124070-39-9Relevant academic research and scientific papers
Synthesis of azaheterocyclic vinylphosphonates by ring-closing metathesis
Garzon, Cecile,Attolini, Mireille,Maffei, Michel
supporting information, p. 3653 - 3657 (2013/07/19)
The title compounds were synthesized by ruthenium-catalyzed ring-closing metathesis of N-tosyl-N-(ω-alkenyl)aminomethylvinyl phosphonates, which were obtained from N-(ω-alkenyl)-N-tosylamides. These compounds, in turn, were prepared from unsaturated alcohols through the Mitsunobu reaction. This methodology gives access to five- and six-membered ring compounds. Additionally, chiral phosphonates can be obtained easily. Organocatalysis and ring-closing metathesis enable a two-step synthesis of azaheterocyclic vinylphosphonates, giving access to five- and six-membered ring compounds. The required (ω-alkenyl) p-toluenesulfonamides were obtained through the Mitsunobu reaction, which allows the synthesis of chiral phosphonates. Copyright
Gold(I)-catalyzed highly regio- and stereoselective decarboxylative amination of allylic N-tosylcarbamates via base-induced aza-Claisen rearrangement in water
Xing, Dong,Yang, Dan
supporting information; experimental part, p. 1068 - 1071 (2010/06/13)
(Figure Presented)A gold(l)-catalyzed decarboxylative animation of allylic N-tosylcarbamates via base-induced aza-Claisen rearrangement has been developed. A variety of substituted W-tosyl allylic amines were obtained In good yield, excellent regloselectlvity, and high to excellent stereoselectivity. This transformation could be performed either in H2O or In one pot directly from allylic alcohols and therefore represents an efficient and environmentally benign protocol for the synthesis of N-tosyl allylic amines.
Palladium-catalyzed allylic transposition of (allyloxy) iminodiazaphospholidines: A formal [3,3]-aza-phospha-oxa-cope sigmatropic rearrangement for the stereoselective synthesis of allylic amines
Lee, Ernest E.,Batey, Robert A.
, p. 14887 - 14893 (2007/10/03)
The synthesis of N-protected allylic amines has been achieved utilizing a palladium(II)-catalyzed, [3,3]-rearrangement of (allyloxy) iminodiazaphospholidines. This [3,3]-aza-phospha-oxa-Cope sigmatropic rearrangement reaction is thermodynamically driven by a P=N to P=O interconversion and is an alternative to the Overman rearrangement. The overall process involves the nucleophilic displacement of an allylic alcohol onto a P(III) precursor, followed by a Staudinger reaction to generate the (allyloxy) iminodiazaphospholidine precursors. Pd(II)-catalyzed [3,3]-aza-phospha-oxa-Cope rearrangement then gives a phosphoramide, which is readily hydrolyzed under acidic conditions to yield allylic amine derivatives. Pd(II) catalysis is believed to occur in a fashion analogous to that of the rearrangement of allylic imidates. The scope of racemic, diastereoselective, and enantioselective variants of this rearrangement is described. The use of chiral diamine auxiliaries in diastereoselective rearrangements is reported. Rearrangement of chiral N,N′-dimethyl cyclohexanediamine derived diazaphospholidines gives rise to phosphoramides with moderate diastereoselectivities (up to 3.5:1 dr). The same major diastereomeric product in these rearrangements was prepared irrespective of the starting allylic alcohol geometry. An enantioselective variant of the reaction was demonstrated for the rearrangement of cis-(allyloxy) iminodiazaphospholidines with cobalt oxazoline palladacycle (COP-X) catalysts (5 mol %) in high yield and enantioselectivity (up to 96% ee).
Palladium-catalyzed [3,3] sigmatropic rearrangement of (allyloxy) iminodiazaphospholidines: Allylic transposition of C-O and C-N functionality
Lee, Ernest E.,Batey, Robert A.
, p. 1865 - 1868 (2007/10/03)
A PV=N to PV=O interconversion is the thermodynamic driving force for the title reaction. Iminodiazaphospholidines 1 give phosphoramides 2, which are subsequently hydrolyzed under mild acidic conditions to yield primary or tosylamines 3. R = alkyl, phenyl; Ts = p-toluenesulfonyl.
Chiral (OC)Ru(salen)-catalyzed tandem sulfimidation and [2,3]sigmatropic rearrangement: Asymmetric C-N bond formation
Murakami, Masakazu,Katsuki, Tsutomu
, p. 3947 - 3949 (2007/10/03)
Asymmetric C-N bond formation was achieved in a highly enantioselective manner by using (OC)Ru(salen)-catalyzed sulfimidation and the subsequent [2,3]sigmatropic rearrangement: treatment of allyl aryl sulfides with p-toluenesulfonyl azide in the presence of a catalytic amount of (OC)Ru(salen) followed by hydrolysis of the resulting N-allyl-N-arylthio toluenesulfonamides provided N-allyl toluenesulfonamides of high enantiomeric excess.
