Enantioselective synthesis mediated by chiral crystal of achiral hippuric acid in conjunction with asymmetric autocatalysis

Kawasaki, Tsuneomi; Suzuki, Kenta; Hatase, Kunihiko; Otsuka, Masanari; Koshima, Hideko; Soai, Kenso

doi:10.1039/b602442d

Cited by 60 publications

(28 citation statements)

References 47 publications

(3 reference statements)

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“…On the other hand, we continue to study asymmetric autocatalysis (Soai et al 1995(Soai et al , 2001Shibata et al 1999;Soai and Kawasaki 2006Bolm et al 1996;Avalos et al 2000;Todd 2002;Blackmond 2004;Podlech and Gehring 2005;Mikami and Yamanaka 2003;Caglioti et al 2005;Gridnev 2006) mediated by chiral crystals composed of achiral compounds (Kawasaki et al 2005a(Kawasaki et al , 2006a(Kawasaki et al , 2008a. Chirality in the crystalline state can act as the source of chirality in the addition reaction of dialkylzinc and achiral aldehyde to give a highly enantioenriched product in combination with asymmetric autocatalytic amplification of enantiomeric excess (ee) (Sato et al 2003a).…”

Section: Introductionmentioning

confidence: 95%

Asymmetric Autocatalysis Induced by Chiral Crystals of Achiral Tetraphenylethylenes

Kawasaki

Nakaoda

Kaito

et al. 2009

Orig Life Evol Biosph

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The achiral hydrocarbon tetraphenylethylene crystallizes in enantiomorphous forms (chiral space group: P2(1)) to afford right- and left-handed hemihedral crystals, which can be recognized by solid-state circular dichroism spectroscopic analysis. Chiral organic crystals of tetraphenylethylene mediated enantioselective addition of diisopropylzinc to pyrimidine-5-carbaldehyde to give, in conjunction with asymmetric autocatalysis with amplification of chirality, almost enantiomerically pure (S)- and (R)-5-pyrimidyl alkanols whose absolute configurations were controlled efficiently by the crystalline chirality of the tetraphenylethylene substrate. Tetrakis(p-chlorophenyl)ethylene and tetrakis(p-bromophenyl)ethylene also show chirality in the crystalline state, which can also act as a chiral substrate and induce enantioselectivity of diisopropylzinc addition to pyrimidine-5-carbaldehyde in asymmetric autocatalysis to give enantiomerically enriched 5-pyrimidyl alkanols with the absolute configuration correlated with that of the chiral crystals. Highly enantioselective synthesis has been achieved using chiral crystals composed of achiral hydrocarbons, tetraphenylethylenes, as chiral inducers. This chemical system enables significant amplification of the amount of chirality using spontaneously formed chiral crystals of achiral organic compounds as the seed for the chirality of asymmetric autocatalysis.

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Section: Introductionmentioning

confidence: 95%

Asymmetric Autocatalysis Induced by Chiral Crystals of Achiral Tetraphenylethylenes

Kawasaki

Nakaoda

Kaito

et al. 2009

Orig Life Evol Biosph

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“…[CD(À)310nujol]-Cytosine crystal with the opposite chirality induced the production of enantioenriched (S)-alkanol 22. Enantiomorphous crystals of the achiral quaternary ammonium salt tryptamine/p-chlorobenzoic acid [101], hippuric acid [106] and benzil [107] trigger asymmetric autocatalysis.…”

Section: Asymmetric Autocatalysis With Amplification Of Ee Initiated mentioning

confidence: 99%

Amplification of chirality as a pathway to biological homochirality

Kawasaki

Soai

2010

Journal of Fluorine Chemistry

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“…5,8,26,27 Five samples were prepared and measured under the same conditions to avoid artifacts. Solid-State ECD spectra were recorded on a Jasco J-810 spectropolarimeter.…”

Section: Spectra Measurementsmentioning

confidence: 99%

Circular Dichroism Spectroscopy Study of Crystalline‐to‐Amorphous Transformation in Chiral Platinum(II) Complexes

Zhang

Liu

et al. 2013

Chirality

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Two couples of enantiomeric platinum(II) complexes: Pt(L1a )Cl (1a), Pt(L1b )Cl (1b) and Pt(L1a )(C ≡ C - Ph) (2a), Pt(L1b )(C ≡ C - Ph) (2b) (L1a = (+)-1,3-di-(2-(4,5-pinene)pyridyl)benzene, L1b = (-)-1,3-di-(2-(4,5-pinene)pyridyl)benzene) were synthesized and characterized. Their absolute configurations were determined by single crystal X-ray diffraction and further verified by circular dichroism (CD) spectra (including electronic circular dichroism [ECD] and vibrational circular dichroism [VCD]). These complexes show interesting mechanoluminescence and/or vapoluminescence due to crystalline-to-amorphous transformation. The crystalline solids, grinding-induced amorphous powders, and vapor-induced amorphous powders of complexes 2a and 2b were comparatively investigated by solid-state ECD and VCD spectra. The transformation from crystalline solids to amorphous powders was accompanied by significant variances of the spectral feature in both ECD and VCD spectra.

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Enantioselective synthesis mediated by chiral crystal of achiral hippuric acid in conjunction with asymmetric autocatalysis

Abstract: Enantiomorphous crystals composed of achiral hippuric acid, i.e., naturally occurring N-benzoylglycine, have been used successfully as chiral inducers in enantioselective synthesis in combination with asymmetric autocatalysis to afford the product with extremely high enantiomeric excess.

Cited by 60 publications

References 47 publications

Asymmetric Autocatalysis Induced by Chiral Crystals of Achiral Tetraphenylethylenes

Asymmetric Autocatalysis Induced by Chiral Crystals of Achiral Tetraphenylethylenes

Amplification of chirality as a pathway to biological homochirality

Circular Dichroism Spectroscopy Study of Crystalline‐to‐Amorphous Transformation in Chiral Platinum(II) Complexes

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