18094-01-4Relevant academic research and scientific papers
Oxidative Cleavage of Alkenes by O2with a Non-Heme Manganese Catalyst
Bennett, Elliot L.,Brookfield, Adam,Guan, Renpeng,Huang, Zhiliang,Mcinnes, Eric J. L.,Robertson, Craig M.,Shanmugam, Muralidharan,Xiao, Jianliang
, p. 10005 - 10013 (2021/07/19)
The oxidative cleavage of C═C double bonds with molecular oxygen to produce carbonyl compounds is an important transformation in chemical and pharmaceutical synthesis. In nature, enzymes containing the first-row transition metals, particularly heme and non-heme iron-dependent enzymes, readily activate O2 and oxidatively cleave C═C bonds with exquisite precision under ambient conditions. The reaction remains challenging for synthetic chemists, however. There are only a small number of known synthetic metal catalysts that allow for the oxidative cleavage of alkenes at an atmospheric pressure of O2, with very few known to catalyze the cleavage of nonactivated alkenes. In this work, we describe a light-driven, Mn-catalyzed protocol for the selective oxidation of alkenes to carbonyls under 1 atm of O2. For the first time, aromatic as well as various nonactivated aliphatic alkenes could be oxidized to afford ketones and aldehydes under clean, mild conditions with a first row, biorelevant metal catalyst. Moreover, the protocol shows a very good functional group tolerance. Mechanistic investigation suggests that Mn-oxo species, including an asymmetric, mixed-valent bis(μ-oxo)-Mn(III,IV) complex, are involved in the oxidation, and the solvent methanol participates in O2 activation that leads to the formation of the oxo species.
Nickel-Catalyzed Decarboxylative Alkenylation of Anhydrides with Vinyl Triflates or Halides
Chen, Hui,Sun, Shuhao,Liao, Xuebin
supporting information, p. 3625 - 3630 (2019/05/24)
Decarboxylative cross-coupling of aliphatic acid anhydrides with vinyl triflates or halides was accomplished via nickel catalysis. This methodology works well with a broad array of substrates and features abundant functional group tolerance. Notably, our approach addresses the issue of safe and environmental installation of methyl or ethyl group into molecular scaffolds. The method possesses high chemoselectivity toward alkyl groups when aliphatic/aromatic mixed anhydrides are involved. Furthermore, diverse ketones could be modified with our strategy.
Triflimide-catalysed sigmatropic rearrangement of N-allylhydrazones as an example of a traceless bond construction
Mundal, Devon A.,Avetta Jr., Christopher T.,Thomson, Regan J.
supporting information; experimental part, p. 294 - 297 (2010/09/12)
The recognition of structural elements (that is, retrons) that signal the application of specific chemical transformations is a key cognitive event in the design of synthetic routes to complex molecules. Reactions that produce compounds without an easily identifiable retron, by way of either substantial structural rearrangement or loss of the atoms required for the reaction to proceed, are significantly more difficult to apply during retrosynthetic planning, yet allow for non-traditional pathways that may facilitate efficient acquisition of the target molecule. We have developed a triflimide (Tf 2 NH)-catalysed rearrangement of N-allylhydrazones that allows for the generation of a sigma bond between two unfunctionalized sp 3 carbons in such a way that no clear retron for the reaction remains. This new traceless bond construction displays a broad substrate profile and should open avenues for synthesizing complex molecules using non-traditional disconnections.
Cobalt-catalyzed regioselective dehydrohalogenation of alkyl halides with dimethylphenylsilylmethylmagnesium chloride
Kobayashi, Tsuneyuki,Ohmiya, Hirohisa,Yorimitsu, Hideki,Oshima, Koichiro
supporting information; body text, p. 11276 - 11277 (2009/02/05)
Cobalt-catalyzed reactions of haloalkanes with dimethylphenylsilylmethylmagnesium chloride result in highly regioselective dehydrohalogenation. The reaction does not follow the conventional E2 elimination mechanism but includes β-hydride elimination from the corresponding alkylcobalt intermediate. The interesting reaction mechanism of the cobalt-catalyzed dehydrohalogenation offered unique transformations that are otherwise difficult to attain. Copyright
Deoxygenative dimerization of benzylic and allylic alcohols, and their ethers and esters using lanthanum metal and chlorotrimethylsilane in the presence of a catalytic amount of iodine and copper(I) iodide
Nishino, Toshiki,Nishiyama, Yutaka,Sonoda, Noboru
, p. 635 - 641 (2007/10/03)
Benzylic and allylic alcohols were deoxygenatively dimerized by a treatment with lanthanum metal and chlorotri-methylsilane in the presence of a catalytic amount of iodine, giving the corresponding coupling products, alkanes, in moderate-to-good yields. This dimerization reaction was dramatically accelerated by the addition of a catalytic amount of copper(I) iodide. Similarly, ethers and esters were deoxygenatively dimerized by La/Me3SiCl/cat.I2/cat.CuI system in the presence of a catalytic amount of H2O.
A Facile Method for Synthesis of Alkyl Phenyl Selenides. The Reaction of Diphenyl Diselenide with Oxygen-containing Compounds Using La/Me 3SiCl/cat.I2/cat.CuI System
Nishino, Toshiki,Nishiyama, Yutaka,Sonoda, Noboru
, p. 918 - 919 (2007/10/03)
Alcohols, ethers, and esters were directly converted to the corresponding alkyl phenyl selenides by the reaction of diphenyl diselenide and the La/Me 3SiCl/cat.I2/cat.CuI. It was suggested that alkyl phenyl sele
Reduction of organic halides with lanthanum metal: A novel generation method of alkyl radicals
Nishino, Toshiki,Watanabe, Toshihisa,Okada, Mitsuo,Nishiyama, Yutaka,Sonoda, Noboru
, p. 966 - 969 (2007/10/03)
Results of the reaction of alkyl halides with lanthanum metal have been shown. The reduction of alkyl iodide with 1/3 equiv of lanthanum metal efficiently proceeded to give the corresponding reductive dimerized products along with the formation of reduction and dehydroiodination products. In the case of alkyl bromides and chlorides, the reaction did not proceed under the same reaction conditions as that of alkyl iodides; however, the reaction was dramatically promoted by the addition of a catalytic amount of iodine. A reaction pathway including alkyl radicals was suggested.
Zirconium complexes of 9-phenyl-9-borataanthracene. Synthesis, structural characterization, and reactivity
Lee, Rip A.,Lachicotte, Rene J.,Bazan, Guillermo C.
, p. 6037 - 6046 (2007/10/03)
Lithium 9-phenyl-9-borataanthracene (3·Li(THF)(x), (x) = 2 or 3) is obtained quantitatively from the deprotonation of 9-phenyl-9,10-dihydro-9-borataanthracene (6) with LiTMP (TMP 2,2,6,6-tetramethylpiperidide) in THF. A comparison of the crystallographica
Molybdenum catalyzed dehydration of tertiary alcohols to olefins
Kantam,Prasad,Santhi
, p. 45 - 48 (2007/10/02)
Molybdenyl (VI) acetylacetonate is shown to be an effective catalyst for easy conversion of tertiary alcohols to the corresponding olefins in high yields.
Tertiary Carbinamines by Addition of Organocerium Reagents to Nitriles and Ketimines
Ciganek, Engelbert
, p. 4521 - 4527 (2007/10/02)
Organocerium reagents, prepared by reaction of aromatic and primary and secondary alkyllithium reagents with anhydrous cerium chloride, add to nitriles twice to give tertiary carbinamines in often excellent yields.Addition of n-BuCeCl2 to acetophenone is about 4 times faster than addition to benzonitrile.Only 1,2-diaddition is observed in the reaction of MeCeCl2 with cinnamonitrile.The species formed in the double addition of organocerium reagents to nitriles are sufficiently basic to generate a benzyne intermediate by abstraction of an aromatic proton and nucleophilic enough to undergo an intramolecular Chichibabin reaction.Reaction of N-unsubstituted ketimines or their lithium salts with organocerium reagents permits the synthesis of tertiary carbinamines with three different groups on the tertiary carbon center.
