Tandem Pseudopericyclic Reactions: [1,5]-X Sigmatropic Shift/6π-Electrocyclic Ring Closure ConvertingN-(2-X-Carbonyl)phenyl Ketenimines into 2-X-Quinolin-4(3H)-ones

Citations Over TimeTop 12% of 2006 papers

Abstract

N-(2-X-Carbonyl)phenyl ketenimines undergo, under mild thermal conditions, [1,5]-migration of the X group from the carbonyl carbon to the electron-deficient central carbon atom of the ketenimine fragment, followed by a 6pi-electrocyclic ring closure of the resulting ketene to provide 2-X-substituted quinolin-4(3H)-ones in a sequential one-pot manner. The X groups tested are electron-donor groups, such as alkylthio, arylthio, arylseleno, aryloxy, and amino. When involving alkylthio, arylthio, and arylseleno groups, the complete transformation takes place in refluxing toluene, whereas for aryloxy and amino groups the starting ketenimines must be heated at 230 degrees C in a sealed tube in the absence of solvent. The mechanism for the conversion of these ketenimines into quinolin-4(3H)-ones has been studied by ab initio and DFT calculations, using as model compounds N-(2-X-carbonyl)vinyl ketenimines bearing different X groups (X = F, Cl, OH, SH, NH(2), and PH(2)) converting into 4(3H)-pyridones. This computational study afforded two general reaction pathways for the first step of the sequence, the [1,5]-X shift, depending on the nature of X. When X is F, Cl, OH, or SH, the migration occurs in a concerted mode, whereas when X is NH(2) or PH(2), it involves a two-step sequence. The order of migratory aptitudes of the X substituents at the acyl group is predicted to be PH(2) > Cl > SH > NH(2) > F> OH. The second step of the full transformation, the 6pi-electrocyclic ring closure, is calculated to be concerted and with low energy barriers in all the cases. We have included in the calculations an alternative mode of cyclization of the N-(2-X-carbonyl)vinyl ketenimines, the 6pi-electrocyclic ring closure leading to 1,3-oxazines that involves its 1-oxo-5-aza-1,3,5-hexatrienic system. Additionally, the pseudopericyclic topology of the transition states for some of the [1,5]-X migrations (X = F, Cl, OH, SH), for the 6pi-electrocyclization of the ketene intermediates to the 4(3H)-pyridones, and for the 6pi-electrocyclization of the starting ketenimines into 1,3-oxazines could be established on the basis of their geometries, natural bond orbital analyses, and magnetic properties. The calculations predict that the 4(3H)-pyridones are the thermodynamically controlled products and that the 1,3-oxazines should be the kinetically controlled ones.

Related Papers

• → Hiscotropic Rearrangements: Hybrids of Electrocyclic and Sigmatropic Reactions(2006)48 cited
• → Total syntheses of (.+-.)-physovenine and (.+-.)-physostigmine. An application of tandem electrocyclic-[3,3]sigmatropic reaction of benzocyclobutenes(1986)52 cited
• → Synthesis of 6H-Thieno[3,2-b]pyridin-7-ones from N-(2-X-Carbonyl)-3-thienyl Ketenimines (X = RS, ArO, R2N) via Consecutive [1,5]-X Sigmatropic Rearrangement and 6π-Electrocyclization(2007)9 cited
• → THE COMPETITION BETWEEN ELECTROCYCLIC REACTION AND [1,5]SIGMATROPIC REACTION IN THE THERMOLYSIS OF 1,1-DISUBSTITUTED BENZOCYCLOBUTENES(1984)28 cited
• → Pericyclic reactions 2: sigmatropic and electrocyclic reactions(2012)2 cited