Unknown

Dataset Information

0

An investigation of the observed, but counter-intuitive, stereoselectivity noted during chiral amine synthesis via N-chiral-ketimines.


ABSTRACT: The default explanation for good to high diastereomeric excess when reducing N-chiral imines possessing only mediocre cis/trans-imine ratios (>15% cis-imine) has invariably been in situ cis-to-trans isomerization before reduction; but until now no study unequivocally supported this conclusion. The present study co-examines an alternative hypothesis, namely that some classes of cis-imines may hold conformations that erode the inherent facial bias of the chiral auxiliary, providing more of the trans-imine reduction product than would otherwise be expected. The ensuing experimental and computational (DFT) results favor the former, pre-existing, explanation.

SUBMITTER: Nugent TC 

PROVIDER: S-EPMC3817511 | biostudies-literature | 2013

REPOSITORIES: biostudies-literature

altmetric image

Publications

An investigation of the observed, but counter-intuitive, stereoselectivity noted during chiral amine synthesis via N-chiral-ketimines.

Nugent Thomas C TC   Williams Richard Vaughan RV   Dragan Andrei A   Méndez Alejandro Alvarado AA   Iosub Andrei V AV  

Beilstein journal of organic chemistry 20131015


The default explanation for good to high diastereomeric excess when reducing N-chiral imines possessing only mediocre cis/trans-imine ratios (>15% cis-imine) has invariably been in situ cis-to-trans isomerization before reduction; but until now no study unequivocally supported this conclusion. The present study co-examines an alternative hypothesis, namely that some classes of cis-imines may hold conformations that erode the inherent facial bias of the chiral auxiliary, providing more of the tra  ...[more]

Similar Datasets

| S-EPMC8179053 | biostudies-literature
| S-EPMC6053974 | biostudies-literature
| S-EPMC7479099 | biostudies-literature
| S-EPMC4497610 | biostudies-literature
| S-EPMC6517380 | biostudies-literature
| S-EPMC4947188 | biostudies-literature
| S-EPMC2862162 | biostudies-literature
| S-EPMC6719113 | biostudies-literature
| S-EPMC3005816 | biostudies-literature
| S-EPMC10661061 | biostudies-literature