62419-04-9Relevant articles and documents
Enantioselective Preparation, Conformational Analysis and Absolute Configuration of Highly Substituted Aziridines
Bencivenni, Giorgio,Righi, Paolo,Lunazzi, Lodovico,Ranieri, Silvia,Mancinelli, Michele,Mazzanti, Andrea
, p. 875 - 887 (2015/11/16)
The first example of organocatalytic aziridination reaction of α-substituted-α,β-unsaturated ketones is presented. The reaction was found to be highly enantio- and diastereoselective, yielding N-tosylated aziridines. Low-temperature nuclear magnetic reson
Asymmetric formal trans -dihydroxylation and trans -aminohydroxylation of α,β-unsaturated aldehydes via an organocatalytic reaction cascade
Albrecht, Lukasz,Jiang, Hao,Dickmeiss, Gustav,Gschwend, Bjoern,Hansen, Signe Grann,Jorgensen, Karl Anker
supporting information; experimental part, p. 9188 - 9196 (2010/08/21)
This study demonstrates the first formal asymmetric trans-dihydroxylation and trans-aminohydroxylation of α,β-unsaturated aldehydes in an organocatalytic multibond forming one-pot reaction cascade. This efficient process converts α,β-unsaturated aldehydes into optically active trans-2,3-dihydroxyaldehydes and trans-3-amino-2-hydroxyaldehydes with the aldehyde moiety protected as an acetal. The elaborated one-pot protocol proceeds via the formation of 2,3-epoxy and 2,3-aziridine aldehyde intermediates, which subsequently participate in a novel NaOMe-initiated rearrangement reaction leading to the formation of acetal protected trans-2,3-dihydroxyaldehydes and trans-3-amino-2-hydroxyaldehydes in a highly stereoselective manner. Advantageously, this multibond forming reaction cascade can be performed one-pot, thereby minimizing the number of manual operations and purification procedures required to obtain the products. Additionally, for the purpose of trans-aminohydroxylation of the α,β-unsaturated aldehydes, a new enantioselective aziridination protocol using 4-methyl-N-(tosyloxy) benzenesulfonamide as the nitrogen source has been developed. The mechanism of the formal trans-dihydroxylation and trans-aminohydroxylation of α,β-unsaturated aldehydes is elucidated by various investigations including isotopic labeling studies. Finally, the products obtained were applied in the synthesis of numerous important molecules.
ESR study of free radical decomposition of N,N-bis(arylsulfonyl)hydroxylamines in organic solution
Balakirev, Maxim Yu.,Khramtsov, Valery V.
, p. 7263 - 7269 (2007/10/03)
Decomposition of N,N-bis(p-tolylsulfonyl)hydroxylamine (BTH) in chloroform and benzene solutions has been studied and was found to involve the formation of several radical intermediates. This process has been found to be accelerated by oxygen, resulting in the formation of p-toluenesulfonic acid and N,N,O-tris(p-tolylsulfonyl)hydroxylamine (TTH) as the main decay products. In addition, a small amount of p-toluenesulfonyl chloride has been isolated from chloroform solution, suggesting the chlorine abstraction from solvent. The formation of nitric oxide (NO) from BTH has been shown by mass spectrometry in gaseous phase and using nitronyl nitroxide as an NO trap in solution. It was proposed that liberation of NO proceeds through the homolytic cleavage of the S-N bond of p-tolylsulfonyl nitrite existing in equilibrium with BTH in solution. The formation of p-tolylsulfonyl radicals has been proved by spin trapping using 2-methyl-2-nitrosopropane (MNP) and 5,5-dimethyl-1-pyrroline N-oxide (DMPO). The rate of NO production in the presence of nitronyl nitroxide and the rate of oxygen consumption revealed linear plots in BTH concentration with the rate constants 0.0044 s-1 and 0.0016 s-1, respectively. It was found also that nitrogen dioxide formed during NO oxidation reacts readily with BTH to produce the organic analog of Fremy's radical. This radical recombines with p-tolylsulfonyl radical yielding N,N,O-trisubstituted hydroxylamine TTH.
REDUCTIVE DEIMINATION OF SULFOXIMIDES AND SULFILIMIDES WITH P-TOLUENESULFONYL NITRITE, A NEW NITROSATING AGENT
Oae, Shigeru,Iida, Kazayuki,Takata, Toshikazu
, p. 573 - 576 (2007/10/02)
Reductive deiminations of diaryl sulfilimides and dialkyl and aryl alkyl sulfoximides with p-toluenesulfonyl nitrite, a new nitrosating reagent, has been investigated.
REDUCTIVE DEIMINATION OF SULFOXIMIDES AND SULFIMIDES WITH P-TOLUENESULFONYL NITRITE AND T-BUTYL THIONITRATE
Oae, Shigeru,Iida, Kazuyuki,Takata, Toshikazu
, p. 103 - 114 (2007/10/02)
Reduction of sulfimides and sulfoximides with p-toluenesulfonyl nitrite, a new nitrosating agent, gave nearly quantitatively the corresponding deimination products, sulfides and sulfoxides, respectively.In the reaction of dialkyl and aryl alkyl sulfoximides with t-butyl thionitrate, N-t-butylthiosulfoximides were obtained besides the usual deimination products, although diaryl sulfoximides were readily deiminated to the corresponding sulfoxides in good yields in the same treatment. t-Butyl thionitrsate was also found to deiminate diphenyl sulfimide to give diphenyl sulfide in good yield.Sulfoximides reacted sluggishly with t-butyl thionitrite, however, eventually affording a small amount of sulfoxides.
Physical Properties and Various Reactions of Thionitrites and Related Substances
Oae, Shigeru,Shinhama, Koichi,Fujimori, Ken,Kim, Yong Hae
, p. 775 - 784 (2007/10/02)
Several new sulfenyl or sulfonyl derivatives, thionitrates (RSNO2), sulfonyl nitrites (RSO2NO), were successfully isolated by treating corresponding thiols and sulfinic acids with dinitrogen tetraoxide (N2O4).Spectroscopic data of both stable and many rather unstable compounds were determined and compared with those of corresponding alkyl nitrites (RONO) or alkyl nitrates (RONO2).Chemical reactivities of these uncommon, novel S-nitroso and S-nitro compounds were investigated.
