66323-99-7Relevant articles and documents
Kinetic enolate formation by lithium arylamide: Effects of basicity on selectivity
Xie, Linfeng,Vanlandeghem, Keith,Isenberger, Kurt M.,Bernier, Carolyn
, p. 641 - 643 (2003)
Five ketones R1COCH2R2 (1a-e) were enolized in tetrahydrofuran solvent employing lithium arylamides with different electron-withdrawing and -donating substituents on the phenyl ring (4a-e). Enolate selectivity is unaffecte
Highly Steroselective Kinetic Enolate Formation: Steric vs Electronic Effects
Xie, Linfeng,Isenberg, Kurt M.,Held, Gary,Dahl, Linnea M.
, p. 7516 - 7519 (1997)
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β-Diazocarbonyl Compounds: Synthesis and their Rh(II)-Catalyzed 1,3 C?H Insertions
Jiang, Liyin,Wang, Zhaofeng,Armstrong, Melanie,Suero, Marcos G.
supporting information, p. 6177 - 6184 (2021/02/01)
Herein, we describe the first electrophilic diazomethylation of ketone silyl enol ethers with diazomethyl-substituted hypervalent iodine reagents that gives access to unusual β-diazocarbonyl compounds. The potential of this unexplored class of diazo compounds for the development of new reactions was demonstrated by the discovery of a rare Rh-catalyzed intramolecular 1,3 C?H carbene insertion that led to complex cyclopropanes with excellent stereocontrol.
The Cyclopropane Ring as a Reporter of Radical Leaving-Group Reactivity for Ni-Catalyzed C(sp3)-O Arylation
Mills, L. Reginald,Monteith, John J.,Dos Passos Gomes, Gabriel,Aspuru-Guzik, Alán,Rousseaux, Sophie A. L.
supporting information, p. 13246 - 13254 (2020/09/01)
The ability to understand and predict reactivity is essential for the development of new reactions. In the context of Ni-catalyzed C(sp3)-O functionalization, we have developed a unique strategy employing activated cyclopropanols to aid the design and optimization of a redox-active leaving group for C(sp3)-O arylation. In this chemistry, the cyclopropane ring acts as a reporter of leaving-group reactivity, since the ring-opened product is obtained under polar (2e) conditions, and the ring-closed product is obtained under radical (1e) conditions. Mechanistic studies demonstrate that the optimal leaving group is redox-active and are consistent with a Ni(I)/Ni(III) catalytic cycle. The optimized reaction conditions are also used to synthesize a number of arylcyclopropanes, which are valuable pharmaceutical motifs.
Organosilicon Reducing Reagents for Stereoselective Formations of Silyl Enol Ethers from α-Halo Carbonyl Compounds
Pramanik, Suman,Rej, Supriya,Kando, Shun,Tsurugi, Hayato,Mashima, Kazushi
, p. 2409 - 2417 (2018/02/23)
Salt-free stereoselective synthesis of silyl enol ethers was achieved by treating α-halo carbonyl compounds with 2,3,5,6-tetramethyl-1,4-bis(trimethylsilyl)-1,4-dihydropyrazine. In this reaction, easily removable trimethylsilyl halides and 2,3,5,6-tetramethylpyrazine were generated as the reaction byproducts. Due to the inertness of the reaction byproducts, we found a one-pot transformation of the in situ generated silyl enol ethers into various α-functionalized carbonyls by reaction with Togni-II reagent or aldehydes.