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

被引：1

作者：

Shang, Wen ^{[1
]}

Schlam, Roxana F. ^{[1
]}

Hickey, Magali B. ^{[1
]}

Zhou, Jingye ^{[1
]}

Wheeler, Kraig A. ^{[1
]}

de Delgado, Graciela C. Diaz ^{[1
]}

Chen, Chun-Hsing ^{[1
]}

Snider, Barry B. ^{[1
]}

Foxman, Bruce M. ^{[1
]}

机构：

[1] Brandeis Univ, Dept Chem, Waltham, MA 02453 USA

来源：

CRYSTAL GROWTH & DESIGN | 2021年 / 21卷 / 01期

基金：

美国国家科学基金会;

关键词：

CHAIN-REACTION; RADIATION-CHEMISTRY; METAL-SALTS; POLYMERIZATION; ACID; REACTIVITY; PHOTOCHEMISTRY; TOPOCHEMISTRY; ESTERS; AUTOXIDATION;

D O I：

10.1021/acs.cgd.0c01466

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

gamma-Irradiation of crystalline hexaaquamagnesium trans-2-butenoate dihydrate affords rel-(3S,4R)-1-hexene-3,4-dicarboxylate by a single-crystal-to-single-crystal reaction. The reaction proceeds by a radical chain mechanism with anti addition to the butenoate double bond, as established by deuterium labeling. The product structure is that expected from the orientation of trans-2-butenoates in the pristine crystal. The same dicarboxylate is formed by heating crystalline sodium trans-2-butenoate at 300 degrees C, but the thermal ene reaction was shown by deuterium labeling to proceed by syn addition to the butenoate double bond as expected for a concerted ene reaction. gamma-Irradiation of sodium trans-2-butenoate forms a single trimer chemo-, regio-, and stereospecifically. The structure of sodium trans-2-butenoate was determined, and the crystal packing is consistent with both the observed ene dimerization and gamma-ray-induced trimerization.

引用

页码：663 / 682

页数：20