184674-48-4Relevant academic research and scientific papers
Diastereoselective and Enantiospecific Synthesis of 1,3-Diamines via 2-Azaallyl Anion Benzylic Ring-Opening of Aziridines
Li, Kangnan,Weber, Alexandria E.,Tseng, Luke,Malcolmson, Steven J.
supporting information, p. 4239 - 4242 (2017/08/23)
The 1,3-diamine motif appears in numerous complex molecules, yet there are few methods for the stereoselective construction of this moiety. Herein, we demonstrate a stereocontrolled synthesis of 1,3-diamines, which bear up to three contiguous stereogenic centers, through benzylic ring-opening of aziridines with 2-azaallyl anion nucleophiles. Reactions proceed efficiently (yield up to 95%), diastereoselectively (dr up to >20:1), site selectively, and enantiospecifically to deliver products with differentiated amino groups.
Enantioselective synthesis of diaryl aziridines using tetrahydrothiophene- based chiral sulfides as organocatalysts
Huang, Meng-Ting,Wu, Hsin-Yi,Chein, Rong-Jie
, p. 1101 - 1103 (2014/01/17)
This work describes catalytic and asymmetric aziridinations (15 examples, 95-98% ee) of benzyl bromide and imines via the imino Corey-Chaykovsky reaction using (thiolan-2-yl)diarylmethanol benzyl ether as an organocatalyst. The catalyst and analogues thereof were prepared through an expeditious and efficient synthetic route featuring a double nucleophilic substitution and Shi epoxidation as key steps.
A versatile tripodal Cu(I) reagent for C-N bond construction via nitrene-transfer chemistry: Catalytic perspectives and mechanistic insights on C-H aminations/amidinations and olefin aziridinations
Bagchi, Vivek,Paraskevopoulou, Patrina,Das, Purak,Chi, Lingyu,Wang, Qiuwen,Choudhury, Amitava,Mathieson, Jennifer S.,Cronin, Leroy,Pardue, Daniel B.,Cundari, Thomas R.,Mitrikas, George,Sanakis, Yiannis,Stavropoulos, Pericles
supporting information, p. 11362 - 11381 (2014/09/17)
A CuI catalyst (1), supported by a framework of strongly basic guanidinato moieties, mediates nitrene-transfer from PhI=NR sources to a wide variety of aliphatic hydrocarbons (C-H amination or amidination in the presence of nitriles) and olefins (aziridination). Product profiles are consistent with a stepwise rather than concerted C-N bond formation. Mechanistic investigations with the aid of Hammett plots, kinetic isotope effects, labeled stereochemical probes, and radical traps and clocks allow us to conclude that carboradical intermediates play a major role and are generated by hydrogen-atom abstraction from substrate C-H bonds or initial nitrene-addition to one of the olefinic carbons. Subsequent processes include solvent-caged radical recombination to afford the major amination and aziridination products but also one-electron oxidation of diffusively free carboradicals to generate amidination products due to carbocation participation. Analyses of metal- and ligand-centered events by variable temperature electrospray mass spectrometry, cyclic voltammetry, and electron paramagnetic resonance spectroscopy, coupled with computational studies, indicate that an active, but still elusive, copper-nitrene (S = 1) intermediate initially abstracts a hydrogen atom from, or adds nitrene to, C-H and C=C bonds, respectively, followed by a spin flip and radical rebound to afford intra- and intermolecular C-N containing products.
An improved and mild wenker synthesis of aziridines
Li, Xinyao,Chen, Ning,Xu, Jiaxi
experimental part, p. 3423 - 3428 (2010/11/21)
The conventional Wenker synthesis of aziridines from vicinal amino alcohols has been modified by employing mild reaction conditions. Amino alcohols were converted into their hydrogen sulfates with chlorosulfonic acid. The sulfates were cyclized with sodium hydroxide, and even with non-nucleophilic sodium carbonate. The current, improved method extends the scope of the typical Wenker synthesis and is applicable to unstable amino alcohols in hot sulfuric acid and to unstable sulfates which favor elimination and hydroxide displacement in the presence of strong base. Georg Thieme Verlag Stuttgart.
Enantioselective chemoenzymatic synthesis of trans-aziridines
Ritzen, Bas,Van Oers, Matthijs C. M.,Van Delft, Floris L.,Rutjes, Floris P. J. T.
supporting information; experimental part, p. 7548 - 7551 (2010/01/06)
(Chemical Equation Presented) A straightforward, five-step procedure for the synthesis of enantiomerically pure 2,3-disubstituted trans-aziridines has been developed starting from commercially available aldehydes. Hydroxynitrile lyase-mediated cyanohydrin
Optically pure trans-2,3-disubstituted N-sulfinyl aziridines. Regio- and stereoselective opening mediated by the sulfinyl group
Arroyo, Yolanda,Meana, ángela,Rodríguez, J. Félix,Santos, Mercedes,Sanz-Tejedor, M. Ascensión,García-Ruano, José L.
, p. 8525 - 8532 (2007/10/03)
A new entry to optically pure trans-2,3-disubstituted N-sulfinyl aziridines starting from 1,2-aminosulfides, involving formation of a sulfonium salt intermediate followed by intramolecular nucleophilic attack by the sulfinamide nitrogen atom, is reported.
Stereoselective synthesis of δ-lactones from 5-oxoalkanals via one-pot sequential acetalization, tishchenko reaction, and lactonization by cooperative catalysis of samarium ion and mercaptan
Hsu,Fang
, p. 8573 - 8584 (2007/10/03)
By the synergistic catalysis of samarium ion and mercaptan, a series of 5-oxoalkanals was converted to (substituted) δ-lactones in efficient and stereoselective manners. This one-pot procedure comprises a sequence of acetalization, Tishchenko reaction and lactonization. The deliberative use of mercaptan, by comparison with alcohol, is advantageous to facilitate the catalytic cycle. The reaction mechanism and stereochemistry are proposed and supported by some experimental evidence. Such samarium ion/mercaptan cocatalyzed reactions show the feature of remote control, which is applicable to the asymmetric synthesis of optically active δ-lactones. This study also demonstrates the synthesis of two insect pheromones, (2S,5R)-2-methylhexanolide and (R)-hexadecanolide, as examples of a new protocol for asymmetric reduction of long-chain aliphatic ketones.
