The S_N2 Reaction in the Solid State. An Unusual, B_Al2 Aminolysis of an Ester Group in Crystalline (±)-2-Amino-2‘-hydroxy-3‘-(methoxycarbonyl)- 1,1‘-binaphthyl Elucidated by X-ray Diffraction and Isotopic Labeling. New Experimental Evidence for Linearity in S_N2 Substitution

Reactivity Controlled by Lattice Interactions in Crystal: Intermolecular Acyl Transfer in (±)-2,4-Di-O-benzoyl-myo-inositol 1,3,5-Orthoformate

“…There are only a few known examples of intermolecular reaction (usually methyl transfer) brought about in the crystalline state . The reaction reported here involves the substrate 1 and the catalyst (Na 2 CO 3 ) in two solid phases.…”

“…However, most of the intermolecular reactions studied in the solid state involved the dimerization of olefinic bonds, mainly because of the higher chances of observing the proper orientations of the double bonds by stacking of the molecule . Other types of reactions involving different chemical entities are only rarely encounteredweak interactions between the prospective reacting functional groups become overwhelmed by numerous other interactions (like hydrogen bonding) in the crystal lattice positioning them away from each other. Herein, we report on a solid-state reaction that proceeds through the nucleophilic addition of a hydroxyl group to a carbonyl group and show how the proper juxtaposition of the two groups leads to a reaction in one system, whereas the absence of such an orientation prevents the reaction from taking place in another system which, nevertheless, was expected to show a greater reactivity …”

When the Solvent Locks the Cage: Theoretical Insight into the Transmetalation of MOF-5 Lattices and Its Kinetic Limitations

“…Overall, the dissociative route follows an S N 2-type mechanism, a process not unprecedented in a solid state. 41 In this particular case, it occurs with inversion of configuration at the metal core, generating a torque on the nearby organic linkers that breaks the planarity of the BDC linkers by twisting the carboxylates. This stress propagates to the other cores and can ease the transmetalation of the nearby centers.…”

Non-Symmetrically Substituted 1,1‘-Binaphthyls in Enantioselective Catalysis

“…Finally, an interesting rearrangement was reported for the NOBIN derivative 18 (Scheme ), prepared by the Cu(II)-mediated coupling of 2-aminonaphthalene with 3-methoxycarbonyl-2-naphthol. Heating of (±)- 18 in the solid state triggers B AL 2 intermolecular migration of the ester CH 3 group to nitrogen, giving methylamino acid (±)- 139 . This rearrangement represents the first example of a B AL 2 reaction in the solid state.…”