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Asymmetric Autocatalysis of Pyrimidyl Alkanol

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Book cover Inventing Reactions

Part of the book series: Topics in Organometallic Chemistry ((TOPORGAN,volume 44))

Abstract

We have discovered an asymmetric autocatalysis in the enantioselective addition of diisopropylzinc to pyrimidine-5-carbaldehyde, where the product, 5-pyrimidyl alkanol, acts as highly efficient asymmetric autocatalyst. Asymmetric autocatalysis proceeded quantitatively (>99%), affording itself as a near enantiomerically pure (>99.5% ee) product. An extremely low enantiomeric excess (ca. 0.00005% ee) can automultiply during three consecutive asymmetric autocatalysis to >99.5% ee. Circularly polarized light, quartz, chiral organic crystals, and statistical fluctuation of ee in racemate, which are considered a possible candidate for the origin of chirality, act as the chiral source in asymmetric autocatalysis. Asymmetric autocatalysis has the enormous power to recognize the isotope chirality arising from the small difference between carbon (carbon-13/carbon-12) and hydrogen (D/H) isotopes.

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Abbreviations

BDL:

Below the detectable level

Bu:

Butyl

CD:

Circular dichroism

CPL:

Circularly polarized light

DAIB:

3-Exo-(dimethylamino) isoborneol

DMNE:

N,N-dimethylnorephedrine

DPMPM:

Diphenyl(1-methylpyrrolidin-2-yl)methanol

ee:

Enantiomeric excess

Et:

Ethyl

i :

Iso

l :

Left-handed

n :

Normal

PEAE:

2-[(1-phenylethyl)amino]-ethanol

Pr:

Propyl

R :

Rectus

r :

Right-handed

S :

Sinister

t :

Tertiary

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Authors and Affiliations

  1. Department of Applied Chemistry and Research Institute for Science & Technology, Tokyo University of Science, Kagurazaka, Shinjuku-ku, Tokyo, 162-8601, Japan

    Kenso Soai & Tsuneomi Kawasaki

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  1. Kenso Soai
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  2. Tsuneomi Kawasaki
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Correspondence to Kenso Soai .

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Editors and Affiliations

  1. , FB Chemie - Organische Chemie, TU Kaiserslautern, Erwin-Schrödinger-Str. 54, Kaiserslautern, 67663, Germany

    Lukas J. Gooßen

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Soai, K., Kawasaki, T. (2012). Asymmetric Autocatalysis of Pyrimidyl Alkanol. In: Gooßen, L. (eds) Inventing Reactions. Topics in Organometallic Chemistry, vol 44. Springer, Berlin, Heidelberg. https://doi.org/10.1007/3418_2012_48

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