Inherently chiral molecular clips: Synthesis, chiroptical properties, and application to chiral discrimination

Gaku Fukuhara; Süreyya Madenci; Jolanta Polkowska; Frank Bastkowski; Frank Gerrit Klärner; Yumi Origane; Masayuki Kaneda; Tadashi Mori; Takehiko Wada; Yoshihisa Inoue

doi:10.1002/chem.200601585

Inherently chiral molecular clips: Synthesis, chiroptical properties, and application to chiral discrimination

Gaku Fukuhara, Süreyya Madenci, Jolanta Polkowska, Frank Bastkowski, Frank Gerrit Klärner, Yumi Origane, Masayuki Kaneda, Tadashi Mori, Takehiko Wada, Yoshihisa Inoue

IMRAM - Division of Organic- and Biomaterials Research

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

20 Citations (Scopus)

Abstract

Inherently chiral molecular clips (MCs). pseudoenantiomeric anti-1 and anti-2, as well as mesoid syn-3, were synthesized by diastereodifferentiating repetitive Diels-Alder reactions of the achiral bisdienophile 6 with chiral diene 5 generated in situ from (-)-menthyl 3,4-bis(dibromomethyl)-benzoate 4. These MCs were success fully separated by chiral HPLC to give optically active anti-1 and anti-2 and almost optically inactive syn-3. The structures of anti-1, anti-2, and syn-3 were assigned by high-resolution NMR and the absolute configurations of anti1 and anti-2 were determined by the exciton-chirality method. Optically active anti-2 can serve as a chiral host. It binds the HCl adduct of D-tryptophan methyl ester (D-TrpOMe·HCl) 3.5 times stronger than the i.-enantiomer (K_D/K_L = 3.5).

Original language	English
Pages (from-to)	2473-2479
Number of pages	7
Journal	Chemistry - A European Journal
Volume	13
Issue number	9
DOIs	https://doi.org/10.1002/chem.200601585
Publication status	Published - 2007

Keywords

Chirality
Circular dichroism
Exciton coupling
Host-guest systems
Molecular clips

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10.1002/chem.200601585

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@article{25e2ba3448764f18b7b7d0631ba0c896,

title = "Inherently chiral molecular clips: Synthesis, chiroptical properties, and application to chiral discrimination",

abstract = "Inherently chiral molecular clips (MCs). pseudoenantiomeric anti-1 and anti-2, as well as mesoid syn-3, were synthesized by diastereodifferentiating repetitive Diels-Alder reactions of the achiral bisdienophile 6 with chiral diene 5 generated in situ from (-)-menthyl 3,4-bis(dibromomethyl)-benzoate 4. These MCs were success fully separated by chiral HPLC to give optically active anti-1 and anti-2 and almost optically inactive syn-3. The structures of anti-1, anti-2, and syn-3 were assigned by high-resolution NMR and the absolute configurations of anti1 and anti-2 were determined by the exciton-chirality method. Optically active anti-2 can serve as a chiral host. It binds the HCl adduct of D-tryptophan methyl ester (D-TrpOMe·HCl) 3.5 times stronger than the i.-enantiomer (KD/KL = 3.5).",

keywords = "Chirality, Circular dichroism, Exciton coupling, Host-guest systems, Molecular clips",

author = "Gaku Fukuhara and S{\"u}reyya Madenci and Jolanta Polkowska and Frank Bastkowski and Kl{\"a}rner, {Frank Gerrit} and Yumi Origane and Masayuki Kaneda and Tadashi Mori and Takehiko Wada and Yoshihisa Inoue",

note = "Funding Information: This work was supported by NSF grant ECS-8352220, tthhee IIBBMM FFaaccuullttyy DDeevveellooppmmeenntt AAwwaarrdd PPrrooggrraamm aanndd aann AATT &&TT Bell Laboratories PPhhDD SScchhoollaarrsshhiipp.. Funding Information: This work was supported by NSF grant ECS-8352220, the IBM Faculty Development Award Program and an AT&T Bell Laboratories PhD Scholarship.",

year = "2007",

doi = "10.1002/chem.200601585",

language = "English",

volume = "13",

pages = "2473--2479",

journal = "Chemistry - A European Journal",

issn = "0947-6539",

publisher = "Wiley-VCH Verlag",

number = "9",

}

TY - JOUR

T1 - Inherently chiral molecular clips

T2 - Synthesis, chiroptical properties, and application to chiral discrimination

AU - Fukuhara, Gaku

AU - Madenci, Süreyya

AU - Polkowska, Jolanta

AU - Bastkowski, Frank

AU - Klärner, Frank Gerrit

AU - Origane, Yumi

AU - Kaneda, Masayuki

AU - Mori, Tadashi

AU - Wada, Takehiko

AU - Inoue, Yoshihisa

N1 - Funding Information: This work was supported by NSF grant ECS-8352220, tthhee IIBBMM FFaaccuullttyy DDeevveellooppmmeenntt AAwwaarrdd PPrrooggrraamm aanndd aann AATT &&TT Bell Laboratories PPhhDD SScchhoollaarrsshhiipp.. Funding Information: This work was supported by NSF grant ECS-8352220, the IBM Faculty Development Award Program and an AT&T Bell Laboratories PhD Scholarship.

PY - 2007

Y1 - 2007

N2 - Inherently chiral molecular clips (MCs). pseudoenantiomeric anti-1 and anti-2, as well as mesoid syn-3, were synthesized by diastereodifferentiating repetitive Diels-Alder reactions of the achiral bisdienophile 6 with chiral diene 5 generated in situ from (-)-menthyl 3,4-bis(dibromomethyl)-benzoate 4. These MCs were success fully separated by chiral HPLC to give optically active anti-1 and anti-2 and almost optically inactive syn-3. The structures of anti-1, anti-2, and syn-3 were assigned by high-resolution NMR and the absolute configurations of anti1 and anti-2 were determined by the exciton-chirality method. Optically active anti-2 can serve as a chiral host. It binds the HCl adduct of D-tryptophan methyl ester (D-TrpOMe·HCl) 3.5 times stronger than the i.-enantiomer (KD/KL = 3.5).

AB - Inherently chiral molecular clips (MCs). pseudoenantiomeric anti-1 and anti-2, as well as mesoid syn-3, were synthesized by diastereodifferentiating repetitive Diels-Alder reactions of the achiral bisdienophile 6 with chiral diene 5 generated in situ from (-)-menthyl 3,4-bis(dibromomethyl)-benzoate 4. These MCs were success fully separated by chiral HPLC to give optically active anti-1 and anti-2 and almost optically inactive syn-3. The structures of anti-1, anti-2, and syn-3 were assigned by high-resolution NMR and the absolute configurations of anti1 and anti-2 were determined by the exciton-chirality method. Optically active anti-2 can serve as a chiral host. It binds the HCl adduct of D-tryptophan methyl ester (D-TrpOMe·HCl) 3.5 times stronger than the i.-enantiomer (KD/KL = 3.5).

KW - Chirality

KW - Circular dichroism

KW - Exciton coupling

KW - Host-guest systems

KW - Molecular clips

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JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 9

ER -

Inherently chiral molecular clips: Synthesis, chiroptical properties, and application to chiral discrimination

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Keywords

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