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Organocatalytic Enantioselective Higher‐Order Cycloadditions of In Situ Generated Amino Isobenzofulvenes
Author(s) -
Donslund Bjarke S.,
Monleón Alicia,
Palazzo Teresa A.,
Christensen Mette Louise,
Dahlgaard Anne,
Erickson Jeremy D.,
Jørgensen Karl Anker
Publication year - 2018
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201710694
Subject(s) - enantioselective synthesis , cycloaddition , chemistry , indene , catalysis , in situ , organocatalysis , stereochemistry , in silico , combinatorial chemistry , medicinal chemistry , organic chemistry , biochemistry , gene
The [8+2] cycloaddition of indene‐2‐carbaldehydes and nitro olefins is described to provide benzonorbornene scaffolds in a highly peri‐, diastereo‐, and enantioselective fashion in the presence of a C 2 ‐symmetric aminocatalyst. This reaction, which proceeds through a transient semi‐aromatic amino isobenzofulvene, represents the first example of catalytic formation and transformation of these species. Quantum chemical calculations suggest a kinetically controlled stepwise mechanism where the stereochemistry is determined in the first bond‐forming event. Beyond the useful [8+2] cycloadducts, [10+4] cycloadducts have been identified in silico as potential off‐pathway intermediates.