Jump to main content
Jump to site search


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

Author affiliations

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

Back to tab navigation

Supplementary files

Article information


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

New J. Chem., 2020, Advance Article
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, Advance Article , DOI: 10.1039/C9NJ05166J

Social activity

Search articles by author

Spotlight

Advertisements