Department of Chemistry and Applied Biosciences, Laboratory of Organic Chemistry, ETH Zürich, 8093 Zurich, Switzerland.
Published: October 2023
AI Article Synopsis
Article Abstract
Unactivated olefins are converted to alkyl azides with bench-stable NaN in the presence of FeCl·6HO under blue-light irradiation. The products are obtained with anti-Markovnikov selectivity, and the reaction can be performed under mild ambient conditions in the presence of air and moisture. The transformation displays broad functional group tolerance, which renders it suitable for functionalization of complex molecules. Mechanistic investigations are conducted to provide insight into the hydroazidation reaction and reveal the role of water from the iron hydrate as the H atom source.
We report a continuous flow approach generating bicyclic cyclobutanes from unactivated alkenes in a metal-free manner that is inspired by the Kochi-Salomon reaction. A filtered Hg-lamp in combination with a simple flow set-up and acetone as UV light-absorbing co-solvent are crucial for this method thus showcasing attractive features for further exploitations.
We report an electrophotocatalytic process that enables the thiocyanation and sulfonylation/cyclization of alkenes. It is applicable to a wide range of unactivated alkenes, using the inexpensive photocatalyst 2,4,6-triphenylpyrylium tetrafluoroborate (TPPT) to produce a diverse array of heterocycles containing sulfonyl and thiocyano groups with good functional group tolerance. The protocol operates under mild, chemical oxidant- and transition-metal-free, with a broad scope of substrates.
West China School of Public Health and West China Fourth Hospital, West China-PUMC C.C. Chen Institute of Health, and State Key Laboratory of Biotherapy, Sichuan University, Chengdu 610041, China.
The hydroalkylation reaction of olefins with alkanes is a highly desirable synthetic transformation toward the construction of C(sp)─C(sp) bonds. However, such transformation has proven to be challenging for unactivated olefins, particularly when the substrates lack directing groups or acidic C(sp)─H bonds. Here, we address this challenge by merging NiH-catalyzed radical relay strategy with a HAT (hydrogen atom transfer) process.
Catalytic regio- and enantioselective hydroamination of less activated internal alkenes presents a challenge to synthetic chemists due to their low reactivity and the difficulty in simultaneously controlling regio- and enantioselectivities. Here, we report an iridium-catalyzed enantioselective hydroamination of internal alkenes directed by an amide. The amide group on the alkene effectively directs the catalyst to overcome the low reactivity and control the regioselectivity and the enantiotopic face selection.
Key Laboratory of Bio-Based Material Science and Technology, Ministry of Education, College of Material Science and Engineering, Northeast Forestry University, Harbin 150040, People's Republic of China.
A visible-light-induced method for the hydrodichloromethylation of unactivated alkenes using chloroform (CHCl) was developed, employing pyridine·BH as the halogen atom transfer (XAT) reagent. The strategy showed a broad functional group tolerance, and 29 examples of unactivated alkenes, including complex natural products or drug derivatives, have been established with good yields. Mechanistic studies indicated that CHCl serves as both the source of a dichloromethyl radical and a hydrogen atom transfer (HAT) reagent, and the borane short-chain reaction process was involved in this system.
