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A silver-catalyzed intramolecular amidation of saturated C--h bonds.
| Content Provider | Semantic Scholar |
|---|---|
| Author | Cui, Yong He, Chuan |
| Copyright Year | 2004 |
| Abstract | Oxidative insertion reactions into saturated C H bonds to form amines and amine derivatives under transition-metal catalysis are attractive synthetic methodologies. Besides providing facile access to various organic structures, these reactions also offer opportunities to study the fundamental mechanism of C H activation. It has been demonstrated that Rhand Ru-based compounds mediate C H amidation reactions particularly well. 14–19] A dirhodium(ii) tetracarboxylate system was shown to catalyze the intramolecular amidation of C H bonds of carbamates and sulfamates with high regioselectivity and good to excellent diastereoselectivity. It is thought that a metal-bound nitrene species might be formed which then inserts oxidatively into saturated C H bonds in these reactions. Despite extensive studies of metalcatalyzed amidations of C H bonds, efficient and practical examples of such processes are limited. We report herein an efficient amidation reaction of saturated C H bonds catalyzed by silver(i). Silver complexes exhibit interesting activity, and silvercatalyzed organic transformations have attracted attention recently. In particular, several nonradical oxidative group-transfer reactions catalyzed by silver were discovered. We reported a disilver(i) compound (1, Scheme 1a) that efficiently catalyzes the aziridination of olefins. Surprisingly, subsequent studies showed that only this disilver complex gave clean aziridine products in the silver-mediated reactions tested with a variety of different ligands. This led us to propose that the disilver structure may be important for the unique activity of this complex, and that the same compound may catalyze other reactions, such as the activation of saturated C H bonds. After several experiments we found that 1 generated in situ catalyzed the efficient intramolecular amidation of saturated C H bonds, as shown in Scheme 1b. With the indanol-derived carbamate 2 as the substrate, AgNO3 (4 mol%) with 4,4’,4’’-tri-tert-butyl-2,2’:6’,2’’terpyridine (tBu3tpy, 4 mol%) as the catalyst, and PhI(OAc)2 (2.0 equiv) as the oxidant, the cyclized product indanooxazolidin-2-one (3) was isolated from the reaction in acetonitrile in 83% yield (Table 1 and entry 2 of Table 2). A color change |
| Starting Page | 495 |
| Ending Page | 502 |
| Page Count | 8 |
| File Format | PDF HTM / HTML |
| Alternate Webpage(s) | http://he-group.uchicago.edu/He%20publication/Y%20Cui%20Angew%2043.pdf |
| PubMed reference number | 15307089v1 |
| Volume Number | 43 |
| Issue Number | 32 |
| Journal | Angewandte Chemie |
| Language | English |
| Access Restriction | Open |
| Subject Keyword | Alkenes Amines Carbamates Catalysis Clinical act of insertion Insertion Mutation Methyl tert-butyl ether:MCnc:Pt:Bld:Qn Oxidants RU 28318 Saturated Dosing Unit Saturated abdominal dressings:Num:Pt:Wound:Qn Silver acetonitrile alphanumeric label - 1A amidation aziridine cell transformation hemoglobin-dextran 10-benzene-tetracarboxylate nitrene |
| Content Type | Text |
| Resource Type | Article |
