18350-99-7Relevant academic research and scientific papers
Development of a Multi Kilogram-Scale, Tandem Cyclopropanation Ring-Expansion Reaction en Route to Hedgehog Antagonist IPI-926
Austad, Brian C.,Hague, Andrew B.,White, Priscilla,Peluso, Stéphane,Nair, Somarajan J.,Depew, Kristopher M.,Grogan, Michael J.,Charette, André B.,Yu, Lin-Chen,Lory, Caroline D.,Grenier, Louis,Lescarbeau, André,Lane, Benjamin S.,Lombardy, Richard,Behnke, Mark L.,Koney, Nii,Porter, James R.,Campbell, Matthew J.,Shaffer, Jeanne,Xiong, Jimin,Helble, Joseph C.,Foley, Michael A.,Adams, Julian,Castro, Alfredo C.,Tremblay, Martin R.
, p. 786 - 798 (2016/05/19)
The formation of the d-homocyclopamine ring system in IPI-926 is the key step in its semisynthesis and proceeds via a chemoselective cyclopropanation followed by a stereoselective acid-catalyzed carbocation rearrangement. In order to perform large-scale cyclopropanation reactions, we developed new iodomethylzinc bis(aryl)phosphate reagents that were found to be both effective and safe. These soluble reagents can be prepared under mild conditions and are stable during the course of the reaction. Importantly, they have favorable energetics relative to other cyclopropanating agents such as EtZnCH2I. Herein, we describe the process optimization studies that led to successful large-scale production of the d-homocyclopamine core necessary for IPI-926.
Neodymium tris-diarylphosphates: Systematic study of the structure-reactivity relationship in butadiene and isoprene polymerisation
Nifant'Ev, Ilya E.,Tavtorkin, Alexander N.,Korchagina, Sof'Ya A.,Gavrilenko, Inna F.,Glebova, Nataliya N.,Kostitsyna, Nataliya N.,Yakovlev, Vladimir A.,Bondarenko, Galina N.,Filatova, Marina P.
, p. 219 - 277 (2014/05/20)
The catalytic properties of neodymium tris-phosphates with various diarylphosphate ligands in the stereoregular 1,4-cis-polymerisation of butadiene and isoprene were studied. The considerable variability of the diaryl phosphate structure allowed for the systematic investigation of the dependence of the catalytic properties of neodymium tris-diarylphosphates on the electronic and steric properties of the ligand. Electron-withdrawing substituents (F, Cl, Br) in the aryl moiety increased the catalyst activity of tris-diarylphosphate. Neodymium aryl phosphates containing lipophilic bulky ligands provided the synthesis of polydienes with a monomodal molecular-weight distribution. The optimal catalytic properties demonstrated that the neodymium aryl phosphate prepared from bis(2,6-dimethyl-4-tert-butylphenyl)-phosphoric acid showed high activity and ensured a monomodal MWD of polydienes (Mw/Mn ～ 2 for polybutadiene and Mw/Mn ～ 3 for polyisoprene) in various conditions.
Preparation of Sterically Hindered Phosphoramidates
Talley, John J.
, p. 221 - 222 (2007/10/02)
Treatment of phosphorus oxychloride with two equivalents of 2,6-dimethylphenol in the presence of magnesium chloride produced the sterically hindered bis(2,6-dimethylphenyl) chlorophosphate in excellent yield.The diaryl phosphorochloridate reacted with a
'O-Phosphobiotine Analogues.' Isolation, X-Ray Structure, and Reactivity of the Intermediate of the Addition of Hindered Phosphoric Esters and Thioesters on the Carbodi-imide Group. ON Phosphoryl Migration versus P-O-P Bond Formation
Blonski, Casimir,Gasc, Maria-Benedicte,Klaebe, Alain,Perie, Jean-Jacques,Roques, Raymond,et al.
, p. 7 - 14 (2007/10/02)
Addition reactions to carbodi-imides using oxy- and thio-phosphoric diesters crowded around phosphorus have been carried out in order to obtain a better understanding of this reaction, and to trap the intermediate, an O-phophobiotin analogue.Oxy-compounds
