13691-23-1Relevant articles and documents
Reductive Amination/Cyclization of Keto Acids Using a Hydrosilane for Selective Production of Lactams versus Cyclic Amines by Switching of the Indium Catalyst
Ogiwara, Yohei,Uchiyama, Takuya,Sakai, Norio
supporting information, p. 1864 - 1867 (2016/02/03)
Described herein is that the catalytic construction of N-substituted five- and six-membered lactams from keto acids with primary amines by reductive amination, using an indium/silane combination. This relatively benign and safe catalyst/reductant system tolerates the use of a variety of functional groups, especially ones that are reduction-sensitive. A direct switch from synthesizing lactams to synthesizing cyclic amines is achieved by changing the catalyst from In(OAc)3 to InI3. This conversion occurs by further reduction of the lactam using the indium/silane pair.
Synthesis of tricyclic nitrogen heterocycles by a sequence of palladium-catalyzed N-H and C(sp3)-H arylations
Guyonnet, Mathieu,Baudoin, Olivier
supporting information; experimental part, p. 398 - 401 (2012/02/15)
A range of tricyclic nitrogen heterocycles were synthesized in a straightforward and efficient manner via a sequence involving palladium-catalyzed N-arylation and C(sp3)-H arylation as the key steps. Whereas the C(sp3)-H arylation furnished fused 6,5,6-membered ring systems efficiently, the formation of the more strained 6,5,5-membered systems proved to be more challenging and required a subtle adjustment of the reaction conditions.
Kinetics and Equilibria of Ring Closure through an Amide Linkage. Part 2. 1-Aryl-2-pyrrolidones
Abdallah, Jassim M.,Moodie, Roy B.
, p. 1243 - 1250 (2007/10/02)
Equilibrium constants, and rate constants for forward and reverse reactions, for ring closure of several 4-(arylamino)butanoic acids to 1-aryl-2-pyrrolidones in aqueous acid, together with ionisation constants of the former group of compounds, are reported.The equilibrium constants K at 50 deg C between neutral protonic forms of open-chain and ring compounds are related to the ionisation constants of the nitrogen-protonated 4-(arylamino)butanoic acids, K1, by the equation: log K=0.70 (pK1)+1.53.The value of K for pyrrolidone itself was measured for comparison.Studies of 18O exchange reveal that (except in the case of the substrate which bears the most electron-withdrawing substituents in the aryl ring, namely 2,4-dinitro) the rate-determining step lies between the tetrahedral intermediate and the ring compound.Substituent effects and solvent deuterium isotope effects on the hydronium-ion catalysed reaction are consisitent with a transition state close to the neutral tetrahedral intermediate.The effects of methyl substituents in the heterocyclic ring on rate and equilibrium constants have also been studied.The variation of K with temperature, and derived thermodynamic parameters, are reported in two cases.
