15332-75-9Relevant academic research and scientific papers
Chemoselective oxidative hydrolysis of EWG protected α-arylamino vinyl bromides to α-arylamino-α′-bromoacetones
Pace, Vittorio,Castoldi, Laura,Hernáiz, María J.,Alcántara, Andrés R.,Holzer, Wolfgang
supporting information, p. 4369 - 4372 (2013/07/26)
Vinyl bromides bearing an arylamino group in the vicinal position are chemoselectively transformed into interesting α-arylamino-α′- bromoacetones through a straightforward oxidative hydrolysis promoted by calcium hypobromite under mild acidic conditions. Significantly, this particular combination [vinyl bromides and Ca(BrO)2] avoids bromination at both the aromatic ring and activated positions in groups substituting the amine nitrogen. The usefulness of this class of brominated ketones has been shown in a Wittig homologation.
Effective monoallylation of anilines catalyzed by supported KF
Pace, Vittorio,Martinez, Fernando,Fernandez, Maria,Sinisterra, Jose V.,Alcantara, Andres R.
, p. 2661 - 2664 (2008/02/08)
Equation Presented A mild and straightforward monoallylation procedure for different anilines is described using the efficient, inexpensive, noncorrosive, and environmentally friendly reagent KF-Celite. By using only a 1/1.2 stoichiometric ratio of electrophilic reagent to aniline, in very short reaction times, the monoallylated products are obtained in high isolated yields via this procedure, which works very effectively regardless of the electronic nature of the substituent on the ring, although electron withdrawing groups make the reactions go even faster.
Cyclizations and Rearrangements of Samarium Diiodide-Generated Vinyl Radicals
Capella, Laura,Montevecchi, Pier Carlo,Navacchia, Maria Luisa
, p. 7424 - 7432 (2007/10/03)
Vinyl bromides 1, 5, 15, 20, 23, 27, 33a,b, 41a-c, 44a-c, 46a,b, 52a,b, 55a, 56a,b, and 60a,b react with samarium diiodide in THF and/or acetonitrile to give the corresponding vinyl radicals.Radicals 3, 7, and 16 afforded products deriving from cyclization on the adjacent triple bond in a 5-(?-exo)exo, 6-(?-endo)exo, and 6-(?-exo)exo mode, respectively.Radical 7 undergoes competitive 1,5-hydrogen translocation.Vinyl radicals 21 and 24 readily cyclize on the proximal double bond, leading to 5- and 6-membered rings, respectively.Thienyl-substituted radical 28 leads to a product deriving from 5-exo cyclization on the thiophene ring and subsequent β-fission of the C-S bond, whereas thienyl-substituted radicals 34a,b undergo almost exclusively 1,5-hydrogen translocation.Aryl-substituted radicals obtained from vinyl bromides 41, 44, 46, 52, and 55 do not form any products deriving from 5-exo or 6-exo cyclization (or ipso cyclization).Finally, naphthyl-substituted radicals 57a and 61a give only direct reduction products, whereas the radical 61b affords, in addition to the direct reduction product, a rearranged product deriving from a 1,3-radical migration of the naphthylthio group.Evidence is reported for the reduction of EWG-substituted benzene rings and thio-substituted naphthalene rings to radical anions, which can fragment on the side chain with the elimination of allyl radicals. α-Oxy(and α-thio)-substituted radicals deriving from 1,5-shift rearrange to alcohols (and thiols) through a Wittig rearrangement or a cyclization/fragmentation process.
N-Substituted Lithium 2-Lithioallylamines: New Intermediates in Synthesis
Barluenga, Jose,Foubelo, Francisco,Fananas, Francisco J.,Yus, Miguel
, p. 553 - 557 (2007/10/02)
N-Phenyl or N-benzoyl 2-halogenoallylamines (5) or (10) react successively with phenyl-lithium and lithium naphthalenide at -78 deg C to give the intermediates (4) or (11), which on reaction with electrophiles (water, deuterium oxide, dimethyl disulphide, aldehydes, ketones, or allyl bromide) yield functionalized allyl amines (6) and (12).The corresponding N-alkyl derivatives (9) afford prop-2-ynylamines (8) under the same reaction conditions.
