A new class of Fe(II)4L4 capsules, based upon a tritopic trialdehyde subcomponent, is reported. One such capsule was prepared diastereoselectively through the incorporation of a chiral amine residue. This amine was displaced by an achiral one, while maintaining the stereochemistry of the cage framework (99% ee); this cage retained its stereochemistry even after 4 days at 90 °C. Mechanistic studies indicate the memory displayed by this capsule to be the result of effective stereochemical communication between the metal centers mediated by the rigid 3-fold-symmetric faces, in combination with a stepwise substitution mechanism.
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http://dx.doi.org/10.1021/ja410117q | DOI Listing |
Acc Chem Res
November 2023
Department of Chemistry, University of California, Irvine, California 92697, United States.
ConspectusNickel-catalyzed reactions of alkyl alcohol derivatives leverage the high prevalence of hydroxyl groups in natural products, medicinal agents, and synthetic intermediates to provide access to C(sp)-rich frameworks. This Account describes our laboratory's development of stereospecific and stereoconvergent C-C bond forming reactions employing C(sp)-O and C(sp)-N electrophiles. In the context of development of new transformations, we also define fundamental characteristics of the nickel catalysts.
View Article and Find Full Text PDFChemistry
December 2021
Max-Planck-Institut für Kohlenforschung, 45470, Mülheim an der RuhrMülheim/Ruhr, Germany.
Alkynyl-B(aam) (aam=anthranilamidato) derivatives are readily available bench-stable compounds that undergo remarkably selective reactions with Bu SnH in the presence of [Cp*RuCl] as the catalyst. The addition follows a stereochemically unorthodox trans-selective course; in terms of regioselectivity, the Bu Sn- unit is delivered with high fidelity to the C-atom of the triple bond adjacent to the boracyclic head group ("alpha,trans-addition"). This outcome is deemed to reflect a hydrogen bonding interaction between the protic -NH groups of the benzo-1,3,2-diazaborininone ring system and the polarized [Ru-Cl] bond in the loaded catalyst, which locks the substrate in place in a favorable orientation relative to the incoming reagent.
View Article and Find Full Text PDFNat Commun
June 2020
School of Chemistry, University of Birmingham, Edgbaston, Birmingham, B15 2TT, UK.
Biocompatible polymers are widely used in tissue engineering and biomedical device applications. However, few biomaterials are suitable for use as long-term implants and these examples usually possess limited property scope, can be difficult to process, and are non-responsive to external stimuli. Here, we report a class of easily processable polyamides with stereocontrolled mechanical properties and high-fidelity shape memory behaviour.
View Article and Find Full Text PDFAnnu Rev Genet
November 2017
Department of Mathematics, North Dakota State University, Fargo, North Dakota 58108, USA.
The standard genetic code (SGC) is virtually universal among extant life forms. Although many deviations from the universal code exist, particularly in organelles and prokaryotes with small genomes, they are limited in scope and obviously secondary. The universality of the code likely results from the combination of a frozen accident, i.
View Article and Find Full Text PDFLife (Basel)
May 2017
National Center for Biotechnology Information, National Library of Medicine, National Institutes of Health, Bethesda, MD 20894, USA.
Nearly 50 years ago, Francis Crick propounded the frozen accident scenario for the evolution of the genetic code along with the hypothesis that the early translation system consisted primarily of RNA. Under the frozen accident perspective, the code is universal among modern life forms because any change in codon assignment would be highly deleterious. The frozen accident can be considered the default theory of code evolution because it does not imply any specific interactions between amino acids and the cognate codons or anticodons, or any particular properties of the code.
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