Abstract
Controlling chiral recognition and chiral information transfer has major implications in areas ranging from drug design and asymmetric catalysis to supra- and macromolecular chemistry. Especially intriguing are phenomena associated with chiral self-recognition. The design of systems that show self-induced recognition of enantiomers, i.e., involving homochiral versus heterochiral dimers, is particularly challenging. Here, we report the chiral self-recognition of α-ureidophosphonates and its application as both a powerful analytical tool for enantiomeric ratio determination by NMR and as a convenient way to increase their enantiomeric purity by simple achiral column chromatography or fractional precipitation. A combination of NMR, X-ray, and DFT studies indicates that the formation of homo- and heterochiral dimers involving self-complementary intermolecular hydrogen bonds is responsible for their self-resolving properties. It is also shown that these often unnoticed chiral recognition phenomena can facilitate the stereochemical analysis during the development of new asymmetric transformations. As a proof of concept, the enantioselective organocatalytic hydrophosphonylation of alkylidene ureas toward self-resolving α-ureidophosphonates is presented, which also led us to the discovery of the largest family of self-resolving compounds reported to date.
Original language | English |
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Pages (from-to) | 23603-23613 |
Number of pages | 11 |
Journal | J. Am. Chem. Soc. |
Volume | 144 |
Issue number | 51 |
DOIs | |
Publication status | Published - 28-Dec-2022 |
Datasets
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CCDC 2193600: Experimental Crystal Structure Determination
Dašková, V. (Contributor), Padín, D. (Contributor) & Feringa, B. L. (Contributor), Cambridge Crystallographic Data Centre, 29-Jul-2022
DOI: 10.5517/ccdc.csd.cc2cmm9y, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc2cmm9y&sid=DataCite
Dataset