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Keywords = carboazidation

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13 pages, 1635 KiB  
Article
Revealing the Iron-Catalyzed β-Methyl Scission of tert-Butoxyl Radicals via the Mechanistic Studies of Carboazidation of Alkenes
by Mong-Feng Chiou, Haigen Xiong, Yajun Li, Hongli Bao and Xinhao Zhang
Molecules 2020, 25(5), 1224; https://doi.org/10.3390/molecules25051224 - 9 Mar 2020
Cited by 11 | Viewed by 5982
Abstract
We describe here a mechanistic study of the iron-catalyzed carboazidation of alkenes involving an intriguing metal-assisted β-methyl scission process. Although t-BuO radical has frequently been observed in experiments, the β-methyl scission from a t-BuO radical into a methyl radical and acetone is still [...] Read more.
We describe here a mechanistic study of the iron-catalyzed carboazidation of alkenes involving an intriguing metal-assisted β-methyl scission process. Although t-BuO radical has frequently been observed in experiments, the β-methyl scission from a t-BuO radical into a methyl radical and acetone is still broadly believed to be thermodynamically spontaneous and difficult to control. An iron-catalyzed β-methyl scission of t-BuO is investigated in this work. Compared to a free t-BuO radical, the coordination at the iron atom reduces the activation energy for the scission from 9.3 to 3.9 ~ 5.2 kcal/mol. The low activation energy makes the iron-catalyzed β-methyl scission of t-BuO radicals almost an incomparably facile process and explains the selective formation of methyl radicals at low temperature in the presence of some iron catalysts. In addition, a radical relay process and an outer-sphere radical azidation process in the iron-catalyzed carboazidation of alkenes are suggested by density functional theory (DFT) calculations. Full article
(This article belongs to the Special Issue Recent Advances in Iron Catalysis)
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10 pages, 2175 KiB  
Article
Two-Step Azidoalkenylation of Terminal Alkenes Using Iodomethyl Sulfones
by Nicolas Millius, Guillaume Lapointe and Philippe Renaud
Molecules 2019, 24(22), 4184; https://doi.org/10.3390/molecules24224184 - 18 Nov 2019
Cited by 8 | Viewed by 4511
Abstract
The radical azidoalkylation of alkenes that was initially developed with α-iodoesters and α-iodoketones was extended to other activated iodomethyl derivatives. By using iodomethyl aryl sulfones, the preparation of γ-azidosulfones was easily achieved. Facile conversion of these azidosulfones to homoallylic azides using a Julia–Kocienski [...] Read more.
The radical azidoalkylation of alkenes that was initially developed with α-iodoesters and α-iodoketones was extended to other activated iodomethyl derivatives. By using iodomethyl aryl sulfones, the preparation of γ-azidosulfones was easily achieved. Facile conversion of these azidosulfones to homoallylic azides using a Julia–Kocienski olefination reaction is reported, making the whole process equivalent to the azidoalkenylation of terminal alkenes. Full article
(This article belongs to the Special Issue Biomimetic Radical Chemistry and Applications)
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