930-30-3Relevant articles and documents
Synthesis of functionalized olefins by cross and ring-closing metatheses [7]
Chatterjee, Arnab K.,Morgan, John P.,Scholl, Matthias,Grubbs, Robert H.
, p. 3783 - 3784 (2000)
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Independent generation of triplet 1,4-biradical intermediates implicated in the photochemical cycloaddition reaction between 2-cyclopentenone and acrylonitrile
Krug,Rudolph,Weedon
, p. 7221 - 7224 (1993)
Norrish Type 1 photochemistry of 3-cyanobicyclo[3.3.0]octane-2,6-dione and 3-cyanobicyclo[3.3.0]octane-2,8-dione is used to generate triplet 1,4-biradicals implicated in the photochemical cycloaddition reaction of 2-cyclopentenone with acrylonitrile. The fates of these biradicals have been determined and they suggest that the photocycloaddition reaction regiochemistry is governed by competition between closure of the biradicals to product and their reversion to ground state starting materials. This provides further evidence against the long-held view that the relative rates of formation of the biradicals mediated by an oriented triplet exciplex governs the reaction regiochemistry. It is also found that the regiochemistry of the photochemical cycloaddition reaction between cyclopentenone and acrylonitrile is reversed from that obtained in the addition of acrylonitrile to 2-cyclohexenone.
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.]
K2S2O8-promoted C-Se bond formation to construct α-phenylseleno carbonyl compounds and α,β-unsaturated carbonyl compounds
Yang, Xue-Yan,Wang, Ruizhe,Wang, Lu,Li, Jianjun,Mao, Shuai,Zhang, San-Qi,Chen, Nanzheng
, p. 28902 - 28905 (2020/08/25)
A novel K2S2O8-promoted C-Se bond formation from cross-coupling under neutral conditions has been developed. A variety of aldehydes and ketones react well using K2S2O8 as the oxidant in the absence of catalyst and afford desired products in moderate to excellent yields. This protocol provides a very simple route for the synthesis of α-phenylseleno carbonyl compounds and α,β-unsaturated carbonyl compounds.