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Issue 8, 2020
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Changing stereoselectivity and regioselectivity in copper(i)-catalyzed 5-exo cyclization by chelation and rigidity in aminoalkyl radicals: synthesis towards diverse bioactive N-heterocycles

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Abstract

The work reveals that a chelate-type interaction in the transition state of a β-aminoalkyl radical in a copper(I)-catalyzed 5-exo-trig radical cyclization step changes the usual stereochemistry of the NH-pyrrolidine ring predicted by the Beckwith–Houk transition state model. In contrast, the rigidity in the fused β-aminoalkyl radical changes the Baldwin's predicted 5-exo to 6-endo cyclization mode, preferentially forming a piperidine ring over a pyrrolidine ring via a geometrically constrained transition state. The resultant diverse NH-pyrrolidines, pyrrolines and piperidines are sources of the bioactive natural product roseophilin and the drug Ritalin among others.

Graphical abstract: Changing stereoselectivity and regioselectivity in copper(i)-catalyzed 5-exo cyclization by chelation and rigidity in aminoalkyl radicals: synthesis towards diverse bioactive N-heterocycles

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Article information


Submitted
13 Oct 2019
Accepted
22 Jan 2020
First published
23 Jan 2020

New J. Chem., 2020,44, 3350-3365
Article type
Paper

Changing stereoselectivity and regioselectivity in copper(I)-catalyzed 5-exo cyclization by chelation and rigidity in aminoalkyl radicals: synthesis towards diverse bioactive N-heterocycles

S. Sadanandan and D. K. Gupta, New J. Chem., 2020, 44, 3350
DOI: 10.1039/C9NJ05166J

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