A Ni-catalyzed borylation via C-F activation is described. This protocol is distinguished by a wide scope, including unactivated fluoroarenes, without compromising its efficiency and scalability, thus representing a significant step-forward towards the implementation of C-F activation protocols.Metal-catalyzed cross-coupling reactions of organic halides have become indispensable tools in modern synthetic chemistry.
Ligand conformational entropy plays an important role in carbohydrate recognition events. Glycans are characterized by intrinsic flexibility around the glycosidic linkages, thus in most cases, loss of conformational entropy of the sugar upon complex formation strongly affects the entropy of the binding process. By employing a multidisciplinary approach combining structural, conformational, binding energy, and kinetic information, we investigated the role of conformational entropy in the recognition of the histo blood‐group antigens A and B by human galectin‐3, a lectin of biomedical interest. We show that these rigid natural antigens are pre‐organized ligands for hGal‐3, and that restriction of the conformational flexibility by the branched fucose (Fuc) residue modulates the thermodynamics and kinetics of the binding process. These results highlight the importance of glycan flexibility and provide inspiration for the design of high‐affinity ligands as antagonists for lectins.
Switchable site-selectivity through catalyst control is achieved in the direct functionalization of picolinamides that contain two distinct C–H sites to construct diverse scaffolds from the same starting material.
We report on as witchable rotaxane molecular shuttle that features ap seudo-meso 2,5-disubstituted pyrrolidine catalytic unit on the axle whose local symmetry is broken according to the position of at hreaded benzylic amide macrocycle.T he macrocycle can be selectively switched (with light in one direction;with catalytic acid in the other) with high fidelity between binding sites located to either side of the pyrrolidine unit. The position of the macrocycle dictates the facial bias of the rotaxane-catalyzed conjugate addition of aldehydes to vinyl sulfones.The pseudo-meso non-interlocked thread does not afford significant selectivity as ac atalyst (2-14 %e e), whereas the rotaxane affords selectivities of up to 40 %e ew ith switching of the position of the macrocycle changing the handedness of the product formed (up to 60 % Dee).
We
report on the preparation of a decapeptide through the parallel
operation of two rotaxane-based molecular machines. The synthesis
proceeds in four stages: (1) simultaneous operation of two molecular
peptide synthesizers in the same reaction vessel; (2) selective residue
activation of short-oligomer intermediates; (3) ligation; (4) product
release. Key features of the machine design include the following:
(a) selective transformation of a thioproline building block to a
cysteine (once it has been incorporated into a hexapeptide intermediate
by one molecular machine); (b) a macrocycle-peptide hydrazine linkage
(as part of the second machine) to differentiate the intermediates
and enable their directional ligation; and (c) incorporation of a
Glu residue in the assembly module of one machine to enable release
of the final product while simultaneously removing part of the assembly
machinery from the product. The two molecular machines participate
in the synthesis of a product that is beyond the capability of individual
small-molecule machines, in a manner reminiscent of the ligation and
post-translational modification of proteins in biology.
We report on as witchable rotaxane molecular shuttle that features ap seudo-meso 2,5-disubstituted pyrrolidine catalytic unit on the axle whose local symmetry is broken according to the position of at hreaded benzylic amide macrocycle.T he macrocycle can be selectively switched (with light in one direction;with catalytic acid in the other) with high fidelity between binding sites located to either side of the pyrrolidine unit. The position of the macrocycle dictates the facial bias of the rotaxane-catalyzed conjugate addition of aldehydes to vinyl sulfones.The pseudo-meso non-interlocked thread does not afford significant selectivity as ac atalyst (2-14 %e e), whereas the rotaxane affords selectivities of up to 40 %e ew ith switching of the position of the macrocycle changing the handedness of the product formed (up to 60 % Dee).
Ligand conformational entropyp laysa ni mportant role in carbohydrate recognition events.G lycans are characterizedb yi ntrinsic flexibility around the glycosidic linkages, thus in most cases,loss of conformational entropyofthe sugar upon complex formation strongly affects the entropyo ft he binding process.B ye mployingamultidisciplinary approach combining structural, conformational, binding energy,a nd kinetic information, we investigated the role of conformational entropyinthe recognition of the histo blood-group antigens A and Bbyhuman galectin-3, alectin of biomedical interest. We show that these rigid natural antigens are pre-organized ligands for hGal-3, and that restriction of the conformational flexibility by the branched fucose (Fuc) residue modulates the thermodynamics and kinetics of the binding process.T hese results highlight the importance of glycan flexibility and provide inspiration for the design of high-affinity ligands as antagonists for lectins.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.org/10.
The Ni-catalyzed C(sp3)–C(sp3) cross-coupling of redox-active esters and organozinc reagents is used for the active template synthesis of ‘impossible’ rotaxanes.
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