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- Title
Secondary Orbital Effect Involving Fluorine is Responsible for Substrate‐Controlled Diastereodivergence in the Catalyzed syn‐aza‐Henry Reaction of α‐Fluoronitroalkanes.
- Authors
Smajlagic, Ivor; Johnston, Jeffrey N.; Dudding, Travis
- Abstract
The fluorine atom is a powerful, yet enigmatic influence on chemical reactions. True to form, fluorine was recently discovered to effect diastereodivergence in an enantioselective aza‐Henry reaction, resulting in a very rare case of syn‐β‐amino nitroalkane products. More bewildering was the observation of an apparent hierarchy of substituents within this substrate‐controlled behavior: Ph>F>alkyl. These cases have now been examined comprehensively by computational methods, including both non‐fluorinated and α‐fluoro nitronate additions to aldimines catalyzed by a chiral bis(amidine) [BAM] proton complex. This study revealed the network of non‐covalent interactions that dictate anti‐ (α‐aryl) versus syn‐selectivity (α‐alkyl) using α‐fluoronitronate nucleophiles, and an underlying secondary orbital interaction between fluorine and the activated azomethine.
- Subjects
ALDIMINES; FLUORINE; ORBITAL interaction; CHEMICAL reactions; SCHIFF bases; NITROALDOL reactions; NUCLEOPHILES
- Publication
Chemistry - A European Journal, 2023, Vol 29, Issue 24, p1
- ISSN
0947-6539
- Publication type
Article
- DOI
10.1002/chem.202204066