50490-74-9Relevant articles and documents
Practical Gram-Scale Synthesis of Iboxamycin, a Potent Antibiotic Candidate
Mason, Jeremy D.,Myers, Andrew G.,Pote, Aditya R.,Terwilliger, Daniel W.
supporting information, p. 11019 - 11025 (2021/08/03)
A gram-scale synthesis of iboxamycin, an antibiotic candidate bearing a fused bicyclic amino acid residue, is presented. A pivotal transformation in the route involves an intramolecular hydrosilylation-oxidation sequence to set the ring-fusion stereocenters of the bicyclic scaffold. Other notable features of the synthesis include a high-yielding, highly diastereoselective alkylation of a pseudoephenamine amide, a convergent sp3-sp2 Negishi coupling, and a one-pot transacetalization-reduction reaction to form the target compound's oxepane ring. Implementation of this synthetic strategy has provided ample quantities of iboxamycin to allow for its in vivo profiling in murine models of infection.
Utilization of 1-Oxa-2,2-(dimesityl)silacyclopentane acetals in the stereoselective synthesis of polyols
Powell, Sharon A.,Tenenbaum, Jason M.,Woerpel
, p. 12648 - 12649 (2007/10/03)
We have developed a route for the stereoselective synthesis of 1-oxa-2,2-(dimesityl)silacyclopentane acetals, intermediates in the synthesis of highly functionalized 1,3-diols. This route involves a diastereoselective conjugate addition reaction of a hydrosilyl anion, a subsequent diastereoselective enolate alkylation, and a fluoride-catalyzed intramolecular hydrosilylation reaction to afford the oxasilacyclopentane acetal. A highly selective nucleophilic substitution reaction, followed by oxidation of the C-Si bond, leads to the desired polyol. Copyright
Synthesis and characterization of sterically hindered diarylsilanes containing 2,4,6-trimethylphenyl and 2,4,6-tris( trifluoromethyl) phenyl substituents. X-ray crystal structure of bisfluorosilane
Braddock-Wilking, Janet,Schieser, Matt,Brammer, Lee,Huhmann, Jean,Shaltout, Raef
, p. 89 - 98 (2007/10/02)
Sterically hindered diarylsilanes have been prepared by two synthetic routes.Dimesitylsilane, Mes2SiH2 (1), (Mes = 2,4,6- trimethylphenyl) was synthesized by reaction of mesityl magnesium bromide with HSiCl3 followed by reduction with LiAlH4, or by reaction of mesityl magnesium bromide with (TfO)2SiH2.The mixed diaryl system, MesPhSiH2 (2), was prepared by reaction of (TfO)PhSiH2, with one equivalent of MesMgBr.Diarylsilanes containing the 2,4,6-tris(trifluoromethyl)phenyl substituent, RF, were prepared by reaction of HSiCl3 with 2 equivalents of RFLi to give (RF)2SiHF (3) through a Cl/F halogen exchange.Reduction of 3 with LiAlH4 afforded (RF)2SiH2 (4) which can also be prepared from RFLi and (TfO)2SiH2.All compounds have been characterized by multinuclear NMR, IR, mass spectrometry and chemical analyses.An X-ray crystallographic study of 3 shows that the immediate geometry about silicon is approximately tetrahedral with a C-Si-C angle of 115.8(1)deg.There are unusual intramolecular interactions in 3 with four short Si . . .F contacts with the ortho-CF3 substituents on the aromatic ring which results in an overall tetracapped tetrahedral geometry about silicon.Crystal data for 3 are as follows: monoclinic, P21/c, with a = 9.827(2) Angstroem, b =15.938(3) Angstroem, c =13.239(3) Angstroem, V = 2072.6(8) Angstroem3, Z = 4; and R = 0.0492 (Rw = 0.0535).The short intramolecular Si . . .F contacts are observed in solution for both 3 and 4 by 29Si NMR spectroscopy.Keywords: Silicon; Group 14; Aryl; Mesityl; Crystal structure; Hindered (bulky) ligands
