81330-01-0Relevant articles and documents
Triiodide-Mediated δ-Amination of Secondary C?H Bonds
Wappes, Ethan A.,Fosu, Stacy C.,Chopko, Trevor C.,Nagib, David A.
, p. 9974 - 9978 (2016/08/16)
The Cδ?H amination of unactivated, secondary C?H bonds to form a broad range of functionalized pyrrolidines has been developed by a triiodide (I3?)-mediated strategy. By in situ 1) oxidation of sodium iodide and 2) sequestration of the transiently generated iodine (I2) as I3?, this approach precludes undesired I2-mediated decomposition which can otherwise limit synthetic utility to only weak C(sp3)?H bonds. The mechanism of this triiodide-mediated cyclization of unbiased, secondary C(sp3)?H bonds, by either thermal or photolytic initiation, is supported by NMR and UV/Vis data, as well as intercepted intermediates.
Synthetic efforts toward the Lycopodium alkaloids inspires a hydrogen iodide mediated method for the hydroamination and hydroetherification of olefins
Leger, Paul R.,Murphy, Rebecca A.,Pushkarskaya, Eugenia,Sarpong, Richmond
, p. 4377 - 4383 (2015/03/14)
Progress toward the total syntheses of a diverse set of fawcettimine-type Lycopodium alkaloids via a "Heathcock-type" 6-5-9 tricycle is disclosed. This route features an intermolecular Diels-Alder cycloaddition to rapidly furnish the 6-5-fused bicycle and a highly chemoselective directed hydrogenation to build the azonane fragment. While conducting these synthetic studies, trimethylsilyl iodide was found to effect a hydroamination reaction to furnish the tetracyclic core of serratine and related natural products. This observation has been expanded into a general method for the room temperature hydroamination of unactivated olefins with tosylamides utilizing catalytic "anhydrous" HI (generated in situ from trimethylsilyl iodide and water). The presence of the iodide anion is critical to the success of this Bronsted acid catalyzed protocol, possibly due to its function as a weakly coordinating anion. These conditions also effect the analogous hydroetherification reaction of alcohols with unactivated olefins.
Gold versus silver-catalyzed intermolecular hydroaminations of alkenes and dienes
Giner, Xavier,Najera, Carmen,Kovacs, Gabor,Lledos, Agusti,Ujaque, Gregori
experimental part, p. 3451 - 3466 (2012/02/04)
Comparative studies about the hydroamination of unactivated alkenes and dienes catalyzed by either cationic gold(I) triphenyl phosphite complexes or silver salts were performed using sulfonamides, anilines and carbamates as nucleophiles. Gold-catalyzed reactions generally, need lower loadings than those carried out with silver salts. Simple alkenes react only with sulfonamides and weak aromatic amines such as p-nitroaniline, whereas for conjugated dienes carbamates can also be used. Carbon-carbon double bond isomerization is observed only with gold similarly to when triflic acid was used, affording mixtures of regioisomeric products in the same cases. Silver-catalyzed hydroaminations failed with terminal alkenes, except with styrenes. Conjugate dienes can be hydroaminated either at 85 °C in toluene or at room temperature in dichloromethane. Non-conjugated 1,4- and 1,5-dienes suffer double hydroamination leading to saturated N-tosylated heterocyclic amines The catalytic cycle for the silver(I)-catalyzed hydroamination process has been computationally analyzed, resembling gold(I)-catalyzed processes, although with some significant differences. Copyright
Pyrrolidine and piperidine formation via copper(II) carboxylate-promoted intramolecular carboamination of unactivated olefins: Diastereoselectivity and mechanism
Sherman, Eric S.,Fuller, Peter H.,Kasi, Dhanalakshmi,Chemler, Sherry R.
, p. 3896 - 3905 (2008/02/01)
(Chemical Equation Presented) An expanded substrate scope and in-depth analysis of the reaction mechanism of the copper(II) carboxylate-promoted intramolecular carboamination of unactivated alkenes is described. This method provides access to N-functionalized pyrrolidines and piperidines. Both aromatic and aliphatic γ- and δ-alkenyl N-arylsulfonamides undergo the oxidative cyclization reaction efficiently. N-Benzoyl-2-allylaniline also underwent the oxidative cyclization. The terminal olefin substrates examined were more reactive than those with internal olefins, and the latter terminated in elimination rather than carbon-carbon bond formation. The efficiency of the reaction was enhanced by the use of more organic soluble copper(II) carboxylate salts, copper(II) neodecanoate in particular. The reaction times were reduced by the use of microwave heating. High levels of diastereoselectivity were observed in the synthesis of 2,5-disubstituted pyrrolidines, wherein the cis substitution pattern predominates. The mechanism of the reaction is discussed in the context of the observed reactivity and in comparison to analogous reactions promoted by other reagents and conditions. Our evidence supports a mechanism wherein the N-C bond is formed via intramolecular syn aminocupration and the C-C bond is formed via intramolecular addition of a primary carbon radical to an aromatic ring.
Gold(I)-catalyzed intra- and intermolecular hydroamination of unactivated olefins
Zhang, Junliang,Yang, Cai-Guang,He, Chuan
, p. 1798 - 1799 (2007/10/03)
Ph3PAuOTf catalyzes efficient intra- and intermolecular hydroamination of unactivated olefins with sulfonamides. Copyright
A Stereocontrolled Organopalladium Route to 2,5-Disubstituted Pyrrolidine Derivatives. Application to the Synthesis of a Venom Alkaloid of the Ant Species Monomorium latinode
Baeckvall, Jan-E.,Schink, Hans E.,Renko, Z. Dolor
, p. 826 - 831 (2007/10/02)
A general method for the preparation of cis- and trans-2,5-disubstituted pyrrolidines from conjugated dienes has been developed.The approach involves a stereocontrolled syn- or anti-1,4-addition of an amino and an oxygen function to the diene via palladiu
Sulphonamidomercuriation of Olefins and Subsequent Reductive Demercuriation or Bromodemercuriation
Barluenga, Jose,Jimenez, Carmen,Najera, Carmen,Yus, Miguel
, p. 721 - 725 (2007/10/02)
The addition of toluene-p-sulphonamide to olefins in the presence of anhydrous mercury(II) nitrate and subsequent sodium borohydride reduction leads to the corresponding N-alkylsulphonamides.The sulphonamidomercuriation-demercuriation of 1,4- and 1,5-dienes yields saturated nitrogen-containing heterocycles.A possible mechanism for the stereoselective synthesis of cis-2,5-dimethyl-N-tosylpyrrolidine is proposed.The treatment of the intermediate organomercurials, isolated as the sodium salts of their bromomercurio derivatives, with bromine gives the corresponding 2-bromoalkylsulphonamides through a regiospecific bromodemercuriation process.
Sulphonamidomercuration; a New Method for Amination of Olefins
Barluenga, Jose,Jimenez, Carmen,Najera, Carmen,Yus, Miguel
, p. 1178 - 1179 (2007/10/02)
The addition of toluene-p-sulphonamide to olefins in the presence of anhydrous mercury(II) nitrate and subsequent sodium borohydride reduction leads to the corresponding N-alkyl-sulphonamides; the use of 1,4- and 1,5-dienes yields saturated nitrogen-containing heterocycles, the synthesis of tosylated pyrrolidine being a stereoselective reaction.
