53175-33-0Relevant articles and documents
Cascade of the Hinsberg / IMDAF reactions in the synthesis 2-arylsulfonyl-3a,6-epoxyisoindoles and 4a,7-epoxyisoquinolines in water
Nadirova, Maryana A.,Khanova, Anastasia V.,Zubkov, Fedor I.,Mertsalov, Dmitriy F.,Kolesnik, Irina A.,Petkevich, Sergey K.,Potkin, Vladimir I.,Shetnev, Anton A.,Presnukhina, Sofia I.,Sinelshchikova, Anna A.,Grigoriev, Mikhail S.,Zaytsev, Vladimir P.
, (2021)
N-Furfuryl allylamines, readily accessible from corresponding furfurals or furfuryl amines, react with a broad range of arylsulfonyl chlorides with the formation of a 3a,6-epoxyisoindole core in one synthetic stage. Usually, in boiling water, the interaction sequence involves two consecutive steps: the Hinsberg reaction and the intramolecular Diels–Alder furanе (IMDAF) reaction. The scope and limitations of the proposed method were thoroughly investigated, and it was revealed that the key [4 + 2] cycloaddition step proceeds through an exo-transition state, giving rise to the exclusive formation of a single diastereomer of the target heterocycle. The method allows the ability to obtain N-sulfaryl-substituted 3a,6-epoxyisoindoles and 4a,7-epoxyisoquinolines, which are potentially useful substrates for further transformations and subsequent bioscreening, in particular antimicrobial activity.
Intramolecular (4?+?3) cycloadditions of nitrogen-tethered epoxy enosilanes for the synthesis of heteropolycycles
He, Jiayun,Lam, Shuk Mei,Ng, Jerome P.L.,Wong, Wing-Tak,Chiu, Pauline
, p. 1523 - 1526 (2019)
Furans bearing epoxy enolsilane units via a tether that incorporates a nitrogen heteroatom, undergo intramolecular (4 + 3) cycloadditions to generate bis-heteroatomic polycyclic adducts having piperidine moieties in their frameworks. The cycloadducts, ultimately derived from furfural, a renewal chemical feedstock, are obtained with up to 4:1 dr and with ee retained from the epoxide.
The 3F Library: Fluorinated Fsp3-Rich Fragments for Expeditious 19F NMR Based Screening
Troelsen, Nikolaj S.,Shanina, Elena,Gonzalez-Romero, Diego,Danková, Daniela,Jensen, Ida S. A.,?niady, Katarzyna J.,Nami, Faranak,Zhang, Hengxi,Rademacher, Christoph,Cuenda, Ana,Gotfredsen, Charlotte H.,Clausen, Mads H.
supporting information, p. 2204 - 2210 (2019/12/30)
Fragment-based drug discovery (FBDD) is a popular method in academia and the pharmaceutical industry for the discovery of early lead candidates. Despite its wide-spread use, the approach still suffers from laborious screening workflows and a limited diversity in the fragments applied. Presented here is the design, synthesis, and biological evaluation of the first fragment library specifically tailored to tackle both these challenges. The 3F library of 115 fluorinated, Fsp3-rich fragments is shape diverse and natural-product-like with desirable physicochemical properties. The library is perfectly suited for rapid and efficient screening by NMR spectroscopy in a two-stage workflow of 19F NMR and subsequent 1H NMR methods. Hits against four diverse protein targets are widely distributed among the fragment scaffolds in the 3F library and a 67 % validation rate was achieved using secondary assays. This collection is the first synthetic fragment library tailor-made for 19F NMR screening and the results demonstrate that the approach should find broad application in the FBDD community.
Cucurbit[7]uril as a Supramolecular Artificial Enzyme for Diels–Alder Reactions
Palma, Aniello,Artelsmair, Markus,Wu, Guanglu,Lu, Xiaoyong,Barrow, Steven J.,Uddin, Najib,Rosta, Edina,Masson, Eric,Scherman, Oren A.
, p. 15688 - 15692 (2017/11/13)
The ability to mimic the activity of natural enzymes using supramolecular constructs (artificial enzymes) is a vibrant scientific research field. Herein, we demonstrate that cucurbit[7]uril (CB[7]) can catalyse Diels–Alder reactions for a number of substituted and unreactive N-allyl-2-furfurylamines under biomimetic conditions, without the need for protecting groups, yielding powerful synthons in previously unreported mild conditions. CB[7] rearranges the substrate in a highly reactive conformation and shields it from the aqueous environment, thereby mimicking the mode of action of a natural Diels–Alderase. These findings can be directly applied to the phenomenon of product inhibition observed in natural Diels–Alderase enzymes, and pave the way toward the development of novel, supramolecular-based green catalysts.
Rhodium-Catalyzed Regiodivergent Hydrothiolation of Allyl Amines and Imines
Kennemur, Jennifer L.,Kortman, Gregory D.,Hull, Kami L.
supporting information, p. 11914 - 11919 (2016/10/06)
The regiodivergent Rh-catalyzed hydrothiolation of allyl amines and imines is presented. Bidentate phosphine ligands with larger natural bite angles (βn ≥ 99°), for example, DPEphos, dpph, or L1, promote a Markovnikov-selective hydrothiolation in up to 88% yield and >20:1 regioselectivity. Conversely, when smaller bite angle ligands (βn ≤ 86°), for example, dppbz or dppp, are employed, the anti-Markovnikov product is formed in up to 74% yield and >20:1 regioselectivity. Initial mechanistic investigations are performed and are consistent with an oxidative addition/olefin insertion/reductive elimination mechanism for each regioisomeric pathway. We hypothesize that the change in regioselectivity is an effect of diverging coordination spheres to favor either Rh-S or Rh-H insertion to form the branched or linear isomer, respectively.
Inter- and intramolecular diels-alder reaction of ethenetricarboxylate derivatives
Yamazaki, Shoko,Sugiura, Hirotaka,Niina, Mamiko,Mikata, Yuji,Ogawa, Akiya
, p. 485 - 510 (2016/04/10)
Inter- and intramolecular [4+2] cycloaddition reactions of highly electron-deficient ethenetricarboxylates have been studied. Intermolecular Diels-Alder reaction of ethenetricarboxylate esters and cyclopentadiene proceeded at room temperature or -20 °C to give cycloadducts with 1:1.5-1.9 endo:exo ratio. Lewis acids such as EtAlCl2, Zn(OTf)2 and Cu(OTf)2 catalyzed reaction at room temperature or -40 °C gave cycloadducts with 3.1-5.4:1 endo:exo ratio. Reaction of N-benzyl- or N-allyl-2-furylmethylamine and 1,1-diethyl 2-hydrogen ethenetricarboxylate in the presence of EDCI/HOBt/Et3N at room temperature led directly to an intramolecular Diels-Alder adduct stereoselectively. The observed stereoselectivities were explained by the use of DFT calculations.
Selective hydrosilylation of N-allylimines using a (3-iminophosphine)palladium precatalyst
Tafazolian, Hosein,Schmidt, Joseph A.R.
, p. 685 - 689 (2016/02/18)
Hydrosilylation utilizing a (3-iminophosphine)palladium catalyst leads to the selective reduction of the imine unit of allylimines. Successful reduction of twenty-five different substituted aromatic and alkyl allylimines demonstrated the scope and selecti
Intramolecular diels - Alder cycloaddition of N-allyl-N-(2-furylmethyl)amides - First step of a new route towards the synthesis of a densely functionalized pyrrolizidine ring
Ghelfi, Franco,Parsons, Andrew F.,Tommasini, Daniele,Mucci, Adele
, p. 1845 - 1852 (2007/10/03)
The intramolecular Diels - Alder reaction of N-allyl-N-(2-furylmethyl)amides to exo-N-acyl-3-aza-10-oxatricyclo [5.2.1.01-5]dec-8-enes is described. The cycloaddition is controlled not only by the size of the amide appendage, but also by electronegativity of the amide. An example of a new approach towards the synthesis of a highly functionalized pyrrolizidine ring, which links this Diels - Alder cycloaddition to an halogen atom transfer radical cyclization, is reported.
On the use of removable steric buttresses in cycloaddition reactions
Choony, Nandeo,Dadabhoy, Anjum,Sammes, Peter G.
, p. 2017 - 2021 (2007/10/03)
Use of bulky protecting groups, such as the trityl group, can be utilised to encourage cycloaddition reactions that otherwise do not proceed. Thus N-allylfurfurylamines, bearing the appropriate N-protecting group, can thermally cyclise; subsequent removal
The trityl group as a removable steric buttress in cycloaddition reactions
Choony, Nandeo,Dadabhoy, Anjum,Sammes, Peter G.
, p. 513 - 514 (2007/10/03)
The trityl group is utilised as an effective, temporary, steric buttress in an intramolecular Diels-Alder reaction between an alkene and furan ring.
