Intermolecular Radical Addition and Addition/Cyclization Reactions of Alkoxyamines onto Nonactivated Alkenes

Abstract

[reaction: see text] Alkoxyamines A, which are readily prepared from commercially available starting materials, undergo efficient thermal radical carboaminoxylations onto various nonactivated alkenes to provide 1,4-functionalized malonates B in good to excellent yields. The experiments are very easy to conduct. The carboaminoxylations can be combined with radical cyclization and fragmentation processes.

Tin‐Free Radical Alkoxyamine Addition and Isomerization Reactions by Using the Persistent Radical Effect: Variation of the Alkoxyamine Structure

“…Intermolecular processes—Radical alkoxyamine additions : We next decided to study nitroxide‐mediated intermolecular alkoxyamine additions, so‐called carboaminoxylations 22. Along with the strength of the CO bond, the reactivity of the C‐centered radical in the intermolecular addition has to be considered.…”

Nitroxides: Applications in Synthesis and in Polymer Chemistry

“…Heating alkoxyamine 102 in dichloroethane for three days with 1-octene (5 equiv) afforded adduct 103 in 66 % yield (Scheme 44). [211] It was found that replacing the TEMPO moiety in the starting alkoxyamine with sterically more hindered nitroxides provides compounds which undergo thermal radical carboaminoxylation with 1-octene in higher yields (up to 86 % yield) in a much shorter reaction time (1.5 h). [212] The reaction time for the radical carboaminoxylation of 1-octene with alkoxyamine 102 to give 103 was reduced to ten minutes by switching to microwave heating.…”

Nitroxide decomposition: Implications toward nitroxide design for applications in living free‐radical polymerization

“…These unusual properties have led to a wide range of applications spanning their use in biology as spin labels [1][2][3][4][5][6] to the development of organomagnetic materials. 7 In organic chemistry, nitroxides have been used in kinetic studies, [8][9][10][11] as oxidizing species in the form of the corresponding N-oxo ammonium salts, [12][13][14][15][16][17][18][19][20][21][22][23] as temporary caps for transient carbon radicals, [24][25][26][27][28][29][30][31] and as probes for stereocontrol with prochiral carbon radicals. [32][33][34][35][36] In polymer chemistry, nitroxide-mediated polymerization (NMP) [37][38][39][40][41][42][43][44][45][46][47] has become popular as a method for preparing living polymers ...…”