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A Structure‐Reactivity Relationship of the Tandem Asymmetric Dihydroxylation on a Biologically Relevant Diene: Influence of Remote Stereocenters on Diastereofacial Selectivity.
- Source :
-
European Journal of Organic Chemistry . 12/15/2019, Vol. 2019 Issue 46, p7568-7577. 10p. - Publication Year :
- 2019
-
Abstract
- The Sharpless asymmetric dihydroxylation (AD) finds widespread use in natural product and drug molecule syntheses, in part, due to its efficiency and predictability. However, the tandem AD of dienes is much less studied, but important in complex molecular synthesis. Herein, a biologically relevant tandem AD is reported, and several anomalies are discovered with the accepted model. These include the formation of unpredicted diastereoisomers, with matched and mismatched stereocenters contradicting the Sharpless mnemonic device. From a structural analysis of the tandem AD, we present a strategy to improve asymmetric induction in sterically hindered alkenes using double diastereodifferentiation from a 9‐bond distant stereocenter. A theoretical justification for the unpredicted stereoselectivity, accounting for the influence of steric hindrance and pre‐installed chirality, is proposed. [ABSTRACT FROM AUTHOR]
Details
- Language :
- English
- ISSN :
- 1434193X
- Volume :
- 2019
- Issue :
- 46
- Database :
- Academic Search Index
- Journal :
- European Journal of Organic Chemistry
- Publication Type :
- Academic Journal
- Accession number :
- 140846090
- Full Text :
- https://doi.org/10.1002/ejoc.201901474