639860-75-6Relevant academic research and scientific papers
Readily Accessible 1,2-Amino Ether Ligands for Enantioselective Intramolecular Carbolithiation
Guyon, Hélène,Boussonnière, Anne,Castanet, Anne-Sophie
, p. 4949 - 4957 (2017/05/12)
A new class of chiral 1,2-amino ether ligands, readily accessible from naturally occurring α-amino- or α-hydroxy acids, was found to provide high levels of both conversion and stereocontrol (up to 95:5 er) in intramolecular carbolithiation reactions, outperforming the benchmark ligand (?)-sparteine. The ligand could be used in a substoichiometric amount (0.25 equiv) without significant loss of enantioselectivity.
Hemilabile Ligands in Organolithium Chemistry: Substituent Effects on Lithium Ion Chelation
Ramirez, Antonio,Lobkovsky, Emil,Collum, David B.
, p. 15376 - 15387 (2007/10/03)
The lithium diisopropylamide-mediated 1,2-elimination of 1-bromocyclooctene to provide cyclooctyne is investigated using approximately 50 potentially hemilabile polyethers and amino ethers. Rate laws for selected ligands reveal chelated monomer-based pathways. The dependence of the rates on ligand structure shows that anticipated rate accelerations based on the gem-dimethyl effect are nonexistent and that substituents generally retard the reaction. With the aid of semiempirical and DFT computational studies, the factors influencing chelation are discussed. It seems that severe buttressing within chelates of the substitutionally rich ligands precludes a net stabilization of the chelates relative to nonchelated (η 1-solvated) forms. One ligand-MeOCH2CH2NMe 2-appears to promote elimination uniquely by a higher-coordinate monomer-based pathway.
