93663-32-2Relevant academic research and scientific papers
Iron-Catalyzed Dioxygenation of Alkenes and Terminal Alkynes by using (Diacetoxyiodo)benzene as Oxidant
Srinivas,Rawat, Vikas S.,Sreedhar, Bojja
supporting information, p. 3587 - 3596 (2016/01/25)
An iron-catalyzed syn-diacetoxylation of alkenes and 1,2-oxyacetoxylation of terminal alkynes has been developed using (diacetoxyiodo)benzene as oxidant. A broad range of internal and terminal alkenes, including electron-rich as well as electron-deficient alkenes, gave the desired products in good to excellent yields with high diastereoselectivity (up to >99:1 dr). In addition the high catalytic activity of iron catalysis for the 1,2-oxyacetoxylation of terminal alkynes is also reported. The roles of catalyst, oxidant and other reaction parameters were evaluated for activation of the unsaturated bond.
"Site Selective" Formation of Low-Valent Titanium Reagents: An "Instant" Procedure for the Reductive Coupling of Oxo Amides to Indoles
Fuerstner, Alois,Hupperts, Achim,Ptock, Arne,Janssen, Edo
, p. 5215 - 5229 (2007/10/02)
Aromatic acylamido carbonyl compounds are readily cyclized to indole derivatives upon treatment with low-valent titanium reagents of the formal oxidation states 0, +1, and +2.Other strong reducing agents such as SmI2 and low-valent zirconium, niobium, and tungsten complexes are also capable of effecting such intramolecular alkylidenation reactions of amides.From the preparative point of view these heterocycle syntheses are best effected with an active titanium species which is prepared in the presence of the carbonyl compound upon coordination of TiCln (n = 3, 4) to the oxo amide substrate and reduction of this complex with zinc dust ("instant" method).This procedure turned out to be as effective as the titanium-graphite-based methodology previously described but is much easier to perform as all hazardous reagents are avoided. "Instant" cyclizations can also be run in nonetheral solvents such as DMF, ethyl acetate, or acetonitrile and turned out to be compatible with many functional groups.The method was used to cyclize oxo amide 15 to (+)-aristoteline, and it applies nicely to the synthesis of strained indole derivatives, the formation of benzofurans, conventional McMurry reactions of aldehydes and ketones, and the dimerization of alkynes.Metals such as zirconium can also be activated in situ by reduction of ZrCl4 in the presence of a carbonyl compound.On the basis of the results obtained with substrates bearing appropriate structural probes a mechanism for such intramolecular keto-amide coupling processes is proposed.Carbonyl dianions, formed upon two-electron reduction of the keto group, are the most likely reactive intermediates.Electrochemical investigations support this mechanistic interpretation.
Reactions of Substituted Phenacyl Bromides with Various Bases. o- and p-Nitrophenacyl Bromide. I
Scott, James H.,Smith, Thomas A.,Hutchinson, James H.
, p. 903 - 904 (2007/10/02)
The product obtained from the reaction of o- and p-nitrophenacyl bromide with various bases is described.
