Enantioselective synthesis of 3-methylisochromans and determination of their absolute configurations by circular dichroism

Gábor Kerti, T. Kurtán, Tünde Zita Illyés, K. Kövér, Sándor Sólyom, Gennaro Pescitelli, Naoko Fujioka, Nina Berova, S. Antus

Research output: Contribution to journalArticle

35 Citations (Scopus)

Abstract

Seven (S)-3-methylisochromans with different substitution patterns on their aromatic rings, and hence with different directions of their sum electric transition moments, were synthesized by ring-closure of optically active (S)-1-arylpropan-2-ol derivatives. The (S)-1-arylpropan-2-ols were obtained by kinetic resolution and their absolute configurations were determined with the aid of a zinc porphyrin tweezer and by Mosher's method. A systematic CD study of substituted isochroman derivatives revealed that, unlike in the cases of chiral tetralin and 2,3-dihydrobenzo[b]furan chromophores, the presence of achiral substituents of large spectroscopic moment (e.g., OMe) on the aromatic ring does not change the helicity rule of the "unsubstituted" isochroman chromophore: (P)/(M) helicity of the isochromen heteroring resulted in positive/negative 1Lb band Cotton effects (CE) regardless of the nature(s) and position(s) of the substituent(s). (S)-3-Methylisochromans were oxidized at C-1, allowing access to the corresponding dihydroisocoumarins, in which positive CE of the n→-π* transitions were correlated with (P) helicity and (S) absolute configuration. On DDQ-assisted oxidation, two trans-1-methoxy-3-methylisochrornan derivatives were prepared and used to study the effect of the axial benzylic C-1 methoxy group on the conformation of the heteroring and the 1Lb band CE.

Original languageEnglish
Pages (from-to)296-305
Number of pages10
JournalEuropean Journal of Organic Chemistry
Issue number2
DOIs
Publication statusPublished - 2007

Fingerprint

Circular Dichroism
Cotton
Chromophores
Derivatives
Conformations
Substitution reactions
Oxidation
Kinetics
Direction compound
zinc hematoporphyrin
furan
tetralin

Keywords

  • Chirality
  • Configuration determination
  • Kinetic resolution

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Enantioselective synthesis of 3-methylisochromans and determination of their absolute configurations by circular dichroism. / Kerti, Gábor; Kurtán, T.; Illyés, Tünde Zita; Kövér, K.; Sólyom, Sándor; Pescitelli, Gennaro; Fujioka, Naoko; Berova, Nina; Antus, S.

In: European Journal of Organic Chemistry, No. 2, 2007, p. 296-305.

Research output: Contribution to journalArticle

Kerti, Gábor ; Kurtán, T. ; Illyés, Tünde Zita ; Kövér, K. ; Sólyom, Sándor ; Pescitelli, Gennaro ; Fujioka, Naoko ; Berova, Nina ; Antus, S. / Enantioselective synthesis of 3-methylisochromans and determination of their absolute configurations by circular dichroism. In: European Journal of Organic Chemistry. 2007 ; No. 2. pp. 296-305.
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AU - Kurtán, T.

AU - Illyés, Tünde Zita

AU - Kövér, K.

AU - Sólyom, Sándor

AU - Pescitelli, Gennaro

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AU - Berova, Nina

AU - Antus, S.

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AB - Seven (S)-3-methylisochromans with different substitution patterns on their aromatic rings, and hence with different directions of their sum electric transition moments, were synthesized by ring-closure of optically active (S)-1-arylpropan-2-ol derivatives. The (S)-1-arylpropan-2-ols were obtained by kinetic resolution and their absolute configurations were determined with the aid of a zinc porphyrin tweezer and by Mosher's method. A systematic CD study of substituted isochroman derivatives revealed that, unlike in the cases of chiral tetralin and 2,3-dihydrobenzo[b]furan chromophores, the presence of achiral substituents of large spectroscopic moment (e.g., OMe) on the aromatic ring does not change the helicity rule of the "unsubstituted" isochroman chromophore: (P)/(M) helicity of the isochromen heteroring resulted in positive/negative 1Lb band Cotton effects (CE) regardless of the nature(s) and position(s) of the substituent(s). (S)-3-Methylisochromans were oxidized at C-1, allowing access to the corresponding dihydroisocoumarins, in which positive CE of the n→-π* transitions were correlated with (P) helicity and (S) absolute configuration. On DDQ-assisted oxidation, two trans-1-methoxy-3-methylisochrornan derivatives were prepared and used to study the effect of the axial benzylic C-1 methoxy group on the conformation of the heteroring and the 1Lb band CE.

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