81454-71-9Relevant academic research and scientific papers
Photoredox-Catalyzed Isomerization of Highly Substituted Allylic Alcohols by C?H Bond Activation
Guo, Kai,Huang, Jun,Li, Anding,Li, Yuanhe,Yang, Zhen,Zhang, Zhongchao
supporting information, p. 11660 - 11668 (2020/05/25)
Photoredox-catalyzed isomerization of γ-carbonyl-substituted allylic alcohols to their corresponding carbonyl compounds was achieved for the first time by C?H bond activation. This catalytic redox-neutral process resulted in the synthesis of 1,4-dicarbonyl compounds. Notably, allylic alcohols bearing tetrasubstituted olefins can also be transformed into their corresponding carbonyl compounds. Density functional theory calculations show that the carbonyl group at the γ-position of allylic alcohols are beneficial to the formation of their corresponding allylic alcohol radicals with high vertical electron affinity, which contributes to the completion of the photoredox catalytic cycle.
Grubbs cross-metathesis pathway for a scalable synthesis of γ-keto-α,β-unsaturated esters
Nair, Reji N.,Bannister, Thomas D.
, p. 1467 - 1472 (2014/03/21)
A direct and scalable route to γ-keto-α,β-unsaturated esters, useful intermediates in medicinal chemistry and natural products synthesis, is reported. The key step involves the use of Grubbs' second-generation olefin metathesis catalyst for cross-metathes
Cross metathesis of allyl alcohols: How to suppress and how to promote double bond isomerization
Schmidt, Bernd,Hauke, Sylvia
, p. 4194 - 4206 (2013/07/05)
Under standard conditions the cross metathesis of allyl alcohols and methyl acrylate is accompanied by the formation of ketones, resulting from uncontrolled and undesired double bond isomerization. By conducting the CM in the presence of phenol, the catalyst loading and the reaction time required for quantiative conversion can be reduced, and isomerization can be suppressed. On the other hand, consecutive isomerization can be deliberately promoted by evaporating excess methyl acrylate after completing cross metathesis and by adding a base or silane as chemical triggers.
γ-oxygenation of α,β-unsaturated esters by vinylogous O-nitroso mukaiyama aldol reaction
Tian, Guo-Qiang,Yang, Jiong,Rosa-Perez, Kellymar
supporting information; experimental part, p. 5072 - 5074 (2010/12/25)
A practical procedure has been developed for γ-oxygenation of α,β-unsaturated esters by a vinylogous O-nitroso Mukaiyama aldol reaction followed by a one-pot N-O bond heterolysis of the in situ generated γ-aminoxy-α,β-unsaturated esters.
On the Preparation and Rearrangement of Some Vinylic Sulphoxides
Cass, Quezia B.,Jaxa-Chamiec, Albert A.,Kunec, Ellen K.,Sammes, Peter G.
, p. 2683 - 2686 (2007/10/02)
The condensation of methyl benzenesulphinylacetate 1 with a series of aldehydes has been explored using different catalysts.With zinc chloride, the enolate of 1 produces the conjugated ester directly.A base-catalysed rearrangement of these conjugated este
A novel palladium-catalyzed deoxygenation of enediols to 1,3-dienes
Trost,Tometzki
, p. 1235 - 1245 (2007/10/02)
Hydroxylative Knoevenagel condensation of aldehydes followed by reduction provides a simple entry to 1,4-enediols. Subjecting the dicarbonate to a palladium(0) catalyst in the presence of triisopropyl phosphite achieves a mild vinylogous deoxygenation to (E)-1,3-dienes. Stereocontrolled synthesis of the sex pheromone of the red bollworm moth, (E)-9,11-dodecadienyl acetate, and a formal synthesis of the cotton boll weevil antifeedant, α-eleostearic acid, demonstrate the utility of this new methodology.
Preparation and Rearrangement of Some Conjugated Phenylsulphinylacetate Derivatives
Cass, Quezia B.,Jaxa-Chamiec, Albert A.,Sammes, Peter G.
, p. 1248 - 1250 (2007/10/02)
The direct condensation of saturated or unsaturated aldehydes with methyl phenylsulphinylacetate can be effected with the products undergoing base-catalysed rearrangements, those from saturated aldehydes yielding γ-hydroxy-αβ-unsaturated esters, whilst crotonaldehyde gives rise to methyl 6-phenylsulphinylhexa-2,4-dienoate.
