40463-08-9Relevant articles and documents
Dirhodium(II)-Mediated Alkene Epoxidation with Iodine(III) Oxidants
Nasrallah, Ali,Grelier, Gwendal,Lapuh, Maria Ivana,Duran, Fernando J.,Darses, Benjamin,Dauban, Philippe
supporting information, p. 5836 - 5842 (2018/11/24)
Dirhodium(II) complexes and iodine(III) oxidants have found useful applications in synthetic nitrene chemistry. In this study, the combination of the dirhodium(II) complex Rh2(tpa)4 (tpa = triphenylacetate) with the iodine(III) oxidant PhI(OPiv)2 is shown to promote the epoxidation of alkenes in the presence of 2 equivalents of water. The reaction can be applied to diversely substituted alkenes and the corresponding epoxides are isolated with yields of up to 90 %. A possible mechanism involves the dirhodium(II) complex as a Lewis acid species that would tune the oxidizing character of the iodine(III) reagent.
Expedient Access to 2,3-Dihydropyridines from Unsaturated Oximes by Rh(III)-Catalyzed C-H Activation
Romanov-Michailidis, Fedor,Sedillo, Kassandra F.,Neely, Jamie M.,Rovis, Tomislav
supporting information, p. 8892 - 8895 (2015/08/03)
α,β-Unsaturated oxime pivalates are proposed to undergo reversible C(sp2)-H insertion with cationic Rh(III) complexes to furnish five-membered metallacycles. In the presence of 1,1-disubstituted olefins, these species participate in irreversible migratory insertion to give, after reductive elimination, 2,3-dihydropyridine products in good yields. Catalytic hydrogenation can then be used to convert these molecules into piperidines, which are important structural components of numerous pharmaceuticals.
New metal-free one-pot synthesis of substituted allenes from enones
Tang, Meng,Fan, Chun-An,Zhang, Fu-Min,Tu, Yong-Qiang,Zhang, Wen-Xue,Wang, Ai-Xia
supporting information; experimental part, p. 5585 - 5588 (2009/06/18)
(Chemical Equation Presented) A new metal-free, one-pot synthesis of substituted allenes from enones was discovered for the first time, in which a tertiary amine as a base was found to be an effective promoter in such novel transformations. The present synthetic protocol proceeded readily with high compatibility of sensitive functional groups, and it provides a new efficient way to access a series of synthetically important allenes without the use of metallic reagents or catalysts.
Superbase-promoted rearrangement of oxiranes to cyclopropanes
Mordini, Alessandro,Peruzzi, Daniela,Russo, Francesco,Valacchi, Michela,Reginato, Gianna,Brandi, Alberto
, p. 3349 - 3360 (2007/10/03)
Aryl- and alkenyl substituted oxiranes, when submitted to treatment with superbasic reagents, undergo a highly regio- and stereoselective rearrangement leading to cyclopropylmethanol derivatives. The process can also be applied to mono- and dihydroxy subs
New molybdenum catalysts for alkyl olefin epoxidation. Their implications for the mechanism of oxygen atom transfer
Mitchell,Finney
, p. 862 - 869 (2007/10/03)
We report here the design, synthesis, and characterization of new (dioxo)Mo(VI) epoxidation catalysts based on monoanionic tridentate ligands. Two important features distinguish these catalysts from those previously reported. First, their coordination env
Cyclialkylation of arylalkyl epoxides with solid acid catalysts
Elings, Jacob A.,Downing, Roger S.,Sheldon, Roger A.
, p. 837 - 846 (2007/10/03)
Solid acids, such as zeolites and clays, catalyse the intramolecular hydroxyalkylation (cyclialkylation) of several arylalkyl epoxides in moderate to excellent conversions and selectivities. The use of solid acids in these cyclialkylations provides a cleaner, better alternative to conventional Lewis and Bronsted acids, enabling a more facile workup of reaction mixtures and, in several cases, better selectivities.
