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221.
Efficient Copper‐Catalyzed Direct Intramolecular Aminotrifluoromethylation of Unactivated Alkenes with Diverse Nitrogen‐Based Nucleophiles
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Dr. Jin‐Shun Lin Ya‐Ping Xiong Can‐Liang Ma Li‐Jiao Zhao Prof. Dr. Bin Tan Prof. Dr. Xin‐Yuan Liu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(5):1332-1340
A mild, convenient, and step‐economical intramolecular aminotrifluoromethylation of unactivated alkenes with a variety of electronically distinct, nitrogen‐based nucleophiles in the presence of a simple copper salt catalyst, in the absence of extra ligands, is described. Many different nitrogen‐based nucleophiles (e.g., basic primary aliphatic and aromatic amines, sulfonamides, carbamates, and ureas) can be employed in this new aminotrifluoromethylation reaction. The aminotrifluoromethylation process allows straightforward access to diversely substituted CF3‐containing pyrrolidines or indolines, in good to excellent yields, through a direct difunctionalization strategy from the respective acyclic starting materials. Mechanistic studies were conducted and a plausible mechanism was proposed. 相似文献
222.
Bertrand Schweitzer‐Chaput Joachim Demaerel Hauke Engler Dr. Martin Klussmann 《Angewandte Chemie (International ed. in English)》2014,53(33):8737-8740
Based on a mechanistic study, we have discovered a Brønsted acid catalyzed formation of ketone radicals. This is believed to proceed via thermally labile alkenyl peroxides formed in situ from ketones and hydroperoxides. The discovery could be utilized to develop a multicomponent radical addition of unactivated ketones and tert‐butyl hydroperoxide to olefins. The resulting γ‐peroxyketones are synthetically useful intermediates that can be further transformed into 1,4‐diketones, homoaldol products, and alkyl ketones. A one‐pot reaction yielding a pharmaceutically active pyrrole is also described. 相似文献
223.
Dr. Jeffrey Y. W. Mak Dr. Rebecca H. Pouwer Assoc. Prof. Craig M. Williams 《Angewandte Chemie (International ed. in English)》2014,53(50):13664-13688
Well over a hundred years ago, Professor Julius Bredt embarked on a career pursuing and critiquing bridged bicyclic systems that contained ring strain induced by the presence of a bridgehead olefin. These endeavors founded what we now know as Bredt’s rule (Bredtsche Regel). Physical, theoretical, and synthetic organic chemists have intensely studied this premise, pushing the boundaries of such systems to arrive at a better understood physical phenomenon. Mother nature has also seen fit to construct molecules containing bridgehead double bonds that encompass Bredt’s rule. For the first time, this topic is reviewed in a natural product context. 相似文献
224.
Caitlin M. McMahon Prof. Erik J. Alexanian 《Angewandte Chemie (International ed. in English)》2014,53(23):5974-5977
A palladium‐catalyzed, intermolecular Heck‐type coupling of alkyl iodides and alkenes is described. This process is successful with a variety of primary and secondary unactivated alkyl iodides as reaction partners, including those with hydrogen atoms in the β position. The mild catalytic conditions enable intermolecular C? C bond formations with a diverse set of alkyl iodides and alkenes, including substrates containing base‐ or nucleophile‐sensitive functionality. 相似文献
225.
Dr. Wangqing Kong Dr. Estíbaliz Merino Prof. Dr. Cristina Nevado 《Angewandte Chemie (International ed. in English)》2014,53(20):5078-5082
Two radical‐mediated processes of activated alkenes, namely arylphosphonylation and arylazidation, are described. The difunctionalization of alkenes by a tandem process that involves radical addition, 1,4‐aryl migration, and desulfonylation generates α‐aryl‐β‐heterofunctionalized amides bearing a quaternary stereocenter when the substituent on the nitrogen atom is an aryl group. Alternatively, heterooxindoles or spirobicycles can be obtained with excellent regioselectivity in the presence of an alkyl substituent on the nitrogen atom. 相似文献
226.
Copper‐Catalyzed Aerobic Oxidative CC Bond Cleavage for CN Bond Formation: From Ketones to Amides
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A novel copper‐catalyzed aerobic oxidative C(CO)? C(alkyl) bond cleavage reaction of aryl alkyl ketones for C? N bond formation is described. A series of acetophenone derivatives as well as more challenging aryl ketones with long‐chain alkyl substituents could be selectively cleaved and converted into the corresponding amides, which are frequently found in biologically active compounds and pharmaceuticals. 相似文献
227.
Copper‐Catalyzed Aerobic Oxidative Transformation of Ketone‐Derived N‐Tosyl Hydrazones: An Entry to Alkynes
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Xianwei Li Xiaohang Liu Huoji Chen Dr. Wanqing Wu Dr. Chaorong Qi Prof. Dr. Huanfeng Jiang 《Angewandte Chemie (International ed. in English)》2014,53(52):14485-14489
A novel strategy involving Cu‐catalyzed oxidative transformation of ketone‐derived hydrazone moiety to various synthetic valuable internal alkynes and diynes has been developed. This method features inexpensive metal catalyst, green oxidant, good functional group tolerance, high regioselectivity and readily available starting materials. Oxidative deprotonation reactions were carried out to form internal alkynes and symmetrical diynes. Cross‐coupling reactions of hydrazones with halides and terminal alkynes were performed to afford functionalized alkynes and unsymmetrical conjugated diynes. A mechanism proceeding through a Cu‐carbene intermediate is proposed for the C? C triple bond formation. 相似文献
228.
Gold(I)‐Catalyzed Diazo Coupling: Strategy towards Alkene Formation and Tandem Benzannulation
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Daming Zhang Guangyang Xu Dong Ding Chenghao Zhu Dr. Jian Li Prof. Dr. Jiangtao Sun 《Angewandte Chemie (International ed. in English)》2014,53(41):11070-11074
A gold(I)‐catalyzed cross‐coupling of diazo compounds to afford tetrasubstituted alkenes has been developed by taking advantage of a trivial electronic difference between two diazo substrates. A N‐heterocyclic‐carbene‐derived gold complex is the most effective catalyst for this transformation. Based on this new strategy, a gold(I)‐initiated benzannulation has been achieved through a tandem reaction involving a diazo cross‐coupling, 6π electrocyclization, and oxidative aromatization. 相似文献
229.
Dr. Congde Huo Yong Yuan Mingxia Wu Dr. Xiaodong Jia Dr. Xicun Wang Fengjuan Chen Jing Tang 《Angewandte Chemie (International ed. in English)》2014,53(49):13544-13547
The unprecedented title reaction between glycine derivatives and indoles, as well as the auto‐oxidative Povarov/aromatization tandem reaction of glycine derivatives with olefins are described. The reactions were performed in the absence of redox‐active catalysts and chemical oxidants under mild reaction conditions. Only simple organic solvents and air (or O2) were required. 相似文献
230.
A novel three‐component strategy for the azidotrifluoromethylation of alkenes has been presented here. The reaction proceeded smoothly under gentle temperature and gave the bifunctional olefins in high yields. Furthermore, 1,3‐dipolar reactions between azide‐containing products and phenylacetylene revealed great potential in molecular modification by using this method. 相似文献