of the lone pair; the axial substituents in the former case and the downwards oriented S=O bond in the latter case are placed in a vertical plane. Rings and substituents in the upper-right and lower-left sectors define positive exciton couplets, while the opposite case is characterized by negative exciton-coupled circular dichroism (EC-CD).",
author = "Jeno Varga and J. R{\'a}bai and Ferenc Ruff and {\'A}rp{\'a}d Kucsman and E. Vass and M. Holl{\'o}si and D. Szab{\'o}",
year = "2003",
month = "11",
day = "28",
doi = "10.1016/j.tetasy.2003.09.011",
language = "English",
volume = "14",
pages = "3745--3753",
journal = "Tetrahedron Asymmetry",
issn = "0957-4166",
publisher = "Elsevier Limited",
number = "23",

}

TY - JOUR

T1 - Synthesis and hydrolysis of optically active naphthyl-phenyl-bis(acyloxy) spiro-λ4-sulfane

T2 - Absolute configurations of spiro-λ4-sulfanes, related sulfonium salts and naphthyl phenyl sulfoxides determined by CD spectroscopy using exciton chirality and empirical rules

AU - Varga, Jeno

AU - Rábai, J.

AU - Ruff, Ferenc

AU - Kucsman, Árpád

AU - Vass, E.

AU - Hollósi, M.

AU - Szabó, D.

PY - 2003/11/28

Y1 - 2003/11/28

N2 - (S)-(+)- and (R)-(-)-enantiomers of naphthyl-phenyl-bis(acyloxy)spiro- λ4-sulfane 2 were prepared from the precursors (R)-(-)- and (S)-(+)-naphthyl phenyl sulfoxide dicarboxylic acid 2a with acetic anhydride. The hydrolysis of spiro-λ4-sulfane (R)-(-)-2 in acidic and basic solutions gave as major products sulfoxide (S)-(+)-2a and (R)-(-)-2a, respectively. The selectivity of the reactions was interpreted with the different reactivities of the ortho and peri neighboring carboxylic groups of the sulfoxide 2a, and with the different ability of the five and six-membered rings to be cleaved in spiro-λ4-sulfane 2. The absolute configurations of the enantiomeric spiro-λ4-sulfanes 2 and sulfoxides 2a were determined by CD spectroscopy. Exciton coupling was observed in the spectrum of spiro-λ4-sulfane 2 between the benzene 1La and naphthalene 1Bb transitions, which results in a negative couplet for (R)-(-)-2. Exciton coupling can be expected only for the 1Bb transitions of the S-phenyl and S-naphthyl rings of the sulfoxides, which define a positive couplet for (S)-(+)-2a. Empirical rules were found to be valid for the determination of configuration of spiro-λ4-sulfanes and related sulfonium compound derivatives with a trigonal bipyramidal structure, and for that of naphthyl-phenyl-sulfoxides. Both spiro-λ4-sulfanes and sulfoxides should be viewed from the side of the lone pair; the axial substituents in the former case and the downwards oriented S=O bond in the latter case are placed in a vertical plane. Rings and substituents in the upper-right and lower-left sectors define positive exciton couplets, while the opposite case is characterized by negative exciton-coupled circular dichroism (EC-CD).

AB - (S)-(+)- and (R)-(-)-enantiomers of naphthyl-phenyl-bis(acyloxy)spiro- λ4-sulfane 2 were prepared from the precursors (R)-(-)- and (S)-(+)-naphthyl phenyl sulfoxide dicarboxylic acid 2a with acetic anhydride. The hydrolysis of spiro-λ4-sulfane (R)-(-)-2 in acidic and basic solutions gave as major products sulfoxide (S)-(+)-2a and (R)-(-)-2a, respectively. The selectivity of the reactions was interpreted with the different reactivities of the ortho and peri neighboring carboxylic groups of the sulfoxide 2a, and with the different ability of the five and six-membered rings to be cleaved in spiro-λ4-sulfane 2. The absolute configurations of the enantiomeric spiro-λ4-sulfanes 2 and sulfoxides 2a were determined by CD spectroscopy. Exciton coupling was observed in the spectrum of spiro-λ4-sulfane 2 between the benzene 1La and naphthalene 1Bb transitions, which results in a negative couplet for (R)-(-)-2. Exciton coupling can be expected only for the 1Bb transitions of the S-phenyl and S-naphthyl rings of the sulfoxides, which define a positive couplet for (S)-(+)-2a. Empirical rules were found to be valid for the determination of configuration of spiro-λ4-sulfanes and related sulfonium compound derivatives with a trigonal bipyramidal structure, and for that of naphthyl-phenyl-sulfoxides. Both spiro-λ4-sulfanes and sulfoxides should be viewed from the side of the lone pair; the axial substituents in the former case and the downwards oriented S=O bond in the latter case are placed in a vertical plane. Rings and substituents in the upper-right and lower-left sectors define positive exciton couplets, while the opposite case is characterized by negative exciton-coupled circular dichroism (EC-CD).

UR - http://www.scopus.com/inward/record.url?scp=0344153821&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0344153821&partnerID=8YFLogxK

U2 - 10.1016/j.tetasy.2003.09.011

DO - 10.1016/j.tetasy.2003.09.011

M3 - Article

AN - SCOPUS:0344153821

VL - 14

SP - 3745

EP - 3753

JO - Tetrahedron Asymmetry

JF - Tetrahedron Asymmetry

SN - 0957-4166

IS - 23

ER -