Enantioselective iridium-catalysed intramolecular allylic aminations, using phosphinooxazolines or phosphorus amidites as ligands, provided ee values of >90%, at a catalyst loading of <0.5 mol-%, and displayed a marked preference for intra- over corresponding intermolecular reactions.
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http://dx.doi.org/10.1039/b400023d | DOI Listing |
Chem Commun (Camb)
November 2024
Department of Chemistry, Graduate School of Science, Osaka Metropolitan University, Sumiyoshi, Osaka 558-8585, Japan.
The iridium-catalysed enantioselective [3+2] annulation of -ketoarylboron compounds with conjugated dienes proceeded to give chiral indanol derivatives bearing an all-carbon quaternary stereogenic center in high yields with high enantioselectivity. Chiral phosphoramidite-olefin ligands were effective for the high reactivity and enantioselectivity.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2024
Department of Chemistry, Chemistry Research Laboratory, University of Oxford, 12 Mansfield Road, Oxford, OX1 3TA, UK.
Herein we report the first enantioselective total synthesis of (+)-incargranine A, in nine steps. The total synthesis was enabled by an enantioselective intramolecular organocatalysed desymmetrising Michael addition of a malonamate ester to a linked dienone substrate that established pivotal stereocentres with excellent enantio- and complete diastereoselectivity. Furthermore, a key hemiaminal intermediate was accessed by developing an iridium-catalysed reductive cyclisation, and the scope of this transformation was explored to produce a range of bicyclic hemiaminal motifs.
View Article and Find Full Text PDFOrg Biomol Chem
April 2016
IPOS, The Page Laboratories, Department of Chemical and Biological Sciences, The University of Huddersfield, Queensgate, Huddersfield, HD1 3DH, UK.
The iridium complex of pentamethylcyclopentadiene and (S,S)-1,2-diphenyl-N'-tosylethane-1,2-diamine is an effective catalyst for the asymmetric transfer hydrogenation of imine substrates under acidic conditions. Using the Ir catalyst and a 5 : 2 ratio of formic acid : triethylamine as the hydride source for the asymmetric transfer hydrogenation of 1-methyl-3,4-dihydroisoquinoline and its 6,7-dimethoxy substituted derivative, in either acetonitrile or dichloromethane, shows unusual enantiomeric excess (ee) profiles for the product amines. The reactions initially give predominantly the (R) enantiomer of the chiral amine products with >90% ee but which then decreases significantly during the reaction.
View Article and Find Full Text PDFOrg Biomol Chem
July 2013
Stratingh Institute for Chemistry, University of Groningen, Nijenborgh 4, 9747 AG, Groningen, The Netherlands.
An enantioselective synthesis of almorexant, a potent antagonist of human orexin receptors, is presented. The chiral tetrahydroisoquinoline core structure was prepared via iridium-catalysed asymmetric intramolecular allylic amidation. Further key catalytic steps of the synthesis include an oxidative Heck reaction at room temperature and a hydrazine-mediated organocatalysed reduction.
View Article and Find Full Text PDFChem Commun (Camb)
May 2012
Life Sciences Institute and Departments of Medicinal Chemistry, Chemistry, and Microbiology & Immunology, University of Michigan, Ann Arbor, MI 48109, United States.
A flexible and divergent synthesis of cryptophycin unit A analogues is described. This method relies on iridium-catalysed stereo- and enantioselective crotylation and chemoselective one-pot oxidative olefination to access common intermediate . Heck, cross metathesis, and Suzuki-Miyaura reactions are illustrated for the generation of methyl ester unit A analogues .
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