70107-41-4Relevant academic research and scientific papers
Convenient and easy access to 2-hydroxycyclopent-2-enones from acylcyanohydrins
Pantin, Mathilde,Bodinier, Florent,Saillour, Jordan,Youssouf, Yassine M.,Boeda, Fabien,Pearson-Long, Morwenna S.M.,Bertus, Philippe
, p. 4657 - 4662 (2019/07/16)
A convenient access to 2-hydroxycyclopentenones was designed from acylcyanohydrins, by using titanacyclopropane complexes as nucleophilic partners and an intramolecular aldol condensation in basic conditions. The development of a one-pot procedure allows a step- and atom-economic process, and the use of Grignard reagents other than ethylmagnesium bromide provided valuable 3,4-disubstituted 2-hydroxycyclopentenones. The utility of the hydroxy group was illustrated by further functionalization of the α-position using palladium-mediated cross-coupling reactions.
Titanium-mediated addition of grignard reagents to acyl cyanohydrins: Aminocyclopropane versus 1,4-diketone formation
Setzer, Paul,Forcher, Gwenael,Boeda, Fabien,Pearson-Long, Morwenna S. M.,Bertus, Philippe
, p. 171 - 180 (2014/01/06)
The 1,2-dianion reactivity of the reagent generated from EtMgBr and titanium isopropoxide was illustrated when N-acyl cyanohydrins were used as substrates (>20 examples), giving both aminocyclopropane derivatives and 1,4-dicarbonyl compounds. When the reaction was performed in diethyl ether, 5-hydroxy-1,4-diketones were the main product. Under specific conditions (use of tetrahydrofuran and a bulky carboxylic moiety), the cyclopropane derivatives were obtained in good yields. The observed dichotomy may be explained by a ring-opening of the five-membered titanacycle intermediate followed by a nonselective acyl addition. The 1,2-dianion reactivity of the reagent generated from EtMgBr and Ti(OiPr)4 was illustrated when N-acyl cyanohydrins were used as substrates (>20 examples). When the reaction was performed in diethyl ether, 1,4-diketones were mainly isolated. Under certain conditions, cyclopropane derivatives were also obtained in good yields. A mechanism rationalizing this dichotomy is presented. Copyright
Titanium-mediated synthesis of 1,4-diketones from grignard reagents and acyl cyanohydrins
Setzer, Paul,Beauseigneur, Alice,Pearson-Long, Morwenna S. M.,Bertus, Philippe
supporting information; experimental part, p. 8691 - 8694 (2011/01/10)
Double duty: In the presence of titanium isopropoxide, Grignard reagents were found to react with acyl cyanohydrins to give substituted 5-hydroxy-1,4-diketones (see scheme). This new reaction involves a formal addition of a 1,2-dianion equivalent to both the ester and nitrile moieties.
Alternatives to α-Diazo Ketones for Tandem Cyclization-Cycloaddition and Carbenoid-Alkyne Metathesis Strategies. Novel Cyclic Enol-Ether Formation via Carbonyl Ylide Rearrangement Reactions
Fairfax, David J.,Austin, David J.,Xu, Simon L.,Padwa, Albert
, p. 2837 - 2844 (2007/10/02)
Attempts to form carbonyl ylides from free carbenes derived from diazirines or diazo compounds lacking electron-withdrawing substituents resulted in azine formation or Wolff rearrangement, respectively.Iodonium ylides proved to be a possible alternative to α-diazo compounds for metallocarbenoid generation, similar reactivity being observed for both systems.Studies into the rearrangement chemistry of carbonyl ylides provided a novel cyclic enol-ether synthesis via a 1,4-hydrogen shift process.
Addition of Aldehydes to Activated Double Bonds, XXVIII. Preparations and Reactions of Alkoxy- and Acetoxy-2,5-diones
Stetter, Hermann,Mohrmann, Karl-Heinrich,Schlenker, Walter
, p. 581 - 596 (2007/10/02)
Thiazolium salt-catalyzed addition of aliphatic ether-aldehydes and pyrancarbaldehydes leads to corresponding 1-alkoxy-2,5-alkanediones 1-11 and pyranyl-1,4-alkanediones 28 - 47.In the same manner aldehydes react with 1-acetoxy-3-buten-2-one to give 1-acetoxy-2,5-alkanediones 12 - 19, which after saponification yield the 1-hydroxy-5-alkyl-2,5-pentanediones 20 - 27.
