Anionic polymerization of β-nitrostyrene

Electrophilicities oftrans-β-Nitrostyrenes

“…Additions of oxindols to nitroalkenes have been performed under conditions of phase-transfer catalysis, 26 and tandem cycloadditions of nitroalkenes 27,28 have been applied to the synthesis of natural products. 29 Kinetics of the reactions of nitroalkenes with benzylamines, 30 sodium alkoxides, 31 and hydroxide anions 32 have been investigated in order to elucidate the mechanism of nucleophilic additions to the electron-deficient double bond of nitroalkenes. 33 In previous work, we have shown that a large variety of reactions of electrophiles with nucleophiles can be described by eq 1, where N and s N (previously called s) are nucleophilespecific parameters, E is an electrophilicity parameter, and k 2 is the second-order rate constant.…”

“…Kinetics of the reactions of nitroalkenes with benzylamines, sodium alkoxides, and hydroxide anions have been investigated in order to elucidate the mechanism of nucleophilic additions to the electron-deficient double bond of nitroalkenes …”

Zwitterion‐Catalyzed Amino‐Dibromination of Nitroalkenes: Scope, Mechanism, and Application to The Synthesis of Glycinamides

“…2) [7] . However, it is known that nitroalkenes readily undergo anionic polymerization in the presence of catalytic amount of bases such as potassium bicarbonate, [8] sodium methoxide, [9] and 4‐dimethylaminopyridine (DMAP) [10] . For example, c.a.…”

Deciphering the roles of multiple additives in organocatalyzed Michael additions

“…We hypothesized then that nitrostyrene being a strong Michael acceptor could lead to undesirable side reactions and catalyst deactivation through the formation of polymers initiated by a catalytic intermediate. 12,13 The formation of side product 3b was minimal under both conditions B and C (always below 4 mol% formation), and depended essentially on the amount of AcOH present. Increasing amounts of AcOH decreased the formation of 3b under both conditions B and C, as it is shown in the ESI † (page S10).…”

“…This suggested that several molecules of 1 might be involved in those intermediates, in accordance with its tendency to polymerize. 12,13 Finally, we must add that under ''added water'' conditions (conditions C), the reaction mixture remained a pale yellow solution, whereas a dark, turbid solution appeared throughout the time when no extra water was added, indicating the formation of some unknown side product (Fig. 1C and ESI, † page S34).…”