59995-48-1Relevant articles and documents
Total synthesis of (±)-hippolachnin A
Ruider, Stefan A.,Sandmeier, Tobias,Carreira, Erick M.
, p. 2378 - 2382 (2015)
The first total synthesis of the marine polyketide (±)-hippolachnin A has been achieved in nine linear steps and an overall yield of 9%. Rapid access to the oxacyclobutapentalene core structure was secured by strategic application of an ene cyclization.
Asymmetric synthesis of chiral cycloalkenone derivatives via palladium catalysis
Trost, Barry M.,Masters, James T.,Lumb, Jean-Philip,Fateen, Dahlia
, p. 1354 - 1360 (2014/03/21)
The palladium-catalyzed oxidative desymmetrization of meso-dibenzoates yields γ-benzoyloxy cycloalkenones in good yields and with excellent levels of enantioselectivity. These compounds serve as precursors to a broad range of substituted cycloalkenones, including well-established synthetic building blocks and elaborated cycloalkanone derivatives. The ability to prepare both enantiomers of the oxidative desymmetrization products enables a unified strategy toward stereochemically diverse epoxyquinoid natural products.
Stereodivergent synthesis of enantioenriched 4-hydroxy-2-cyclopentenones
Singh, Gurpreet,Meyer, Angelica,Aube, Jeffrey
, p. 452 - 458 (2014/01/17)
Protected 4-hydroxycyclopentenones (4-HCPs) constitute an important class of intermediates in chemical synthesis. A route to this class of compound has been developed. Key steps include Noyori reduction (which establishes the stereochemistry of the produc
Enantioselective synthesis of 4-heterosubstituted cyclopentenones
Ulbrich, Kathrin,Kreitmeier, Peter,Vilaivan, Tirayut,Reiser, Oliver
, p. 4202 - 4206 (2013/06/04)
Racemic 4-hydroxycyclopentenone, readily derived from furfuryl alcohol, can be transformed via its O-Boc derivative to 4-acyloxy, 4-aryloxy-, 4-amino-, or 4-thio-substituted cyclopentenones with high enantioselectivity by palladium-catalyzed kinetic resolution via nucleophilic allylic substitutions. Applying this methodology, a short formal synthesis of ent-noraristeromycin was readily accomplished.
Formation of cyclopentene nitro-ester and derivatives
-
, (2012/08/14)
Disclosed is a method of synthesizing new optically pure heterocyclic compounds using Pd(0) catalyzed intramolecular cyclizations. Analogs of cyclopentanes, like isoxazoline-2-oxide and furan, with similar framework to the cyclopentanes act as anti-HIV and anticancer agents which opens a whole new field for application of these compounds. Starting from a meso-diol, optically pure compounds were prepared without utilizing chiral ligands at any stage of the synthesis. The stereochemical outcome of the product (>99% ee) was influenced by desymmetrization catalyzed by Pseudomonas cepacia lipase and the stereoselective nature of the palladium catalyzed transformations.
Divergent synthesis and chemical reactivity of bicyclic lactone fragments of complex rearranged spongian diterpenes
Schnermann, Martin J.,Beaudry, Christopher M.,Genung, Nathan E.,Canham, Stephen M.,Untiedt, Nicholas L.,Karanikolas, Breanne D. W.,Suetterlin, Christine,Overman, Larry E.
supporting information; experimental part, p. 17494 - 17503 (2011/12/04)
The synthesis and direct comparison of the chemical reactivity of the two highly oxidized bicyclic lactone fragments found in rearranged spongian diterpenes (8-substituted 6-acetoxy-2,7-dioxabicyclo[3.2.1]octan-3-one and 6-substituted 7-acetoxy-2,8-dioxabicyclo[3.3.0]octan-3-one) are reported. Details of the first synthesis of the 6-acetoxy-2,7-dioxabicyclo[3.2.1]octan-3- one ring system, including an examination of several possibilities for the key bridging cyclization reaction, are described. In addition, the first synthesis of 7-acetoxy-2,8-dioxabicyclo[3.3.0]octanones containing quaternary carbon substituents at C6 is disclosed. Aspects of the chemical reactivity and Golgi-modifying properties of these bicyclic lactone analogs of rearranged spongian diterpenes are also reported. Under both acidic and basic conditions, 8-substituted 2,7-dioxabicyclo[3.2.1]octanones are converted to 6-substituted-2,8-dioxabicyclo[3.3.0]octanones. Moreover, these dioxabicyclic lactones react with primary amines and lysine side chains of lysozyme to form substituted pyrroles, a conjugation that could be responsible for the unique biological properties of these compounds. These studies demonstrate that acetoxylation adjacent to the lactone carbonyl group, in either the bridged or fused series, is required to produce fragmented Golgi membranes in the pericentriolar region that is characteristic of macfarlandin E.
Synthesis of functionalized bicyclo[3.2.0]heptanes - A study of the [2+2] photocycloaddition reactions of 4-hydroxycyclopent-2-enone derivatives
Le Liepvre, Matthieu,Ollivier, Jean,Aitken, David J.
experimental part, p. 5953 - 5962 (2010/03/03)
A selection of 4-hydraxycyclopent-2-enone derivatives were prepared in enantiomerically pure form, and their photochemical [2+2] cycloaddition reactions with a variety of alkenes were studied, with a view to providing diversely functionalized bicyclo[3.2.0]heptanes. Intermolecular reactions provided the target structures in reasonable yields as a mixture of exo and endo adducts, in proportions which varied very little as a. function of the steric bulk of the reactants or the reaction conditions, The system was suitably adapted for an intramolecular reaction, which provided a single, stereochemically pure product, the convenient precursor of a rigid, concave, trioxygenated skeleton.
Pd(0) catalyzed intramolecular alkylation: stereoselective synthesis of furan and isoxazoline-2-oxide analogs
Khan, Pasha M.,Wu, Ruizhi,Bisht, Kirpal S.
, p. 1116 - 1126 (2007/10/03)
New optically pure isoxazoline-2-oxide and furan analogs have been synthesized using Pd(0) catalyzed intramolecular cyclizations. Starting from a meso-diol, optically pure compounds were prepared without utilizing chiral ligands at any stage of the synthesis. The stereochemical outcome of the product (>99% ee) was influenced by desymmetrization catalyzed by Pseudomonas cepacia lipase and the stereoselective nature of the palladium catalyzed transformations.
An electrochemical approach to the guanacastepenes
Hughes, Chambers C.,Miller, Aubry K.,Trauner, Dirk
, p. 3425 - 3428 (2007/10/03)
(Chemical Equation Presented) An asymmetric approach toward the [6-7-5] ring system of the guanacastepenes is described.
Toward the total syntheses of pepluanin A and euphosalicin: Concise route to a highly oxygenated cyclopentane as a common intermediate
Gilbert, Michael W.,Galkina, Anna,Mulzer, Johann
, p. 2558 - 2562 (2007/10/03)
A substrate controlled asymmetric synthesis is described of a highly functionalized cyclopentanyl vinyl triflate which serves as an advanced intermediate in the total synthesis of the novel multidrug resistance reversing jatrophanes pepluanin A and euphosalicin. Key steps are a Claisen-Eschenmoser rearrangement followed by hydroxy-lactonization, intramolecular trans-lactonization, Davis hydroxylation and regioselective enoltriflate formation.