Synthetic Applications and Inversion Dynamics of Configurationally Stable 2-Lithio-2-arylpyrrolidines and -piperidines

by Beng, T. K.; Woo, J. S.; Gawley, R. E.

In diethyl ether, N-Boc-2-lithio-2-arylpiperidines have been found to be configurationally stable at -80 degrees C, whereas N-Boc-2-lithio-2-arylpyrrolidines are configurationally stable at -60 degrees C. Several tertiary benzylic carbanions derived from enantioenriched 2-aryl heterocycles have been successfully alkylated or acylated with little to no loss of enantiopurity. The scope of the reactions has been explored. The enantiomerization dynamics of N-Boc-2-lithio-2-phenylpyrrolidine and N-Boc-2-lithio-2-phenylpiperidine have been studied in the presence of different solvents and achiral ligands.

Journal
Journal of the American Chemical Society
Volume
134
Issue
36
Year
2012
Start Page
14764-14771
URL
https://dx.doi.org/10.1021/ja306276w
ISBN/ISSN
1520-5126; 0002-7863
DOI
10.1021/ja306276w