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Highly Enantio‐ and Diastereoselective Catalytic Asymmetric Tamura Cycloaddition Reactions
Author(s) -
Collar Aarón Gutiérrez,
Trujillo Cristina,
Con Stephen J.
Publication year - 2019
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/chem.201900119
Subject(s) - cycloaddition , bifunctional , catalysis , chemistry , combinatorial chemistry , enantioselective synthesis , catalytic cycle , computational chemistry , organic chemistry
The first broad‐scope catalytic asymmetric Tamura cycloaddition reactions are reported. Under the influence of anion‐binding bifunctional catalysis a wide range of α,β‐unsaturated N ‐trityl imines undergo reactions with enolisable anhydrides to form highly synthetically useful α‐tetralone structures with excellent enantio‐ and ‐diastereocontrol. In stark contrast to the previous literature benchmarks, doubly activated or highly electron deficient alkenes are not required. A facile two‐step, high yielding sequence can convert the cycloadducts to α‐haloketones (challenging to generate catalytically by other means) with the net formation of two new C−C bonds and three new contiguous stereocentres with exquisite stereocontrol. A DFT study has provided insight into the catalyst mode of action and the origins of the observed enantiocontrol.