830-13-7Relevant articles and documents
EFFECT OF RING SIZE ON THE ACID-CATALYSED HYDROLYSIS OF CYCLIC α,β-EPOXYSILANES
Nagendrappa, Gopalpur,Vidyapati, T. J.
, p. 31 - 38 (1985)
Acid-catalysed hydrolysis of epoxysilanes derived from common-, medium- and large-ring vinylsilanes is described.Whereas the large epoxysilanes give ketones, the medium-ring epoxysilanes give transannular products and the common-ring epoxysilanes provide α,β-dihydroxysilanes.The results are explained as due to the conformational rigidity in the common-ring silyldiols and the conformational freedom in the large-ring silyldiols to achive antiperiplanar geometry for 1,2-elimination of trimethylsilanol.
The effect of ligand variation on the rate of cyclododecane oxidation under modified GoAgg(II) conditions
About-Jaudet,Barton,Csuhai,Ozbalik
, p. 1657 - 1660 (1990)
The effect of various ligands on the GoAgg(II) oxidation of cyclododecane to cyclododecanone has been investigated. The addition of picolinic acid and a number of its congeners increases the rate of oxidation up to fiftyfold. On the other hand, the addition of pyridine-2-phosphonic acid stops oxidation completely.
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McCormick
, p. 1701 (1974)
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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
supporting information, 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.
Efficient oxidation of cycloalkanes with simultaneously increased conversion and selectivity using O2 catalyzed by metalloporphyrins and boosted by Zn(AcO)2: A practical strategy to inhibit the formation of aliphatic diacids
Shen, Hai-Min,Wang, Xiong,Ning, Lei,Guo, A-Bing,Deng, Jin-Hui,She, Yuan-Bin
, (2020/11/20)
The direct sources of aliphatic acids in cycloalkanes oxidation were investigated, and a strategy to suppress the formation of aliphatic acids was adopted through enhancing the catalytic transformation of oxidation intermediates cycloalkyl hydroperoxides to cycloalkanols by Zn(II) and delaying the emergence of cycloalkanones. Benefitted from the delayed formation of cycloalkanones and suppressed non-selective thermal decomposition of cycloalkyl hydroperoxides, the conversion of cycloalkanes and selectivity towards cycloalkanols and cycloalkanones were increased simultaneously with satisfying tolerance to both of metalloporphyrins and substrates. For cyclohexane, the selectivity towards KA-oil was increased from 80.1% to 96.9% meanwhile the conversion was increased from 3.83 % to 6.53 %, a very competitive conversion level with higher selectivity compared with current industrial process. This protocol is not only a valuable strategy to overcome the problems of low conversion and low selectivity lying in front of current cyclohexane oxidation in industry, but also an important reference to other alkanes oxidation.
Electrochemically driven desaturation of carbonyl compounds
Gnaim, Samer,Takahira, Yusuke,Wilke, Henrik R.,Yao, Zhen,Li, Jinjun,Delbrayelle, Dominique,Echeverria, Pierre-Georges,Vantourout, Julien C.,Baran, Phil S.
, p. 367 - 372 (2021/03/31)
Electrochemical techniques have long been heralded for their innate sustainability as efficient methods to achieve redox reactions. Carbonyl desaturation, as a fundamental organic oxidation, is an oft-employed transformation to unlock adjacent reactivity through the formal removal of two hydrogen atoms. To date, the most reliable methods to achieve this seemingly trivial reaction rely on transition metals (Pd or Cu) or stoichiometric reagents based on I, Br, Se or S. Here we report an operationally simple pathway to access such structures from enol silanes and phosphates using electrons as the primary reagent. This electrochemically driven desaturation exhibits a broad scope across an array of carbonyl derivatives, is easily scalable (1–100 g) and can be predictably implemented into synthetic pathways using experimentally or computationally derived NMR shifts. Systematic comparisons to state-of-the-art techniques reveal that this method can uniquely desaturate a wide array of carbonyl groups. Mechanistic interrogation suggests a radical-based reaction pathway. [Figure not available: see fulltext.]