18448-47-0Relevant articles and documents
Synthesis of α,β-unsaturated ketones and esters using polymer-supported selenium bromide
Sheng, Shou-Ri,Liu, Xiao-Ling,Wang, Xing-Cong
, p. 279 - 281 (2003)
Treatment of the polymer-supported α-phenylseleno ketones and esters prepared from polymer-supported selenium bromide with ketone and ester enolates with hydrogen peroxide afford α,β-unsaturated ketones and esters in good yields and high purities.
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Overberger,Kabasakalian
, p. 1124,1126 (1956)
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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.]
Photoredox/Cobalt Dual-Catalyzed Decarboxylative Elimination of Carboxylic Acids: Development and Mechanistic Insight
Cartwright, Kaitie C.,Joseph, Ebbin,Comadoll, Chelsea G.,Tunge, Jon A.
, p. 12454 - 12471 (2020/09/09)
Recently, dual-catalytic strategies towards the decarboxylative elimination of carboxylic acids have gained attention. Our lab previously reported a photoredox/cobaloxime dual catalytic method that allows the synthesis of enamides and enecarbamates directly from N-acyl amino acids and avoids the use of any stoichiometric reagents. Further development, detailed herein, has improved upon this transformation's utility and further experimentation has provided new insights into the reaction mechanism. These new developments and insights are anticipated to aid in the expansion of photoredox/cobalt dual-catalytic systems.
Synthetic method for 3-acetoxy-2-cyclohexenyl-1-one and derivatives thereof
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, (2019/10/01)
The invention discloses a synthetic method for 3-acetoxy-2-cyclohexenyl-1-one and derivatives thereof. The synthetic method comprises the following steps: (1) reacting a substance as described in thespecification with nitromethane at 110 DEG C to obtain a product I as described in the specification, wherein R in the product I is H or CH3; (2) reacting the product I of the step (1) with sodium nitrite and acetic acid at 37 DEG C to obtain a product II as described in the specification; (3) reacting the product II of the step (2) with methanol and concentrated sulfuric acid at 88 DEG C to obtain a product III as described in the specification; and (4) weighing the product III of the step (3), potassium carbonate, palladium on activated carbon and t-butyl hydroperoxide, adding the weighed materials into dichloromethane, carrying out a reaction at 0 DEG C, and allowing temperature to naturally rise to room temperature so as to obtain a product IV, wherein R in the product IV is H or CH3.The synthetic method of the invention is simpler and more efficient, and has high total yield; the toxicity of reagents used in the preparation is smaller than the toxicity of m-methoxybenzoic acid, thionyl chloride and the like used in the prior art; and the method is low in cost, simple and convenient in separation and purification, applicable to large-scale preparation and capable of realizingindustrial mass production. The synthetic method is applicable as a general synthetic method for 3-acetoxy-2-cyclohexenyl-1-one and 4-substituted derivatives thereof.
