80865-95-8Relevant academic research and scientific papers
N,2-Dilithioalkylamines from Aziridines by Naphthalene-Catalyzed Reductive Opening. Synthetic Applications
Almena, Juan,Foubelo, Francisco,Yus, Miguel
, p. 3210 - 3215 (1994)
The reductive opening of aziridines 1a-c with lithium in the presence of a catalytic amount of naphthalene at -78 deg C led to the corresponding dianionic intermediates 2a-c, which are stable species under these reaction conditions and react with electrophilic reagents , (EtO)2CO, CH2=CHCO2Me, , PhCH=NPh, MeI, and CH2=CHCH2Br> to give, after hydrolysis with water, the corresponding difunctionalized compounds 3-5.When the reductive opening and the reaction with electrophiles were carried out on chiral aziridines 8 and 9, enantiomerically pure difunctionalized compounds 12 were obtained with the same stereochemistry, independently of the stereochemistry of diastereomeric starting aziridines 8 and 9.
β-Substituted Organoalkaline Tri- and Tetra-anions; Preparation, Stability, and Reactivity
Barluenga, Jose,Fananas, Francisco J.,Villamana, Jorge,Yus, Miguel
, p. 2685 - 2692 (2007/10/02)
New β,γ-, β,β'-disubstituted organometallic trianions of the type C(Y)C(Y')C(8) and C(Y)CC(Y') (18) (Y = or (*) Y' = O, PhN), β-substituted organodimetallic trianions of the type CC(PhN)C (25) with alkali-metal cations (Li, Na, and K), and a lithiated tetra-anion of the type CC(PhN)C(PhN)C (32) are obtained from the corresponding substituted organomercury(II) compounds via low-temperature mercury-alkali metal transmetallation.The starting organomercurials can be obtained by solvomercuriation from suitable unsaturated systems.These polyanion derivatives are stable species only at temperatures in the range -78 to -100 deg C; at higher temperatures rapid decomposition takes place via either a β-elimination process or proton abstraction from the reaction media.The new polyanionic compounds are characterized by transformation into their deuterio derivatives with deuterium oxide at low temperature.The thermal decomposition of these organometallic intermediates is also reported.The reactivity of the lithiated trianion derived from isopropylaniline (25a) with different agents (ethyl bromide, dimethyl disulphide, and trimethylchlorosilane) in a successive or simultaneous way is studied; this process occurs in a regioselective manner.
β-Substituted Organolithium Compounds. Reaction with Alkyl Halides, Dimethyl Disulfide, and Imines
Barluenga, Jose,Fananas, Francisco J.,Villamana, Jorge,Yus, Miguel
, p. 1560 - 1564 (2007/10/02)
The reaction of β-substituted organolithium derivatives with several electrophiles leads to mono- as well as bifunctionalized organic compounds.Thus, by treatment of these dianions with alkyl halides a direct attack on the carbanionic carbon atom is performed, giving as a result substituted amines.When dimethyl disulfide is used, β-amino and β-hydroxy thioethers are obtained.Finally, on reaction with imines, 1-amino-3-hydroxy compounds and 1,3-diamines are obtained.Since these dianions are easily preparated by mercury-lithium transmetalation from β-substituted organomercurials resulting from the addition of mercury(II) salts to olefins, this whole process gives an appropriate way of functionalizing olefins.
