57981-16-5Relevant academic research and scientific papers
Regio- And diastereoselective Pd-catalyzed aminochlorocyclization of allylic carbamates: scope, derivatization, and mechanism
Ariga, Elaine Miho,Carita Correra, Thiago,Matsushima, Jullyane Emi,McIndoe, J. Scott,Moreira Ribeiro, Francisco Wanderson,Omari, Isaac,Papa Spadafora, Bruna,Rodrigues, Alessandro,Soares, Priscila Machado Arruda,Vinhato, Elisangela,de Oliveira-Silva, Diogo
supporting information, p. 5595 - 5606 (2021/07/02)
The regio- and diastereoselective synthesis of oxazolidinonesviaa Pd-catalyzed vicinal C-N/C-Cl bond-forming reaction from internal alkenes of allylic carbamates is reported. The oxazolidinones are obtained in yields of 44 to 95% with high to excellent diastereoselectivities (from 6?:?1 to >20?:?1 dr) from readily available precursors. This process is scalable, and the products are suitable for the synthesis of useful amino alcohols. A detailed theoretical and experimental mechanistic study was carried out to describe that the reaction proceeds through ananti-aminopalladation of the alkene followed by an oxidative C-Pd(ii) cleavage with retention of the carbon stereochemistry to yield the major diastereomer. The role of Cu(ii) in a C-Cl bond-forming mechanism step has also been proposed.
Regioselective Cp*Ir(III)-Catalyzed Allylic C-H Sulfamidation of Allylbenzene Derivatives
Kazerouni, Amaan M.,Nelson, Taylor A. F.,Chen, Steven W.,Sharp, Kimberly R.,Blakey, Simon B.
, p. 13179 - 13185 (2019/09/30)
In this study we report the development of the regioselective Cp*Ir(III)-catalyzed allylic C-H sulfamidation of allylbenzene derivatives, using azides as the nitrogen source. The reaction putatively proceeds through a Cp*Ir(III)-π-allyl intermediate and demonstrates exclusive regioselectivity for the branched position of the π-allyl. The reaction performs well on electron-rich and electron-deficient allylbenzene derivatives and is tolerant of a wide range of functional groups, including carbamates, esters, and ketones. The proposed mechanism for this reaction proceeds via C-N reductive elimination from a Cp*Ir(V) nitrenoid complex at the branched position of the π-allyl.
A New Class of Redox Isomerization of N-Alkylpropargylamines into N-Alkylideneallylamines Catalyzed by a ReBr(CO)5/Amine N-oxide System
Fukumoto, Yoshiya,Okazaki, Natsuki,Chatani, Naoto
, p. 1760 - 1765 (2019/03/11)
Redox isomerization reaction wherein N-alkylpropargylamines are converted into N-alkylideneallylamines in the presence of rhenium(I) complexes as catalysts is described. Among the additives tested, certain pyridine N-oxides and tertiary amine N-oxides wer
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).
ALLYLIC AMINATION OF ALKENES BY TOSYLIMINOIODOBENZENE : MANGANESE PORPHYRINS AS SUITABLE CATALYSTS
Mahy, J. P.,Bedi, G.,Battioni, P.,Mansuy, D.
, p. 1927 - 1930 (2007/10/02)
Manganese-porphyrins and particularly Mn(TPP)(ClO4) were found to be much better catalysts than iron-porphyrins for allylic N-tosylamination of alkenes by tosyliminoiodobenzene.With the former catalyst, cyclohexene was selectively transformed into 3-tosyl
