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Understanding Diastereofacial Selection in Carbohydrate‐Based Domino Cycloadditions: Semiempirical and DFT Calculations
Author(s) -
Avalos Martín,
Babiano Reyes,
Bravo José L.,
Cintas Pedro,
Jiménez José L.,
Palacios Juan C.,
Silva María A.
Publication year - 2000
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/(sici)1521-3765(20000117)6:2<267::aid-chem267>3.0.co;2-e
Subject(s) - chemistry , nitronate , hyperconjugation , computational chemistry , anomeric effect , cycloaddition , ab initio , transition state , alkene , ab initio quantum chemistry methods , density functional theory , substituent , stereochemistry , ether , anomer , organic chemistry , nitro , molecule , alkyl , catalysis
Valuable insights into the mechanism of acyclic stereoselection provided by carbohydrate‐based tethers of definite configuration have been obtained by means of semiempirical and ab inito calculations. An asymmetric version of the well‐established and versatile domino [4+2]/[3+2] cycloaddition of nitroalkanes with vinyl ethers has been studied as a model case. Transition structures (an example is illustrated here) can be used to predict the sterochemical outcome, and such results can also be extended to understand the facial selectivity of related nitrone‐alkene cycloadditions.