2769-45-1Relevant academic research and scientific papers
α-Tetrasubstituted Aldehydes through Electronic and Strain-Controlled Branch-Selective Stereoselective Hydroformylation
Eshon, Josephine,Foarta, Floriana,Landis, Clark R.,Schomaker, Jennifer M.
, p. 10207 - 10220 (2018/09/06)
Hydroformylation utilizes dihydrogen, carbon monoxide, and a catalyst to transform alkenes into aldehydes. This work applies chiral bisdiazaphospholane (BDP)- and bisphospholanoethane-ligated rhodium complexes to the hydroformylation of a variety of alkenes to produce chiral tetrasubstituted aldehydes. 1,1′-Disubstituted acrylates bearing electron-withdrawing substituents undergo hydroformylation under mild conditions (1 mol % of catalyst/BDP ligand, 150 psig gas, 60 °C) with high conversions and yields of tetrasubstituted aldehydes (e.g., 13:1 regioselectivity, 85% ee, and 99% regioselectivity and >19:1 diastereoselectivity to tetrasubstituted aldehydes at rates >50 catalyst turnovers/hour. NMR studies of the noncatalytic reaction of HRh(BDP)(CO)2 with methyl 1-fluoroacrylate enable interception of tertiary alkylrhodium intermediates, demonstrating migratory insertion to acyl species is slower than formation of secondary and primary alkylrhodium intermediates. Overall, these investigations reveal how the interplay of sterics, electronics, and ring strain are harnessed to provide access to valuable α-tetrasubstituted aldehyde synthetic building blocks by promoting branched-selective hydroformylation.
Heterocyclization of iminium salts from some β-amino-β-lactams and their gem-difunctional derivatives
Nisole,Uriac,Huet,Toupet
, p. 1081 - 1098 (2007/10/02)
β-Amino-β-lactams and their gem-difunctional derivatives of two series (1-benzoazepine and linear analog) lead stereospecifically to two types of heterocycles in strong acidic medium. Iminium ions and benzylic carbocations are proposed as reactive intermediates.
