First, a theoretical estimate of the magnitude of the difference in free energy of the two reactions (for a standard state of 1 M) is obtained using a gas-phase statistical thermodynamic approach, which indicates that the intramolecular reaction is energetically favored over its intermolecular ...
Intermolecular/Intramolecular Sequential Aldol Reactiondoi:10.1021/ja413008aThe first example of intermolecular/intramolecular sequential aldol reaction of disilyl enol ethers is described. This strategy enables the formation of five-, six-, and seven-membered ring products. Four or more contiguous ...
The expected open-chain ketone is completely decomposed into products of αβ-ketonic cleavage and a subsequent redox reaction. Differences in ratios of intermolecular to intramolecular acylation (now called o/c ratios) are discussed. In benzene, β-bis-( p-chlorophenyl)propionyl chloride gave, in...
Hydride, hydrogen atom, proton, and electron transfer driving forces of various five-membered heterocyclic organic hydrides and their reaction intermediate... The enthalpy changes of 47 five-membered heterocyclic compounds (ZH) [33 substituted 2,3-dihydro-2-phenylbenzo[d]imidazoles (1H-5H), 9 ...
The intramolecular interaction seems to mimic the binding of proline-rich peptides to the WW tandem, displaying a possible autoinhibitory role. We therefore analyzed the effect of the N-terminal autoinhibition on the binding to different intermolecular polyproline ligands. We performed NMR and ITC ...
The intramolecular interaction seems to mimic the binding of proline-rich peptides to the WW tandem, displaying a possible autoinhibitory role. We therefore analyzed the effect of the N-terminal autoinhibition on the binding to different intermolecular polyproline ligands. We performed NMR and ITC ...
We also attempted intermolecular a-cyclopropanation reactions using simple aldehydes and various electron-rich olefins. Unfortunately, no desired cyclopropane product was obtained under the standard reaction condition. The a-iodo aldehyde interme- diates were the major products. This result suggests a ...
Ruthenium-catalyzed intermolecular coupling reactions of arylamines with ethylene and 1,3-dienes: mechanistic insight on hydroamination vs ortho-C-H bond a... [reaction: see text]. The cationic ruthenium complex [(PCy3)2(CO)(Cl)Ru=CHCH=C(CH3)2]+BF4- was found to be an effective catalyst...
In the Path-endo, the initial intermolecular nucleophilic addition of 5 to the benzyl position on 2a via transition state 6-ts generates enolate complex 7 with a free energy barrier of 8.0 kcal·mol−1. The subsequent intramolecular cyclization leads to the formation of intermediate 9, ...
particularly tolerating -Br and -Cl groups which offer potential for late-stage product modification via cross-coupling technology. It is worth noting that this method is operationally simple, as the reaction can be conveniently performed under bench-top air atmosphere, and is complementary to frequen...