Stereochemical editing logic powered by the epimerization of unactivated tertiary stereocenters

The stereoselective synthesis of complex targets requires the precise orchestration of chemical transformations that simultaneously establish the connectivity and spatial orientation of desired bonds. In this work, we describe a complementary paradigm for the synthesis of chiral molecules and their...

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Bibliographic Details
Published in:Science (American Association for the Advancement of Science) 2022-10, Vol.378 (6618), p.383-390
Main Authors: Zhang, Yu-An, Palani, Vignesh, Seim, Alexander E, Wang, Yong, Wang, Kathleen J, Wendlandt, Alison E
Format: Article
Language:English
Subjects:
Bonding agents
Carbon
Chemical bonds
Configurations
Diastereoisomers
Hydrogen
Hydrogen bonding
Hydrogen bonds
Tungsten
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Summary:The stereoselective synthesis of complex targets requires the precise orchestration of chemical transformations that simultaneously establish the connectivity and spatial orientation of desired bonds. In this work, we describe a complementary paradigm for the synthesis of chiral molecules and their isomers, which tunes the three-dimensional structure of a molecule at a late stage. Key to the success of this strategy is the development of a mild and highly general photocatalytic method composed of decatungstate polyanion and disulfide cocatalysts, which enable the interconversion of unactivated tertiary stereogenic centers that were previously configurationally fixed. We showcase the versatility of this method-and the implementation of stereoediting logic-by the rapid construction of chiral scaffolds that would be challenging to access using existing tools and by the late-stage stereoediting of complex targets.
ISSN:0036-8075
1095-9203
DOI:10.1126/science.add6852