- Visible-Light-Mediated Synthesis of Amidyl Radicals: Transition-Metal-Free Hydroamination and N-Arylation Reactions
-
The development of photoredox reactions of aryloxy-amides for the generation of amidyl radicals and their use in hydroamination-cyclization and N-arylation reactions is reported. Owing to the ease of single-electron-transfer reduction of the aryloxy-amides, the organic dye eosin Y was used as the photoredox catalyst, which results in fully transition-metal-free processes. These transformations exhibit a broad scope, are tolerant to several important functionalities, and have been used in the late-stage modification of complex and high-value N-containing molecules.
- Davies, Jacob,Svejstrup, Thomas D.,Fernandez Reina, Daniel,Sheikh, Nadeem S.,Leonori, Daniele
-
supporting information
p. 8092 - 8095
(2016/07/16)
-
- First examples of intramolecular addition of primary amidyl radicals to olefins
-
The first examples of intramolecular addition of primary amidyl radicals to olefins are described. Amidyl radicals were generated from N-(phenylthio)amides in refluxing benzene using a catalytic amount of 2,2′- azobis(isobutyronitrile) (5 mol%) and tributyltin hydride (sim;2.2 equiv.). The resulting yields of cyclic products ranged from 63% to 85%.
- Gaudreault, Philippe,Drouin, Christian,Lessard, Jean
-
p. 543 - 545
(2007/10/03)
-
- β-tosylethylhydroxylamine: Preparation and use as a hydroxylamine equivalent in amidyl radical-olefin cyclizations
-
An efficient three-step procedure has been developed for synthesis of β-tosylethylhydroxylamine from commercially available starting material. This compound forms hydroxamic acids which undergo amidyl radical-olefin cyclizations promoted by diethyl chloro
- Artman III, Gerald D.,Waldman, Jacob H.,Weinreb, Steven M.
-
p. 2057 - 2063
(2007/10/03)
-
- Development of efficient new methodology for generation, cyclization and functional trapping of iminyl and amidyl radicals
-
New methodology has been devised for the generation and subsequent cyclization of iminyl and amidyl radicals under mild conditions. The process involves either the treatment of oximes with 2,6-dimethylbenzenesulfinyl chloride, or the treatment of hydroxamic acids with tert-butylsulfinyl chloride (-50°C to rt), to give the corresponding nitrogen radicals, followed by cyclization onto pendant olefins. Radical traps such as diphenyl diselenide, diphenyl disulfide, and TEMPO can be used to terminate the cyclizations, thus introducing functionality that provides multiple options for further manipulation. In a more convenient procedure, both iminyl and amidyl radical cyclizations can be initiated using commercially available diethyl chlorophosphite which generally provides similar (with diphenyl disulfide and TEMPO) or significantly higher (with diphenyl diselenide) yields of products.
- Lin, Xichen,Artman III, Gerald D.,Stien, Didier,Weinreb, Steven M.
-
p. 8779 - 8791
(2007/10/03)
-
- Compounds with substituted cyclic hydrocarbon moieties linked by secondary or tertiary oxycarbonyl containing moiety providing reworkable cured thermosets
-
Compounds containing two cyclic hydrocarbon moieties which are substituted to provide crosslinking functionality and which are linked to each other by secondary or tertiary oxycarbonyl containing moiety are basis for compositions which are cured to provid
- -
-
-
- A new class of analogues of the bifunctional radiosensitizer α-(1-aziridinylmethyl)-2-nitro-1H-imidazole-1-ethanol (RSU 1069): The cycloalkylaziridines
-
A series of compounds related to α-(1-aziridinylmethyl)-2-nitro-1H-imidazole-1-ethanol (RSU 1069, 1) were synthesized and evaluated as selective hypoxic cell cytotoxic agents and as radiosensitizers. The aziridine moiety was replaced with a number of other potential alkylating groups including cycloalkylaziridines and azetidines. The data indicated that modification of the aziridine of 1 resulted in a substantial decrease in the ability of the compounds to selectively kill hypoxic cells. However, these modifications did not affect the compounds' in vitro radiosensitizing activity since many of the derivatives were as potent as 1. All of the compounds that were evaluated in vivo were less toxic than 1, and several members of this series had significant activity. The best compound was trans-α-[[(4-bromotetrahydro-2H-pyran-3-yl)amino]methyl]-2-nitro-1H- imidazole-1-ethanol (18), which, due to its activity and log P value, is a candidate for additional in vivo studies.
- Suto,Stier,Werbel,Arundel-Suto,Leopold,Elliott,Sebolt-Leopold
-
p. 2484 - 2488
(2007/10/02)
-
- Novel class of acyl-derivatives of carnitine process for preparing same and therapeutic use thereof
-
A novel class of acyl-derivatives of carnitine is disclosed wherein the acyl radical is either the radical of unsaturated organic acids (typically, acrylic acid) or the radical of saturated organic acids substituted with tert-alkyl, cycloalkyl, cycloalkenyl, alkoxyl, heterocyclic and carboalkoxylradicals, or with aldehyde or hydroxy groups. These acyl-derivatives of carnitine are useful therapeutical agents in the treatment of cardiac disorders, hyperlipidaemias and hyperlipoproteinaemias.
- -
-
-
- SYNTHESIS OF CYCLOHEXENYL-SUBSTITUTED ACRYLIC AND 3-HYDROXYPROPIONIC ACIDS AND THEIR HOMOLOGS
-
The corresponding 3-cyclohexenyl-substituted Z- and E-acrylic and 3-hydroxypropionic acids were synthesized from 3-cyclohexene-1-carbaldehyde and its methyl derivatives.Dehydration of the products under various conditions leads to the formation of the E isomers of the substituted acrylic acid and also isomerization, aromatization, and cyclization products.
- Gramenitskaya, V. N.,Inozemtseva, L. V.,Koz'mina, E. A.,Vul'fson, N. S.
-
p. 2260 - 2267
(2007/10/02)
-
- Solvolytic Rearrangements of Azabicyclic Compounds. Part 1. Identification of Products
-
The products of solvolysis of 2β-hylogeno-derivatives of 7-methyl-7-azabicycloheptane, 8-methyl-8-azabicyclooctane, 9-methyl-9-azabicyclo-- and --nonane, and 7-methyl-7-azabicyclooctane, have been isolated and characteri
- Bastable, John W.,Cooper, Anthony J.,Dunkin, Ian R.,Hobson, John D.,Riddell, William D.
-
p. 1339 - 1345
(2007/10/02)
-