ChemRxiv
These are preliminary reports that have not been peer-reviewed. They should not be regarded as conclusive, guide clinical practice/health-related behavior, or be reported in news media as established information. For more information, please see our FAQs.
1/1
2 files

Catalyst-Control over Sixfold Stereogenicity

preprint
submitted on 29.04.2020, 11:12 and posted on 30.04.2020, 06:24 by Xingxing Wu, Reto M. Witzig, Rodolphe Beaud, Christian Fischer, Daniel Häussinger, Christof Sparr
Governing higher-order stereogenicity is a long-standing goal in stereoselective catalysis, because it allows to achieve selectivity for more than a twofold number of stereoisomers per stereogenic unit. Current methods warrant control over the power of two stereoisomers and the configurations are routinely assigned using the descriptors ( R ) and ( S ), or related binary codes. In contrast, conformational analysis ranges beyond this dualistic treatment of stereoisomerism, which constitutes an unmet challenge for catalyst stereocontrolled processes. Herein, we now report that sixfold stereogenicity can be governed by stereoselective catalysis. By controlling a configurationally stable stereogenic axis with six large rotational barriers, a catalytic [2+2+2]-cyclotrimerization selectively governs the formation of one out of six stereoisomers with up to 0:0:2:98:0:0 stereocontrol. The underpinnings of conformational analysis and stereoselective catalysis are thereby conceptually reunited. Novel molecular architectures featuring distinct chemical topologies and unexplored chemical designs are anticipated from catalystcontrol over higher-order stereogenicities

Funding

Stereoselective, Catalytic Annulation Methods to Create Structurally Well-Defined Scaffolds

Swiss National Science Foundation

Find out more...

NCCR MSE: Molecular Systems Engineering (phase II)

Swiss National Science Foundation

Find out more...

University of Basel

History

Email Address of Submitting Author

christof.sparr@unibas.ch

Institution

University of Basel

Country

Switzerland

ORCID For Submitting Author

0000-0002-4213-0941

Declaration of Conflict of Interest

The authors declare no conflict of interests

Version Notes

First Version

Exports