70836-95-2Relevant articles and documents
Instantaneous SmI2/H2O/amine-mediated reductions in THF
Dahlen, Anders,Hilmersson, Goeran
, p. 1123 - 1128 (2003)
The SmI2-mediated reductions of ketones, imines, and α,β-unsaturated esters have been shown to be instantaneous in the presence of H2O and an amine in THF. The SmI2-mediated reductions are not only shown to be fast and quantitative by the addition of H2O and an amine, but the workup procedures are also simplified. Competing experiments with SmI2/H2O/amine confirmed that α,β-unsaturated esters could be selectively reduced in the presence of ketones or imines. Comparison of analogue ligands showed that nitrogen and phosphorus ligands are superior to oxygen and sulfur ligands in these reductions. The trialkylphosphine 1,2-bis(dimethylphosphino)ethane (DMPE) provided a primary kinetic isotope effect, yielding a kH/kD of 4.5.
Continuous flow multistep synthesis of α-functionalized esters via lithium enolate intermediates
von Keutz, Timo,Strauss, Franz J.,Cantillo, David,Kappe, C. Oliver
, p. 3113 - 3117 (2017/11/29)
This manuscript describes a continuous flow protocol for the α-alkylation of esters. The method is based on the generation of lithium enolate intermediates from the esters and in situ delivered LDA. The process is then integrated with the electrophilic addition step and a quench in line. A series of α-functionalized ester have been prepared using this procedure with moderate to good yields. Key reaction parameters such as temperature and residence time and their influence on the reaction outcome are discussed in detail.
Overturning established chemoselectivities: Selective reduction of arenes over malonates and cyanoacetates by photoactivated organic electron donors
Doni, Eswararao,Mondal, Bhaskar,O'Sullivan, Steven,Tuttle, Tell,Murphy, John A.
supporting information, p. 10934 - 10937 (2013/08/23)
The prevalence of metal-based reducing reagents, including metals, metal complexes, and metal salts, has produced an empirical order of reactivity that governs our approach to chemical synthesis. However, this reactivity may be influenced by stabilization of transition states, intermediates, and products through substrate-metal bonding. This article reports that in the absence of such stabilizing interactions, established chemoselectivities can be overthrown. Thus, photoactivation of the recently developed neutral organic superelectron donor 5 selectively reduces alkyl-substituted benzene rings in the presence of activated esters and nitriles, in direct contrast to metal-based reductions, opening a new perspective on reactivity. The altered outcomes arising from the organic electron donors are attributed to selective interactions between the neutral organic donors and the arene rings of the substrates.
