Topic
Intramolecular reaction
About: Intramolecular reaction is a research topic. Over the lifetime, 5015 publications have been published within this topic receiving 138213 citations.
Papers published on a yearly basis
Papers
More filters
TL;DR: A lithiation-intramolecular cyclization reaction of N-Boc chloroalkyl secondary amines is reported to provide the 2-aryl-substituted pyrrolidine and piperidines (6), (7), (9), and (11) and a series of 2-azabicyclo[3.1.0] derivatives as discussed by the authors.
Abstract: A lithiation-intramolecular cyclization reaction of N-Boc chloroalkyl secondary amines is reported to provide the 2-aryl-substituted pyrrolidine and piperidines (6), (7), (9), and (11) and a series of 2-azabicyclo[3.1.0] derivatives (14-25), including cyclopropane derivatives of proline and of the indolizidine-pyrrolizidine alkaloid ring system. Lithiation-substitutions of N-Boc-N-ethylcyclopropylamine to give (27-29) and lithiation-silylations of N-Boc aziridines to give (31-33) also are reported
74 citations
73 citations
TL;DR: Generalization of this approach based on reversible intramolecular trapping of a reactive intermediate by a ligand with multiple recognition subdomains has the potential for wide-ranging applications in targeting nucleic acids and proteins.
Abstract: Selective alkylation of a chosen sequence of DNA typically relies on ligand-directed delivery of a compound that expresses an intrinsic reactivity. A significant and biologically relevant enhancement in specificity is theoretically possible if such an intrinsic reactivity could be replaced by a latent activity induced solely by the target of interest, but examples of this are rare and not easily emulated. A simple strategy for target-promoted alkylation is now illustrated by an intramolecular adduct formed by an oligonucleotide–quinone methide conjugate. This adduct persists in the absence of a complementary sequence of DNA for at least 8 days, yet remarkably is able to alkylate target DNA upon duplex hybridization. Neither formation of the intramolecular self-adduct nor transfer of the quinone methide to its target is significantly quenched by 450-fold excess 2-mercaptoethanol. Similarly, noncomplementary DNA is neither subject to alkylation by the self-adduct nor able to effect its consumption. Reversible trapping of the nascent quinone methide through an intramolecular reaction thus appears efficient enough to inhibit competing intermolecular reaction. Only complementary base pairing induces a conformational change necessary to promote intermolecular transfer of the quinone methide. Generalization of this approach based on reversible intramolecular trapping of a reactive intermediate by a ligand with multiple recognition subdomains has the potential for wide-ranging applications in targeting nucleic acids and proteins.
73 citations
TL;DR: In this article, an electroreductive intramolecular coupling of γ- and δ-cyano ketones in one of the key steps was proposed. But the results were not as good as those obtained in this paper.
Abstract: Electroreduction of γ- and δ-cyano ketones in i-PrOH with Sn cathode gave α-hydroxy ketones and their dehydroxylated ketones as the intramolecularly coupled products. Guaiazulene, (-)-valeranone, polyquinanes, dihydrojasmone, methyl dihydrojasmonate, and rosaprostol have been synthesized by utilizing this electroreductive intramolecular coupling of γ- and δ-cyano ketones in one of the key steps. Similarly, electroreduction of a mixture of ketone and nitrile gave the corresponding intermolecularly coupled product
73 citations
TL;DR: In this paper, the ene reaction of singlet oxygen (1O2) was examined using time-resolved techniques and by an intramolecular trapping reaction, and it was shown that the rate of 1O2 with simple olefins is controlled by ΔS.
73 citations