86428-59-3Relevant academic research and scientific papers
Beyond Chemoselectivity: Catalytic Site-Selective Aldolization of Diketones and Exploitation for Enantioselective Alzheimer's Drug Candidate Synthesis
Nugent, Thomas C.,Najafian, Foad Tehrani,Hussein, Hussein Ali El Damrany,Hussain, Ishtiaq
supporting information, p. 14342 - 14348 (2016/09/23)
Site selectivity, differentiating instances of the same functional group type on one substrate, represents a forward-looking theme within chemistry: reduced dependence on protection/deprotection protocols for increased overall yield and step-efficiency. Despite these potential benefits and the expanded tactical advantages afforded to synthetic design, site selectivity remains elusive and especially so for ketone-based substrates. Herein, site-selective intermolecular mono-aldolization has been demonstrated for an array of prochiral 4-keto-substituted cyclohexanones with concomitant regio-, diastereo-, and enantiocontrol. Importantly, the aldol products allow rapid access to molecularly complex ketolactones or keto-1,3-diols, respectively containing three and four stereogenic centers. The reaction conditions are of immediate practical value and general enough to be applicable to other reaction types. These findings are applied in the first enantioselective, formal, synthesis of a leading Alzheimer's research drug, a γ-secretase modulator (GSM), in the highest known yield.
Simultaneous functional group manipulation in the Meerwein-Ponndorf- Verley reduction process catalyzed by bidentate aluminum reagent
Ooi, Takashi,Itagaki, Yoshifumi,Miura, Tomoya,Maruoka, Keiji
, p. 2137 - 2138 (2007/10/03)
Simultaneous reduction/oxidation sequence of hydroxy carbonyl substrates through Meerwein-Ponndorf-Verley reduction can be facilitated in the presence of bidentate aluminum catalyst, (2,7-dimethyl-1,8- biphenylenedioxy)bis(dimethylaluminum). This new appr
Drastic ring transformation reactions of fused bicyclic rings to bridged bicyclic rings
Yamamoto, Takayoshi,Eki, Toshiko,Nagumo, Shinji,Suemune, Hiroshi,Sakai, Kiyoshi
, p. 4517 - 4524 (2007/10/02)
By treatment with BF3-etheratelethylene glycol, cyclohexanone with a carbonyl function at the 2′-(or 3′-) position of γ-side chain underwent novel ring transformation to afford five- (or six-) membered rings, and the fused bicyclic rings (bicyc
DECOMPOSITION DU PERCARBONATE DE O,O-t-BUTYLE ET O-ISOPROPENYLE EN SOLUTION-2. ACETONYLATION DE CYCLANONES ET OXACYCLANES.
Jaouhari, R.,Maillard, B.,Filliatre, C.,Villenave, J. J.
, p. 1559 - 1566 (2007/10/02)
The decomposition of O,O-tert-butyl and O-isopropenyl peroxycarbonate in cyclanones and oxycyclanes leads to acetonylated derivatives of these solvents.Although the reaction mechanism involves in both cases the addition of free radicals derived from solvent to the double bond of the peroxycarbonate, the orientation of the whole process depends on the solvent.In the case of oxacyclanes the relative ratios of α-,β-and γ-(with regard to the heteroatom) acetonylated products are likely to express the reactivity of t-butoxy radicals towards the differenet carbon atoms of the solvent.On the contrary, in the case of cyclanones transfer reactions occur from β- or γ-radicals (with regard to the carbonyl group) to α-carbon atoms of other solvent molecules and the relative ratios of α-, β- and γ-acetonylated products depend on on the peroxycarbonate concentration: when it is high, about 25percent β and γ isomers are formed; when it is low, only the α isomer is obtained.
Reactions radicalaires du percarbonate de O,O-tert-butyle et O-isopropenyle: acetonylations assistees par un co-amorceur
Jaouhari, Rabih,Filliatre, Claude,Villenave, Jean-Jacques
, p. 2295 - 2298 (2007/10/02)
By decomposition in alkanes, ethers, ketones, acids, esters and nitriles of equimolecular mixtures of O,O-tert-butyl and O-isopropenyl peroxicarbonate and tert-butyl peroxyacetate, the "assisted" acetonylation of the solvents has been accomplished.The presence of the co-initiator allows the yield of the free radical acetonylation to be markedly improved: the formation of the by-product acetonylacetone is avoided and the yield of acetonylated derivatives is strongly enhanced while the regioselectivity of the processes is preserved and even increased in some cases.
