Stereospecific γ‐Ray‐Induced Trimerization of Crystalline Sodium trans‐2‐Butenoate

Abstract

pounds 2 and 3 also exhibited identical cleavage profiles (Fig. 3, lanes 7 and 9), but different from that of 1 (Fig. 3, lane 1). The susceptibility of conjugated sulfones to nucleophilic attack is also in line with the proposed mechanism. ['3] The selectivity of compounds 1-3 in recognizing DNA regions may reflect not only their reactivity towards individual bases, but also local DNA shapes. This selectivity may be amplified synergistically by attaching these new DNA-cleaving moieties onto sequence-specific delivery systems.

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

“…g-Irradiation of lithium trans-2-butenoate (11) As hypothesized from the orientation of the trans-2-butenoates in the crystal, constant-beam 60 Co g-irradiation converts lithium trans-2-butenoate (11) cleanly to dilithium trans-5-methyl-2heptenedioate (13a) with a maximum yield of $32% after a 442 kGy dose (Fig. 1 and Scheme 4).…”

“…We were delighted to find that irradiation of 1 with 60 Co g-rays (156 kGy) initiates a radical chain reaction that affords one of eight possible diastereomers of trisodium 2,4-dimethyl-6-heptene-1,3,5-tricarboxylate (3) in 55% yield. 11 Owing to the rather poor crystal quality of 1, we were unable to carry out an X-ray structure determination in order to establish detailed structure-reactivity relationships. 11 However, the efficient conversion of 1 to 3 suggested that further exploration of the radical chemistry of crystalline trans-2-butenoates would be productive.…”

“…11 Owing to the rather poor crystal quality of 1, we were unable to carry out an X-ray structure determination in order to establish detailed structure-reactivity relationships. 11 However, the efficient conversion of 1 to 3 suggested that further exploration of the radical chemistry of crystalline trans-2-butenoates would be productive. We began with trans-2-butenoate salts and complexes of metals with small radii and coordination numbers of 6 or less, which would be most likely to contain the necessary short contacts between the unsaturated groups.…”

Structure and γ-Ray-Induced Solid-State Polymerization of Sodium Propynoate: Influence of Bilayer Formation on Solid-State Reactivity

“…Second, for compact structures with low coordination numbers (such as one might "nd with a sodium ion), the metal}metal distance and the carboxylate}carboxylate distance within the bilayer will be in the vicinity of 3.5 A > , near the van der Waals separation for the unsaturated ligands, which will be close-packed and suitably positioned to undergo a solid-state reaction. Sodium trans-2-butenoate, which has a 3.47 A > lattice repeat distance and undergoes a stereospeci"c -ray-induced trimerization reaction, likely packs in a bilayer structure (25). Presumably, other sodium-containing phases, as well as phases containing other small cations, will exhibit unusual solid-state reactivity.…”

Crystal and Molecular Structure of Crotonohydroxamic Acid, and a Preliminary Investigation of the Solid-State Reactivity of the Acid and Its Salts

“…Thus, heating sodium trans-2-butenoate 1 leads to one of two possible diastereomers of disodium 1-hexene-3,4-dicarboxylate 2 [1], while 60 Co (c-irradiation of 1 leads to trimer 3 [2], one of eight possible diastereomeric products. Irradiation of the calcium salt leads to cyclodimer 4, one of four possible diastereomers [3].…”