Reversal of Stereoselectivity in Cycloadditions of
Five-Membered Cyclic Nitrones Derived from Hexoses

J 2017

Reversal of Stereoselectivity in Cycloadditions of Five-Membered Cyclic Nitrones Derived from Hexoses

MALATINSKY, T., M. SPISAKOVA, M. BABJAK, J. DOHANOSOVA, Jaromír MAREK et. al.

Basic information

Original name

Reversal of Stereoselectivity in Cycloadditions of Five-Membered Cyclic Nitrones Derived from Hexoses

Authors

MALATINSKY, T. (703 Slovakia), M. SPISAKOVA (703 Slovakia), M. BABJAK (703 Slovakia), J. DOHANOSOVA (703 Slovakia), Jaromír MAREK (203 Czech Republic, guarantor, belonging to the institution), J. MONCOL (703 Slovakia) and R. FISCHER (703 Slovakia)

Edition

European Journal of Organic Chemistry, Weinheim, WILEY-VCH, 2017, 1434-193X

Other information

Language

English

Type of outcome

Článek v odborném periodiku

Field of Study

10401 Organic chemistry

Country of publisher

Germany

Confidentiality degree

není předmětem státního či obchodního tajemství

References:

URL

Impact factor

Impact factor: 2.882

RIV identification code

RIV/00216224:14740/17:00100421

Organization unit

Central European Institute of Technology

DOI

http://dx.doi.org/10.1002/ejoc.201601488

UT WoS

000394901700008

Keywords in English

Heterocycles; Nitrones; Carbohydrates; Cycloaddition; Diastereoselectivity

Abstract

V originále

Two five-membered cyclic nitrones derived from hexoses, a newly synthesized D-allo-configured nitrone and an already known D-talo-configured nitrone, have been examined in 1,3-dipolar cycloaddition reactions with vinyl acetate, allyl benzoate, methyl acrylate, acrylonitrile, and vinylene carbonate. The reactions of the D-allo-configured nitrone proceeded preferentially through the expected exo-anti transition state, but all the cycloadditions of the D-talo-configured nitrone surprisingly showed high exo-syn selectivity. This reversal of stereoselectivity has been explained by 3D analysis of the preferred conformations of the nitrones, obtained from X-ray data. The structures were further inspected using CONFLEX, PM5, and DFT calculations. All these methods revealed that the dioxolane substituents attached to C-5 of both nitrones had opposite spatial locations.

Links

LM2015043, research and development project

Name: Česká infrastruktura pro integrativní strukturní biologii (Acronym: CIISB)

Investor: Ministry of Education, Youth and Sports of the CR

Citovat

MALATINSKY, T., M. SPISAKOVA, M. BABJAK, J. DOHANOSOVA, Jaromír MAREK, J. MONCOL and R. FISCHER. Reversal of Stereoselectivity in Cycloadditions of Five-Membered Cyclic Nitrones Derived from Hexoses. European Journal of Organic Chemistry. Weinheim: WILEY-VCH, 2017, vol. 2018, No 6, p. 1086-1098. ISSN 1434-193X. Available from: https://dx.doi.org/10.1002/ejoc.201601488.

@article{1411802,
   author = {Malatinsky, T. and Spisakova, M. and Babjak, M. and Dohanosova, J. and Marek, Jaromír and Moncol, J. and Fischer, R.},
   article_location = {Weinheim},
   article_number = {6},
   doi = {http://dx.doi.org/10.1002/ejoc.201601488},
   keywords = {Heterocycles; Nitrones; Carbohydrates; Cycloaddition; Diastereoselectivity},
   language = {eng},
   issn = {1434-193X},
   journal = {European Journal of Organic Chemistry},
   title = {Reversal of Stereoselectivity in Cycloadditions of Five-Membered Cyclic Nitrones Derived from Hexoses},
   url = {https://onlinelibrary.wiley.com/doi/epdf/10.1002/ejoc.201601488},
   volume = {2018},
   year = {2017}
}

TY  - JOUR
ID  - 1411802
AU  - Malatinsky, T. - Spisakova, M. - Babjak, M. - Dohanosova, J. - Marek, Jaromír - Moncol, J. - Fischer, R.
PY  - 2017
TI  - Reversal of Stereoselectivity in Cycloadditions of Five-Membered Cyclic Nitrones Derived from Hexoses
JF  - European Journal of Organic Chemistry
VL  - 2018
IS  - 6
SP  - 1086-1098
EP  - 1086-1098
PB  - WILEY-VCH
SN  - 1434193X
KW  - Heterocycles
KW  - Nitrones
KW  - Carbohydrates
KW  - Cycloaddition
KW  - Diastereoselectivity
UR  - https://onlinelibrary.wiley.com/doi/epdf/10.1002/ejoc.201601488
N2  - Two five-membered cyclic nitrones derived from hexoses, a newly synthesized D-allo-configured nitrone and an already known D-talo-configured nitrone, have been examined in 1,3-dipolar cycloaddition reactions with vinyl acetate, allyl benzoate, methyl acrylate, acrylonitrile, and vinylene carbonate. The reactions of the D-allo-configured nitrone proceeded preferentially through the expected exo-anti transition state, but all the cycloadditions of the D-talo-configured nitrone surprisingly showed high exo-syn selectivity. This reversal of stereoselectivity has been explained by 3D analysis of the preferred conformations of the nitrones, obtained from X-ray data. The structures were further inspected using CONFLEX, PM5, and DFT calculations. All these methods revealed that the dioxolane substituents attached to C-5 of both nitrones had opposite spatial locations.
ER  -

MALATINSKY, T., M. SPISAKOVA, M. BABJAK, J. DOHANOSOVA, Jaromír MAREK, J. MONCOL and R. FISCHER. Reversal of Stereoselectivity in Cycloadditions of Five-Membered Cyclic Nitrones Derived from Hexoses. \textit{European Journal of Organic Chemistry}. Weinheim: WILEY-VCH, 2017, vol.~2018, No~6, p.~1086-1098. ISSN~1434-193X. Available from: https://dx.doi.org/10.1002/ejoc.201601488.

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