2424-02-4Relevant articles and documents
Synthesis of Oxazolidinones by a Hypervalent Iodine Mediated Cyclization of N-Allylcarbamates
Das, Mirdyul,Rodríguez, Arantxa,Lo, Pui Kin Tony,Moran, Wesley J.
supporting information, p. 1646 - 1650 (2021/02/11)
The preparation of oxazolidinones by the hypervalent iodine mediated cyclization of allylcarbamates is described. A versatile range of substrates can be converted into substituted oxazolidinones primed for further transformations. Derivatization of the products at both ends is demonstrated. A preliminary attempt at the enantioselective formation of an oxazolidinone using a chiral iodane is also presented. (Figure presented.).
Triazinines: Synthesis and proteolytic decomposition of a new class of cyclic triazenes
Schmidt,Schmidt, Brigitte F.,Snyder,Snyder, Emily J.,Carroll,Carroll, Robin M.,Farnsworth,Farnsworth, David W.,Michejda,Michejda, Christopher J.,Smith R.H.,Smith Jr., Richard H.
, p. 8660 - 8665 (2007/10/03)
The reaction of 1-azido-3-chloropropane with various Grignard reagents and subsequent treatment with anhydrous isopropylamine results in the formation of the corresponding azimine. If the initial magnesium-triazene complex if first hydrolyzed with Dowex resin and then concentrated, the resultant linear triazene begins self-catalyzed cyclization to form the six- membered-ring triazenes as the major product, with HCl as the byproduct. Addition of an amine, at reduced temperature, allows for the neutralization of the byproduct, HC1, which would otherwise react with the linear triazene and the cyclic six-membered-ring triazene to form hydrolysis products. We have assigned the trivial name of triazinines to this new class of cyclic triazenes. The hydrolytic decomposition of these compounds in mixed acetonitrile-aqueous buffers predominantly forms 3-(alkylamino)-1-propanol and lesser amounts of the rearranged alcohol 1-(alkylamino)-2-propanol and N- alkyl-2-propenamine. The rate of hydrolysis of 1-alkyltriazinines is approximately equal to that of the analogous 1,3,3-trialkyltriazenes, about three times slower than that of the analogous 1-alkyltriazolines, and varies in the order ethyl > butyl > 3,3-diethoxypropyl > benzyl. As was true for other triazenes, the mechanism of the decomposition was found to be specific acid-catalyzed (A1), involving rapid reversible protonation followed by rate- limiting formation of a 3-(alkylamino)propyldiazonium ion. The slopes of the log k(obs) versus pH plots were near -1.0 The solvent deuterium isotope effect, k(H)2O/k(D)2O, was in all cases 1.0 and ranges from 0.82 for 1- benzyltriazinine to 0.89 for 1-ethyltriazinine. The activation parameters of the proteolytic decomposition of a series, 1-ethyltriazinine, 1- ethyltriazoline, 1,3,3-triethyltriazene, and 1-ethyl-3-methyltriazene, had similar values for ΔH(+) (+9 → 12 kcal/mol) and ΔS(+) (+7 → 15 eu), respectively.
PHOSPHONIUM DIAZA-DIYLIDS AND AZA-YLDIID AS NEW AND EFFICIENT REAGENTS FOR PRIMARY AND SECONDARY AMINES SYNTHESIS
Cristau, Henri-Jean,Garcia, Chantal,Kadoura, Jumah,Torreilles, Eliane
, p. 151 - 154 (2007/10/02)
Metallated aminophosphonium ylids, diaza-diylids and aza-yldiid, are investigated as reagents for primary and secondary amines synthesis.
