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Intramolecular reaction
About: Intramolecular reaction is a research topic. Over the lifetime, 5015 publications have been published within this topic receiving 138213 citations.
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TL;DR: Methods for the synthesis of dihydroazaphenanthrene fused to macrocycles and medium-ring heterocycles, as well as 1,4-benzodiazepine-2,5-diones, are developed to develop a divergent synthesis of two different heterocyclic scaffolds from the same starting materials.
Abstract: Methods for the synthesis of dihydroazaphenanthrene fused to macrocycles (2) and medium-ring heterocycles (4), as well as 1,4-benzodiazepine-2,5-diones (5), are developed. A distinctly different catalytic property of palladium and copper catalysts was uncovered that leads to the development of a divergent synthesis of two different heterocyclic scaffolds from the same starting materials, simply by metal-switching. Thus, starting from linear amide 3, palladium acetate triggers a domino intramolecular N-arylation/C−H activation/aryl−aryl bond-forming process to provide 4, while copper iodide promotes only the intramolecular N-arylation reaction leading to 5. In combination with the Ugi multicomponent reaction (Ugi-4CR) for the preparation of the linear amides, a two-step synthesis of either the 5,6-dihydro-8H-5,7a-diazacyclohepta[jk]phenanthrene-4,7-dione (4) or 1,4-benzodiazepine-2,5-diones (5), by appropriate choice of metal catalyst, is subsequently developed from very simple starting materials.
141 citations
140 citations
TL;DR: A gold-catalyzed cyclialkylation of electron-rich arenes with tethered epoxides afforded 3-chromanols stereospecifically.
Abstract: A gold-catalyzed cyclialkylation of electron-rich arenes with tethered epoxides afforded 3-chromanols stereospecifically.
140 citations
TL;DR: In this paper, the reaction mechanism of primary aliphatic amines with CO2 was investigated, and the final product was formed by the intramolecular dehydration, which was obtained at the optimized conditions that are comparable to the presence of catalyst and solvent.
139 citations
TL;DR: It has been found that hydride or silyl insertion is concerted with the oxidative addition of the H-Si bond and the proposed mechanism rationalizes the observed regio- and stereochemistry of the intramolecular reaction.
Abstract: Density functional calculations have been carried out to understand the anti-addition stereochemistry and Markovnikov regiochemistry of the hydrosilylation of terminal alkynes and the endo-dig product of intramolecular hydrosilylation of homopropargyl alcohols catalyzed by cationic cyclopentadienyl-ruthenium complexes. It has been found that hydride or silyl insertion is concerted with the oxidative addition of the H−Si bond. Hydride insertion is much more favorable than silyl insertion. Such a hydride insertion nicely reproduces the observed regioselectivity, while silyl insertion would predict the opposite result. The hydride insertion leads to the formation of a η2-vinylruthenium intermediate for the reaction of acetylene or a metallacyclopropene intermediate for the reaction of propyne. In the formation of both intermediates, there is a Cα−Cβ bond rotation so that the transferring hydride becomes anti to the silyl group. This is followed by a facile reductive α-silyl migration transition state, which ...
139 citations