125617-35-8Relevant articles and documents
Aza-Bellus-Claisen rearrangement-enabled synthesis of racemic tapentadol and its stereoisomers
Bai, Donghu,Huang, Sha-Hua,Lin, Zuming,Yang, Lin,Dai, Junzeng,Huang, Meng-Yuan,Jia, Xueshun,Hong, Ran
, p. 317 - 320 (2013)
A concise synthesis of racemic Tapentadol and its stereoisomers was presented. The key step was a TiCl4·THF2-catalzyed aza-Bellus-Claisen rearrangement to create two vicinal tertiary carbon stereogenic centers. The subsequent reducti
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.
Intramolecular Povarov Reactions for the Synthesis of Chromenopyridine Fused 2-Pyridone Polyheterocycles Binding to α-Synuclein and Amyloid-β Fibrils
Adolfsson, Dan E.,Tyagi, Mohit,Singh, Pardeep,Deuschmann, Adrian,?dén, J?rgen,Gharibyan, Anna L.,Jayaweera, Sanduni Wasana,Lindgren, Anders E. G.,Olofsson, Anders,Almqvist, Fredrik
supporting information, p. 14174 - 14189 (2020/11/13)
A BF3·OEt2 catalyzed intramolecular Povarov reaction was used to synthesize 15 chromenopyridine fused thiazolino-2-pyridone peptidomimetics. The reaction works with several O-alkylated salicylaldehydes and amino functionalized thiazolino-2-pyridones, to generate polyheterocycles with diverse substitution. The synthesized compounds were screened for their ability to bind α-synuclein and amyloid β fibrils in vitro. Analogues substituted with a nitro group bind to mature amyloid fibrils, and the activity moreover depends on the positioning of this functional group.
Photocatalyzed Diastereoselective Isomerization of Cinnamyl Chlorides to Cyclopropanes
Dykstra, Ryan,Gutierrez, Osvaldo,Martin, Robert T.,Tambar, Uttam K.,Troian-Gautier, Ludovic,Xu, Bin
supporting information, p. 6206 - 6215 (2020/04/27)
Endergonic isomerizations are thermodynamically unfavored processes that are difficult to realize under thermal conditions. We report a photocatalytic and diastereoselective isomerization of acyclic cinnamyl chlorides to strained cyclopropanes. Quantum mechanical calculations (uM06-2X and DLPNO), including TD-DFT calculations, and experimental studies provide evidence for the energy transfer from an iridium photocatalyst to the allylic chloride substrate followed by C-Cl homolytic cleavage. Subsequent Cla￠ radical migration forms a localized triplet 1,3-diradical intermediate that, after intersystem crossing, undergoes ring-closing to form the desired product. The mild reaction conditions are compatible with a broad range of functional groups to generate chlorocyclopropanes in high yields and diastereoselectivities. A more efficient process is developed by addition of a catalytic amount of a nickel complex, and we propose a novel role for this cocatalyst to recycle an allyl chloride byproduct generated in the course of the reaction. The reaction is also shown to be stereoconvergent, as an E/Z mixture of cinnamyl chlorides furnish the anti-chlorocyclopropane product in high diastereoselectivity. We anticipate that the use of a visible light activated photocatalyst to transform substrates in combination with a transition metal catalyst to recycle byproducts back into the catalytic cycle will provide unique opportunities for the discovery of new reactivity.
