Long-distance control in stereoselective reduction of 3-[3-(4'-bromo[ 1,1 '-biphenyl]-4-yl)-3-keto-1-phenylpropyl]-4-hydroxy-2h-1-benzopyran-2- one

Relative configuration of prevailing diastereomer and absolute configuration of its enantiomers

Amir Avdagić, Livius Cotarca, Zdenko Hameršak, M. Hollósi, Zs. Majer, Edina Ljubović, Andreja Šuste, Vitomir Šunjic

Research output: Contribution to journalArticle

Abstract

Depending on the reducing agent and reaction conditions, diastereoselective reduction of 3-[3-(4'-bromo[1,1'-biphenyl]-4-yl)-3-keto- 1-phenylpropyl]-4-hydroxy-2H-1-benzopyran-2-one (2) proceeds with different stereoselectivity; a surprisingly high, approximately 90% d.c. of 4A is achieved with NaBH4 in MeOH at low temperature. Resulting diastereomeric racemates 4A and 4B are separated and their respective syn and anti configurations are assigned on the bases of mechanic considerations, supported by the 1H-NMR spectra and conformational analysis based on MM2 calculations. The syn diastereomer 7A, 4-OMe derivative of 4A, was partially resolved by acylation at C(3)-OH with S-(-)-camphanic acid to camphanyl ester 12 of (-)-7A, leaving (+)-enantiomer 7A. The assignment of absolute 1R,3S- configuration to (-)-7A is based on comparison of its CD spectrum with those of the model compounds S-14 and R-15, which represent partial chromophores 4- hydroxy-2H-1-benzopyran-2-one (4-hydroxycoumarin) A, and 4'-bromo-1,1'- biphenyl B; their exciton coupling in (-)-7A is suggested.

Original languageEnglish
Pages (from-to)512-522
Number of pages11
JournalChirality
Volume9
Issue number5-6
DOIs
Publication statusPublished - 1997

Fingerprint

Phenprocoumon
Coumarins
Stereoselectivity
Acylation
Enantiomers
Reducing agents
Chromophores
Excitons
Esters
Mechanics
Nuclear magnetic resonance
Derivatives
Acids
Reducing Agents
Spectrum Analysis
Temperature
diphenyl

Keywords

  • Asymmetric induction
  • Circular dichroism (CD)
  • Coupled chromophores
  • Stereoselective reduction
  • Syn/anti diasteroselectivity

ASJC Scopus subject areas

  • Analytical Chemistry
  • Drug Discovery
  • Organic Chemistry
  • Pharmacology

Cite this

Long-distance control in stereoselective reduction of 3-[3-(4'-bromo[ 1,1 '-biphenyl]-4-yl)-3-keto-1-phenylpropyl]-4-hydroxy-2h-1-benzopyran-2- one : Relative configuration of prevailing diastereomer and absolute configuration of its enantiomers. / Avdagić, Amir; Cotarca, Livius; Hameršak, Zdenko; Hollósi, M.; Majer, Zs.; Ljubović, Edina; Šuste, Andreja; Šunjic, Vitomir.

In: Chirality, Vol. 9, No. 5-6, 1997, p. 512-522.

Research output: Contribution to journalArticle

@article{4e72b8e0496a403e9ad4c6c47ae883c3,
title = "Long-distance control in stereoselective reduction of 3-[3-(4'-bromo[ 1,1 '-biphenyl]-4-yl)-3-keto-1-phenylpropyl]-4-hydroxy-2h-1-benzopyran-2- one: Relative configuration of prevailing diastereomer and absolute configuration of its enantiomers",
abstract = "Depending on the reducing agent and reaction conditions, diastereoselective reduction of 3-[3-(4'-bromo[1,1'-biphenyl]-4-yl)-3-keto- 1-phenylpropyl]-4-hydroxy-2H-1-benzopyran-2-one (2) proceeds with different stereoselectivity; a surprisingly high, approximately 90{\%} d.c. of 4A is achieved with NaBH4 in MeOH at low temperature. Resulting diastereomeric racemates 4A and 4B are separated and their respective syn and anti configurations are assigned on the bases of mechanic considerations, supported by the 1H-NMR spectra and conformational analysis based on MM2 calculations. The syn diastereomer 7A, 4-OMe derivative of 4A, was partially resolved by acylation at C(3)-OH with S-(-)-camphanic acid to camphanyl ester 12 of (-)-7A, leaving (+)-enantiomer 7A. The assignment of absolute 1R,3S- configuration to (-)-7A is based on comparison of its CD spectrum with those of the model compounds S-14 and R-15, which represent partial chromophores 4- hydroxy-2H-1-benzopyran-2-one (4-hydroxycoumarin) A, and 4'-bromo-1,1'- biphenyl B; their exciton coupling in (-)-7A is suggested.",
keywords = "Asymmetric induction, Circular dichroism (CD), Coupled chromophores, Stereoselective reduction, Syn/anti diasteroselectivity",
author = "Amir Avdagić and Livius Cotarca and Zdenko Hameršak and M. Holl{\'o}si and Zs. Majer and Edina Ljubović and Andreja Šuste and Vitomir Šunjic",
year = "1997",
doi = "10.1002/(SICI)1520-636X(1997)9:5/6<512::AID-CHIR18>3.0.CO;2-R",
language = "English",
volume = "9",
pages = "512--522",
journal = "Chirality",
issn = "0899-0042",
publisher = "Wiley-Liss Inc.",
number = "5-6",

}

TY - JOUR

T1 - Long-distance control in stereoselective reduction of 3-[3-(4'-bromo[ 1,1 '-biphenyl]-4-yl)-3-keto-1-phenylpropyl]-4-hydroxy-2h-1-benzopyran-2- one

T2 - Relative configuration of prevailing diastereomer and absolute configuration of its enantiomers

AU - Avdagić, Amir

AU - Cotarca, Livius

AU - Hameršak, Zdenko

AU - Hollósi, M.

AU - Majer, Zs.

AU - Ljubović, Edina

AU - Šuste, Andreja

AU - Šunjic, Vitomir

PY - 1997

Y1 - 1997

N2 - Depending on the reducing agent and reaction conditions, diastereoselective reduction of 3-[3-(4'-bromo[1,1'-biphenyl]-4-yl)-3-keto- 1-phenylpropyl]-4-hydroxy-2H-1-benzopyran-2-one (2) proceeds with different stereoselectivity; a surprisingly high, approximately 90% d.c. of 4A is achieved with NaBH4 in MeOH at low temperature. Resulting diastereomeric racemates 4A and 4B are separated and their respective syn and anti configurations are assigned on the bases of mechanic considerations, supported by the 1H-NMR spectra and conformational analysis based on MM2 calculations. The syn diastereomer 7A, 4-OMe derivative of 4A, was partially resolved by acylation at C(3)-OH with S-(-)-camphanic acid to camphanyl ester 12 of (-)-7A, leaving (+)-enantiomer 7A. The assignment of absolute 1R,3S- configuration to (-)-7A is based on comparison of its CD spectrum with those of the model compounds S-14 and R-15, which represent partial chromophores 4- hydroxy-2H-1-benzopyran-2-one (4-hydroxycoumarin) A, and 4'-bromo-1,1'- biphenyl B; their exciton coupling in (-)-7A is suggested.

AB - Depending on the reducing agent and reaction conditions, diastereoselective reduction of 3-[3-(4'-bromo[1,1'-biphenyl]-4-yl)-3-keto- 1-phenylpropyl]-4-hydroxy-2H-1-benzopyran-2-one (2) proceeds with different stereoselectivity; a surprisingly high, approximately 90% d.c. of 4A is achieved with NaBH4 in MeOH at low temperature. Resulting diastereomeric racemates 4A and 4B are separated and their respective syn and anti configurations are assigned on the bases of mechanic considerations, supported by the 1H-NMR spectra and conformational analysis based on MM2 calculations. The syn diastereomer 7A, 4-OMe derivative of 4A, was partially resolved by acylation at C(3)-OH with S-(-)-camphanic acid to camphanyl ester 12 of (-)-7A, leaving (+)-enantiomer 7A. The assignment of absolute 1R,3S- configuration to (-)-7A is based on comparison of its CD spectrum with those of the model compounds S-14 and R-15, which represent partial chromophores 4- hydroxy-2H-1-benzopyran-2-one (4-hydroxycoumarin) A, and 4'-bromo-1,1'- biphenyl B; their exciton coupling in (-)-7A is suggested.

KW - Asymmetric induction

KW - Circular dichroism (CD)

KW - Coupled chromophores

KW - Stereoselective reduction

KW - Syn/anti diasteroselectivity

UR - http://www.scopus.com/inward/record.url?scp=0030924018&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0030924018&partnerID=8YFLogxK

U2 - 10.1002/(SICI)1520-636X(1997)9:5/6<512::AID-CHIR18>3.0.CO;2-R

DO - 10.1002/(SICI)1520-636X(1997)9:5/6<512::AID-CHIR18>3.0.CO;2-R

M3 - Article

VL - 9

SP - 512

EP - 522

JO - Chirality

JF - Chirality

SN - 0899-0042

IS - 5-6

ER -