Chemo- and stereospecific solid-state dimerization of lithium trans-2-butenoate and lithium trans-2-butenoate formamide solvate

Chemo- and Stereospecific Solid-State Thermal Dimerization of Sodium trans-2-Butenoate and γ-Ray-Induced Single-Crystal-to-Single-Crystal Dimerization of Hexaaquamagnesium trans-2-Butenoate Dihydrate: Both Give rel-(3S,4R)-1-Hexene-3,4-dicarboxylate but by Different Mechanisms. Stereospecific γ-Ray-Induced Trimerization of Sodium trans-2-Butenoate

“…In the present work, we have discovered a sixth product that can be formed selectively by a γray-induced radical chain reaction of a crystalline alkali or alkaline earth trans-2-butenoate. 3,4 γ-Irradiation of crystalline hexaaquamagnesium trans-2-butenoate dihydrate (12) affords rel-(3S,4R)-1-hexene-3,4-dicarboxylate (2) by a single-crystalto-single-crystal reaction by anti addition to the butenoate double bond, as established by deuterium-labeling experiments. Naruchi reported that the same dicarboxylate 2 is formed by heating crystalline sodium trans-2-butenoate (1) at 300 °C, but this thermal ene reaction has now been shown by deuterium labeling to proceed by syn addition to the butenoate double bond as expected.…”

“…Preparation of Sodium trans-2-Butenoate-2-d (21). trans-2-Butenoic-2-d acid 4 (1.00 g, 12 mmol) was dissolved in 20 mL of water and sodium hydroxide (0.47 g, 12 mmol) was added. The reaction mixture was stirred at room temperature for 1 h and concentrated under reduced pressure to give a colorless solid that was washed with acetone to remove any excess acid and dried to give 1.2 g (96%) of 21 as a colorless solid, mp >220 °C.…”

“…Depending upon the structure of a given material and the observed short contacts, reactivity may occur either solely between molecules within one section (i.e., one-half) of a bilayer 3,23 or between molecules in the two sections of a bilayer. 4 Fourth, with a view to exploring solid-state reactivity of the trans-2-butenoate moiety, we found 147 structures of metal salts and complexes in the current version of the Cambridge Structural Database containing the trans-2-butenoate anion, including our own contributions. 29 We have surveyed many of these, and most do not contain arrangements suitable for γ-ray-induced reactivity.…”

“…The design and discovery of new classes of materials that undergo solid-state transformations to give products unavailable from solution chemistry and the elucidation of the principles that govern their reactivity remain important challenges in the field. − The use of ionizing radiation as an excitation source provides new synthetic opportunities distinct from thermal or photochemical stimuli. 60 Co γ-rays can initiate radical chain reactions in crystals that lead to products from alkenes very different from those obtained photochemically, such as the cyclobutane derivatives obtained by solid-state [2 + 2] photocycloadditions of cinnamates and other highly conjugated alkenes. − Nonetheless, the distance criterion of the topochemical postulate (C···C contacts ≤4.2 Å), first established by Schmidt and co-workers, , appears to hold well for radical chain reactions in the solid state. − 60 Co γ-ray initiated radical chain solid-state polymerization of solid metal acrylates was first discovered nearly 60 years ago. , Ionizing radiation also effectively initiates single-crystal-to-single-crystal solid-state polymerization of a wide range of diacetylenes and muconate esters. − Although 60 Co γ-ray irradiation of solid metal complexes of acrylates, methacrylates, propynoates, and other unsaturated carboxylates showed widespread reactivity, , the polymeric products were mostly amorphous and atactic, with a unique stereoregular example …”

Bridging photochemistry and photomechanics with NMR crystallography: the molecular basis for the macroscopic expansion of an anthracene ester nanorod

“…38 Overall, this minimum displacement reaction pathway is consistent with the Topochemical Principle -the solid-state monomers dimerize with minimal disruption to the crystal packing/ester side chain conformations. [77][78][79] Moving one level out, the effect of these molecular geometry changes on the crystal packing can be seen most clearly by looking at a single layer of herringbone pairs. Figure 5b shows how the atomic-level reconfiguration translates into a net expansion as the now protruding phenyl groups push the herringbone pairs apart.…”