Abstract
The first organocatalytic enantioselective radical polycyclization has been accomplished using singly occupied molecular orbital (SOMO) catalysis. The presented strategy relies on a selective single-electron oxidation of chiral enamines formed by condensation of polyenals with an imidazolidinone catalyst employing a suitable copper(II) oxidant. The reaction proceeds under mildly acidic conditions at room temperature and shows compatibility with an array of electron-poor as well as electron-rich functional groups. Upon termination by radical arylation followed by subsequent oxidation and rearomatization, a range of polycyclic aldehydes were accessed (12 examples, 54?77% yield, 85?93% ee). The enantioselective formation of up to six new carbocycles in a single catalyst-controlled cascade is described. Evidence for a radical-based cascade mechanism is indicated by a series of experimental results.
Original language | English (US) |
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Pages (from-to) | 5027-5029 |
Number of pages | 3 |
Journal | Journal of the American Chemical Society |
Volume | 132 |
Issue number | 14 |
DOIs | |
State | Published - Apr 14 2010 |
All Science Journal Classification (ASJC) codes
- General Chemistry
- Biochemistry
- Catalysis
- Colloid and Surface Chemistry