Diastereoselectivity of polar and radical couplings in electrophilic substitutions of rigid 2-lithio-N-methylpyrrolidines

by Gawley, R. E.; Eddings, D. B.; Santiago, M.; Vicic, D. A.

N-Methyl trans-fused perhydroisoindolines substituted with a tributylstannyl group in the 2-position have been prepared and used as precursors of the corresponding alpha-aminoorganolithiums. The steric course of the reactions of these and other conformationally rigid organolithiums with various electrophiles is summarized and compared with the steric course of the unsubstituted analogs. A mechanistic rationale for the steric course of electrophilic substitutions of these organolithiums is discussed. Pathways involving both polar electrophilic substitutions and radical couplings were observed with different electrophiles.

Journal
Organic and Biomolecular Chemistry
Volume
4
Issue
23
Year
2006
Start Page
4285-4291
URL
https://dx.doi.org/10.1039/b608013h
ISBN/ISSN
1477-0539; 1477-0520
DOI
10.1039/b608013h