62681-85-0Relevant academic research and scientific papers
Rhodium-Catalyzed and Chiral Zinc Carboxylate-Assisted Allenylation of Benzamides via Kinetic Resolution
Mao, Ruxia,Zhao, Yanliang,Zhu, Xiaohan,Wang, Fen,Deng, Wei-Qiao,Li, Xingwei
supporting information, p. 7038 - 7043 (2021/09/18)
Enantioenriched allenes are important building blocks. While they have been accessed by other coupling methodologies, enantioenriched allenes have been rarely obtained via C-H activation. In this work, kinetic resolution of tertiary propargyl alcohols as an allenylating reagent has been realized via rhodium(III)-catalyzed C-H allenylation of benzamides. The reaction proceeded efficiently under mild conditions, and both the allenylated products and the propargyl alcohols were obtained in high enantioselectivities with an s-factor of up to 139. The resolution results from bias of the two propargylic substituents and is assisted by a chiral zinc carboxylate additive.
An evaluation of substituent effects on aromatic edge-to-face interactions and CF-π versus CH-π interactions using an imino torsion balance model
Jennings, W. Brian,O'Connell, Niamh,Malone, John F.,Boyd, Derek R.
, p. 5278 - 5291 (2013/08/23)
A selection of imines derived from phenyl t-butyl ketones and substituted 2-phenylethylamines or phenylalanine exhibit slow rotation around the aryl-imino bond at ambient temperature, resulting in a large non-equivalence of the ortho hydrogens in the 1H NMR spectra. This facilitates assessment of aryl substituent effects on the face tilted-T CH-π interaction between a phenyl ring (A) on the imino carbon proximate to the terminal phenyl ring (B). Analysis of the marked temperature dependence of the chemical shift of the interacting ortho hydrogen affords estimates of the opposing enthalpic and entropic factors involved in the rapid equilibrium between the closed edge-to-face conformation and alternative open conformations devoid of a CH-π interaction while in solution. Above ca. 80 °C the entropy term (TΔS) cancels out the enthalpy (ΔH) favouring the closed conformation and open conformations are preferred. Accordingly, commonly reported binding free energies may not be a good measure of the energetic strength of intramolecular aromatic interactions. Investigation of an ortho fluoro substituted compound indicates that a CF-π interaction is at least 1.0 kcal mol-1 weaker in enthalpy than the CH-π interaction. Several X-ray crystal structures depicting an intramolecular edge-to-face interaction are presented.
Catalyst-free alkanoylation of aromatic rings via arylstannanes. Scope and limitations
Lo Fiego, Marcos J.,Lockhart, María T.,Chopa, Alicia B.
supporting information; experimental part, p. 3674 - 3678 (2010/01/18)
The reaction of alkanoyl chlorides with arylstannanes in 1,2-dichlorobenzene (180 °C) is a simple and direct route for the catalyst-free and regioselective synthesis of tertiary alkyl aryl ketones in good to excellent isolated yields (55-77%). Nevertheles
