162136-06-3Relevant articles and documents
Scalable Biomimetic Syntheses of Paeciloketal B, 1- epi-Paeciloketal B, and Bysspectin A
Brimble, Margaret A.,Davison, Emma K.,Shepperson, Caitlin E.,Wilson, Zoe E.
, p. 2345 - 2351 (2021)
The first total synthesis of the benzannulated 5,5-spiroketal natural products paeciloketal B and 1-epi-paeciloketal B has been achieved in 10 linear steps employing a biomimetic spiroketalization. This approach also furnished the related natural product
Stereoselective Oxidative Cyclization ofN-Allyl Benzamides to Oxaz(ol)ines
Abazid, Ayham H.,Hollwedel, Tom-Niklas,Nachtsheim, Boris J.
supporting information, p. 5076 - 5080 (2021/07/19)
This study presents an enantioselective oxidative cyclization ofN-allyl carboxamides via a chiral triazole-substituted iodoarene catalyst. The method allows the synthesis of highly enantioenriched oxazolines and oxazines, with yields of up to 94% and enantioselectivities of up to 98% ee. Quaternary stereocenters can be constructed and, besidesN-allyl amides, the corresponding thioamides and imideamides are well tolerated as substrates, giving rise to a plethora of chiral 5-memberedN-heterocycles. By applying a multitude of further functionalizations, we finally demonstrate the high value of the observed chiral heterocycles as strategic intermediates for the synthesis of other enantioenriched target structures.
NOVEL SELECTIVE KAPPA OPIOID RECEPTOR ANTAGONISTS AND METHODS RELATED THERETO FOR TREATMENT OF ADDICTION AND NEUROPATHIC PAIN
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Paragraph 00071, (2020/05/28)
Disclosed is a composition and method for a therapeutic treatment that is able to combat certain conditions such as addiction, alcohol dependence, opioid abuse treatment, neurological disorders, neuropathic pain, and combinations thereof. The compounds act by acting as selective antagonist to the kappa (K) opioid receptor, which, when present leads to the inhibition of conditions, providing increased performance over known treatments. The disclosed compounds also shows the ability to cross the blood-brain-barrier in a highly efficient manner. The disclosed compounds are shown to be effective in the nanomolar range.
Evolution of N-Heterocycle-Substituted Iodoarenes (NHIAs) to Efficient Organocatalysts in Iodine(I/III)-Mediated Oxidative Transformations
Boelke, Andreas,Nachtsheim, Boris J.
supporting information, p. 184 - 191 (2019/12/11)
The reactivity of ortho-functionalized N-heterocycle-substituted iodoarenes (NHIAs) as organocatalysts in iodine(I/III)-mediated oxidations was systematically investigated in the α-tosyloxylation of ketones as the model reaction. During a systematic catalyst evolution, it was found that NH-triazoles and benzoxazoles have the most significant positive influence on the reactivity of the central iodine atom. A further catalyst improvement which focused on the substitution pattern of the arene revealed a remarkable ortho-effect. By introduction of an o-OMe group we were able to generate a novel NHIA with a so far unseen catalytic efficiency. This new catalyst is not only easy to synthesize but also enabled the α-tosyloxylation of carbonyl compounds at the lowest reported catalyst loading of only 1 mol%. Finally, the performance of this iodine(I) catalyst was successfully demonstrated in intramolecular oxidative couplings of biphenyls and oxidative rearrangements. (Figure presented.).
Catalytic Enantioselective Synthesis of Atropisomeric Biaryls: A Cation-Directed Nucleophilic Aromatic Substitution Reaction
Armstrong, Roly J.,Smith, Martin D.
supporting information, p. 12822 - 12826 (2016/02/18)
A catalytic enantioselective nucleophilic aromatic substitution reaction which yields axially chiral biaryl derivatives in excellent yields with e.r. values of up to 97:3 has been developed. This process uses a chiral counterion to direct the addition of thiophenolate to a prochiral dichloropyrimidine by a tandem desymmetrization/kinetic resolution mechanism. The products can be derivatized to a range of atropisomeric structures without any reduction in enantioenrichment, thus offering access to unexplored chiral biaryl architectures.
Enantioselective synthesis of multisubstituted biaryl skeleton by chiral phosphoric acid catalyzed desymmetrization/kinetic resolution sequence
Mori, Keiji,Ichikawa, Yuki,Kobayashi, Manato,Shibata, Yukihiro,Yamanaka, Masahiro,Akiyama, Takahiko
supporting information, p. 3964 - 3970 (2013/04/24)
Described herein is the enantioselective synthesis of multisubstituted biaryl derivatives by chiral phosphoric acid catalyzed asymmetric bromination. Two asymmetric reactions (desymmetrization and kinetic resolution) proceeded successively to afford chiral biaryls in excellent enantioselectivities (up to 99% ee). Both experimental and computational studies suggested that this excellent selectivity could be achieved via a highly organized hydrogen bond network among a substrate, a catalyst (chiral phosphoric acid), and a brominating reagent (N-bromophthalimide).
Phosphine/palladium-catalyzed syntheses of alkylidene phthalans, 3-deoxyisoochracinic acid, isoochracinic acid, and isoochracinol
Fan, Yi Chiao,Kwon, Ohyun
, p. 3264 - 3267 (2012/08/28)
In this study we used sequential catalysis-PPh3-catalyzed nucleophilic addition followed by Pd(0)-catalyzed Heck cyclization-to construct complex functionalized alkylidene phthalans rapidly, in high yields, and with good stereoselectivities (E/Z ratios of up to 1:22). The scope of this Michael-Heck reaction includes substrates bearing various substituents around the alkylidene phthalan backbone. Applying this efficient sequential catalysis, we accomplished concise total syntheses of 3-deoxyisoochacinic acid, isoochracinic acid, and isoochracinol.
Total synthesis of cyclo-mumbaistatin analogues through anionic homo-fries rearrangement
Neufeind, Stefan,Huelsken, Nils,Neudoerfl, Joerg-Martin,Schloerer, Nils,Schmalz, Hans-Guenther
supporting information; experimental part, p. 2633 - 2641 (2011/04/16)
The structurally unique polyketide mumbaistatin is the strongest naturally occurring inhibitor of glucose-6-phosphate translocase-1 (G6P-T1), which is a promising target for drugs against type-2 diabetes mellitus and angiogenic processes associated with brain tumor development. Despite its high relevance, mumbaistatin has so far withstood all attempts towards its total synthesis. In the present study an efficient total synthesis of a deoxy-mumbaistatin analogue containing the complete carbon skeleton and a spirolactone motif closely resembling the natural product in its cyclized form was elaborated. Key steps of the synthesis are a Diels-Alder cycloaddition for the construction of the fully functionalized anthraquinone moiety and an anionic homo-Fries rearrangement to build up the tetra-ortho-substituted benzophenone core motif, from which a spiroketal lactone forms in a spontaneous process. The elaborated strategy opens an entry to a variety of new analogs of mumbaistatin and cyclo-mumbaistatin and may be exploited for the total synthesis of the natural product itself in the future.
Design and synthesis of simplified taxol analogs based on the T-Taxol bioactive conformation
Zhao, Jielu,Bane, Susan,Snyder, James P.,Hu, Haipeng,Mukherjee, Kamalika,Slebodnick, Carla,Kingston, David G.I.
scheme or table, p. 7664 - 7678 (2012/01/05)
A series of compounds designed to adopt a conformation similar to the tubulin-binding T-Taxol conformation of the anticancer drug paclitaxel has been synthesized. Both the internally bridged analogs 37-39, 41 and the open-chain analogs 27-29 and 43 were prepared. The bridged analogs 37-39 and 41 were synthesized by Grubbs' metatheses of compounds 30-32 and 33, which, in turn, were prepared by coupling β-lactams 24-26 with alcohols 22 and 23. Both the bridged and the open-chain analogs showed moderate to good cytotoxicity.
Synthesis of methoxy substituted centrally chiral triynes as precursors of functionalised nonracemic helicene-like compounds
Krausova, Zuzana,Sehnal, Petr,Teply, Filip,Stara, Irena G.,Stary, Ivo,Saman, David,Cvacka, Josef,Fidler, Pavel
, p. 1499 - 1522 (2008/09/16)
A modular synthesis of a series of methoxy substituted optically pure aromatic triynes (-)-(S)-5-9 and (-)-(R)-10 is presented. It relies on key operations such as substitution of benzylic bromine with an alkoxy group and aryl-alkyne coupling reaction to
