Anti-Markovnikov Hydroazidation of Alkenes by Visible-Light Photoredox Catalysis.

Published on Mar 7, 2019in Chemistry: A European Journal4.857
· DOI :10.1002/CHEM.201806371
Juan-Juan Wang2
Estimated H-index: 2
(Lanzhou University),
Wei Yu27
Estimated H-index: 27
(Lanzhou University)
Sources
Abstract
: The anti-Markovnikov hydroazidation of alkenes has been accomplished under visible-light irradiation by using [Ir(dF(CF3 )ppy)2 (dtbbpy)]PF6 as the photocatalyst and trimethylsilyl azide as the azidating agent. The reactions were greatly facilitated by water, the beneficial effect of which can be attributed to its participation in the reaction as the hydrogen donor, as indicated by deuterium isotope experiments. The reactions proceed under solvent free conditions in the presence of water. 4-Dimethylaminopyridine also exhibited a beneficial effect on the reactions. The present method enabled hydroazidation of several types of unactivated alkenes with good yields and high regioselectivity.
📖 Papers frequently viewed together
38 Citations
4 Authors (Qing-Yu Lin, ..., Feng-Ling Qing)
81 Citations
2 Citations
References64
Newest
#1Ya-Xuan Zhang (USTC: University of Science and Technology of China)H-Index: 2
#2Ruo-Xing Jin (USTC: University of Science and Technology of China)H-Index: 7
Last. Xi-Sheng Wang (USTC: University of Science and Technology of China)H-Index: 33
view all 5 authors...
A copper-catalyzed dichloromethylazidation of alkenes using commercially available BrCCl2H as a stoichiometric dichloromethylating reagent has been reported. Mechanistic studies indicated that a dichloromethyl radical was involved in the catalytic cycle. This transformation has demonstrated mild conditions, high reactivity, excellent functional-group tolerance, and a broad substrate scope, and thus it has offered a new solution for difunctionalization of alkenes to make diverse transformable dic...
20 CitationsSource
#1Bo Yang (ZJU: Zhejiang University)H-Index: 31
#1Bo Yang (ZJU: Zhejiang University)H-Index: 26
Last. Zhan Lu (ZJU: Zhejiang University)H-Index: 31
view all 5 authors...
15 CitationsSource
#1Wei-Yu Li (XTU: Xiangtan University)H-Index: 1
#2Chuan-Shuo Wu (XTU: Xiangtan University)H-Index: 1
Last. Yang Luo (XTU: Xiangtan University)H-Index: 1
view all 4 authors...
Reported herein is a novel iron-catalyzed, DTBP-mediated carboazidation of alkenes using cycloalkanes, CH2Cl2, CHCl3 and CCl4 as alkylating reagents to generate electrophilic or nucleophilic alkyl radicals. Mechanistic studies suggested that the reaction proceeded via the addition of alkyl radicals to alkenes followed by an iron-mediated ligand transfer process. The reaction is unique as it is applicable not only to diversely functionalized electron rich alkenes, but also to electron-poor olefin...
22 CitationsSource
#1Liang Zhang (SDU: Shandong University)H-Index: 4
#2Shuya Liu (SDU: Shandong University)H-Index: 4
Last. Yao Wang (SDU: Shandong University)H-Index: 22
view all 6 authors...
We describe a (salen)Mn(III)-catalyzed three-component reaction of aldehydes, olefins, and sodium azide for the installation of two useful groups (CO and N3) into the double bond. Traditionally, (salen)Mn(III) in conjunction with iodosobenzene is a classical catalysis system for epoxidation of olefins. Owing to the highly competitive oxygenation approaches, it is a true challenge to establish a distinct strategy for the exploration of new olefin transformations based on this (salen)Mn(III) catal...
9 CitationsSource
#1Saki Ichikawa (MIT: Massachusetts Institute of Technology)H-Index: 6
#2Shaolin Zhu (MIT: Massachusetts Institute of Technology)H-Index: 20
Last. Stephen L. Buchwald (MIT: Massachusetts Institute of Technology)H-Index: 181
view all 3 authors...
: Despite significant recent progress in copper-catalyzed enantioselective hydroamination chemistry, the synthesis of chiral N-arylamines, which are frequently found in natural products and pharmaceuticals, has not been realized. Initial experiments with N-arylhydroxylamine ester electrophiles were unsuccessful and, instead, their reduction in the presence of copper hydride (CuH) catalysts was observed. Herein, we report key modifications to our previously reported hydroamination methods that le...
20 CitationsSource
#1Yujing Zhou (MIT: Massachusetts Institute of Technology)H-Index: 13
#2Oliver D. Engl (MIT: Massachusetts Institute of Technology)H-Index: 2
Last. Stephen L. Buchwald (MIT: Massachusetts Institute of Technology)H-Index: 181
view all 5 authors...
A CuH-catalyzed enantioselective hydroamidation reaction of vinylarenes has been developed using readily accessible 1,4,2-dioxazol-5-ones as electrophilic amidating reagents. This method provides a straightforward and efficient approach to synthesize chiral amides in good yields with high levels of enantiopurity under mild conditions. Moreover, this transformation tolerates substrates bearing a broad range of functional groups.
28 CitationsSource
#1Cong Fei (NKU: Nankai University)H-Index: 1
#2Wei Yongliang (NKU: Nankai University)H-Index: 1
Last. Pingping Tang (NKU: Nankai University)H-Index: 2
view all 3 authors...
The first example of an azidotrifluoromethoxylation of styrenes has been achieved by synergistic visible-light-mediated photoredox and silver catalysis. Trifluoromethyl arylsulfonate (TFMS) and the Zhdankin reagent were used as the trifluoromethoxylation reagent and the azide source, respectively. A good functional group tolerance and mild reaction conditions of this method are applicable to late-stage azidotrifluoromethoxylation of complex small molecules. Furthermore, the mechanistic investiga...
21 CitationsSource
#1Clément Lepori (University of Paris-Sud)H-Index: 5
#2Pablo Gómez-Orellana (Autonomous University of Barcelona)H-Index: 2
Last. Jérôme Hannedouche (University of Paris-Sud)H-Index: 21
view all 7 authors...
A well-defined low-coordinate β-diketiminatocobalt(II) alkyl complex is reported as an active precatalyst for the selective alkene cyclohydroamination of unprotected primary amines under mild conditions (rt–90 °C). The reaction mechanism has been investigated by deuterium-labeling, kinetics, and stoichiometric experiments and in-depth computational DFT studies. On the basis of these studies, we propose a stepwise noninsertive mechanism that features a rate-determining nucleophilic attack of the ...
8 CitationsSource
#1Shou-Jie Shen (GSU: Georgia State University)H-Index: 3
#2Cheng-Liang Zhu (GSU: Georgia State University)H-Index: 9
Last. Hao Xu (GSU: Georgia State University)H-Index: 18
view all 4 authors...
We herein report an iron-catalyzed direct diazidation method via activation of bench-stable peroxyesters promoted by nitrogen-based ligands. This method is effective for a broad range of olefins and N-heterocycles, including those that are difficult substrates for the existing olefin diamination and diazidation methods. Notably, nearly a stoichiometric amount of oxidant and TMSN3 are sufficient for high-yielding diazidation for most substrates. Preliminary mechanistic studies elucidated the simi...
26 CitationsSource
#1Samuel N. Gockel (UIUC: University of Illinois at Urbana–Champaign)H-Index: 3
#2Travis L. Buchanan (UIUC: University of Illinois at Urbana–Champaign)H-Index: 1
Last. Kami L. Hull (UIUC: University of Illinois at Urbana–Champaign)H-Index: 17
view all 3 authors...
Copper-catalyzed intermolecular carboamination of alkenes with α-halocarbonyls and amines is presented with 42 examples. Electron rich, electron poor, and internal styrenes, as well as α-olefins, are functionalized with α-halocarbonyls and aryl or aliphatic amines. Mechanistic investigations suggest the reaction is proceeding through addition of a carbon-centered radical across an olefin followed by oxidation to form a 5-membered oxocarbenium intermediate and subsequent nucleophilic ring opening...
41 CitationsSource
Cited By10
Newest
#1Paramasivam Sivaguru (Northeast Normal University)H-Index: 12
#2Yongquan Ning (Northeast Normal University)H-Index: 8
Last. Xihe Bi (Northeast Normal University)H-Index: 14
view all 3 authors...
Aliphatic azides are a versatile class of compounds found in a variety of biologically active pharmaceuticals. These compounds are also recognized as useful precursors for the synthesis of a range of nitrogen-based scaffolds of therapeutic drugs, biologically active compounds, and functional materials. In light of the growing importance of aliphatic azides in both chemical and biological sciences, a vast array of synthetic strategies for the preparation of structurally diverse aliphatic azides h...
4 CitationsSource
#1Jiabin Shen (Zhejiang University of Technology)H-Index: 2
#2Jun Xu (Hangzhou Normal University)H-Index: 12
Last. Pengfei Zhang (Hangzhou Normal University)H-Index: 20
view all 8 authors...
The first example of a photoinduced rapid multicomponent cascade reaction of aryldiazonium salts with unactivated alkenes and trimethylsilyl azide (TMSN3) under oxidant-free conditions is described. This approach provides the synthetic route for a wide range of unsymmetric azo compounds. The compounds are obtained in good to excellent yields under mild reaction conditions. This transformation is applicable to various aryldiazonium salts and alkenes, providing an alternative route for the synthes...
3 CitationsSource
#1Liang Ge (CAS: Chinese Academy of Sciences)H-Index: 8
#1Liang Ge (CAS: Chinese Academy of Sciences)H-Index: 23
Last. Hongli Bao (CAS: Chinese Academy of Sciences)H-Index: 18
view all 4 authors...
Abstract The azido group is found in large numbers of natural products, drugs, biochemicals and materials and to date, many elegant and useful methods for the synthesis of organic azides and their transformations have been documented. In this review, we provide a summary of the state of the art of radical azidation for the construction of C(sp3)-N3 bonds. There is a specific emphasis on the synthetic reactions involving C(sp3)-H azidation, decarboxylative azidation and difunctionalized azidation...
12 CitationsSource
#1Li-Ting Cheng (CCU: National Chung Cheng University)
#2Sheng-Qi Luo (CCU: National Chung Cheng University)
Last. Gene-Hsiang Lee (NTU: National Taiwan University)H-Index: 74
view all 6 authors...
Incorporation of water has been revealed to successfully facilitate visible-light photoredox catalysis of indole leading to increased production of C2-quaternary indolinone. The water-promoted photoreaction of indole under catalyst-free conditions by a household compact fluorescence light was also demonstrated. The antiproliferative activity of the synthesized indolinones was evaluated against three human cancer cell lines.
Source
#1Yu-Zhao Wang (Lanzhou University)H-Index: 4
#2Wu-Jie Lin (Lanzhou University)H-Index: 1
Last. Xue‐Yuan Liu (Lanzhou University)H-Index: 53
view all 5 authors...
3 CitationsSource
#1Salvatore Santamaria (Imperial College London)H-Index: 14
#2Doretta Cuffaro (UniPi: University of Pisa)H-Index: 5
Last. Josefin Ahnstroem (Imperial College London)
view all 10 authors...
ADAMTS-5 is a major protease involved in the turnover of proteoglycans such as aggrecan and versican. Its aggrecanase activity has been directly linked to the etiology of osteoarthritis (OA), identifying ADAMTS-5 as a pharmaceutical target for OA treatment. However, most existing ADAMTS-5 inhibitors target its active site and therefore suffer from poor selectivity. Here, using a novel approach, we have designed a new class of sugar-based arylsulfonamide inhibitors, which are selective for ADAMTS...
Source
#1Manuel AlgarraH-Index: 25
#2Juan Soto (UMA: University of Málaga)H-Index: 25
Last. Manuel Algarra (University of Madeira)H-Index: 2
view all 2 authors...
This work studies the photochemical and thermal decompositions of azidoacetonitrile (N 3 CH 2 CN) from both the experimental and theoretical points of view. The data of the photochemical experiments are taken from the literature, while the thermal decomposition have been carried out by us. In addition, we have performed ab initio calculations of the multiconfigurational type [complete active space self-consistent field (CASSCF) and the multistate multireference perturbation theory (MS-CASPT2)]. ...
4 CitationsSource
Last. David A. NicewiczH-Index: 37
view all 4 authors...
Organic azides serve as synthetically useful surrogates for primary amines, a functional group which is ubiquitous in bioactive and medicinally relevant molecules. Historically, the formal hydroazidation of simple activated olefins and styrenes has proven difficult due to the inherent propensity of these compounds to oligomerize. Herein is disclosed a method for the anti-Markovnikov hydroazidation of activated olefins, catalyzed by an organic acridinium salt under irradiation from blue LEDs. Thi...
4 CitationsSource
#1Peng Wang (HUST: Huazhong University of Science and Technology)H-Index: 2
#2Yunxuan Luo (HUST: Huazhong University of Science and Technology)H-Index: 1
Last. Yuefa Gong (HUST: Huazhong University of Science and Technology)H-Index: 11
view all 5 authors...
5 CitationsSource
#1Xiaonan Li (CAS: Chinese Academy of Sciences)H-Index: 2
#2Pinhong Chen (CAS: Chinese Academy of Sciences)H-Index: 38
Last. Guosheng Liu (CAS: Chinese Academy of Sciences)H-Index: 58
view all 3 authors...
Anti-Markovnikov hydroazidation of unactivated alkenes using ABX2014;N3 as an initiator has been developed at room temperature, wherein hydrogen azide (HN3) acts as both hydrogen and azidating agent. Notably, the HN3 reagent was generated from azidotrimethylsilane (TMSN3) and acetic acid in situ. The reaction itself displays broad substrate scope, good yields and excellent regioselectivities.
4 CitationsSource