41010-04-2Relevant articles and documents
Electrophilic Chlorine from Chlorosulfonium Salts: A Highly Chemoselective Reduction of Sulfoxides
Acosta-Guzmán, Paola,Mahecha-Mahecha, Camilo,Gamba-Sánchez, Diego
supporting information, p. 10348 - 10354 (2020/07/13)
Herein, we describe a selective late-stage deoxygenation of sulfoxides based on a novel application of chlorosulfonium salts and demonstrate a new process using these species generated in situ from sulfoxides as the source of electrophilic chlorine. The use of highly nucleophilic 1,3,5-trimethoxybenzene (TMB) as the reducing agent is described for the first time and applied in the deoxygenation of simple and functionalized sulfoxides. The method is easy to handle, economic, suitable for gram-scale operations, and readily applied for poly-functionalized molecules, as demonstrated with more than 45 examples, including commercial medicines and analogues. We also report the results of competition experiments that define the more reactive sulfoxide and we present a mechanistic proposal based on substrate and product observations.
Dealkenylative Thiylation of C(sp3)-C(sp2) Bonds
Smaligo, Andrew J.,Kwon, Ohyun
supporting information, p. 8592 - 8597 (2019/10/14)
Carbon-carbon bond fragmentations are useful methods for the functionalization of molecules. The value of such cleavage events is maximized when paired with subsequent bond formation. Herein we report a protocol for the cleavage of an alkene C(sp3)-C(sp2) bond, followed by the formation of a new C(sp3)-S bond. This reaction is performed in nonanhydrous solvent and open to the air, employs common starting materials, and can be used to rapidly diversify natural products.
Intermolecular Radical Mediated Anti-Markovnikov Alkene Hydroamination Using N-Hydroxyphthalimide
Lardy, Samuel W.,Schmidt, Valerie A.
supporting information, p. 12318 - 12322 (2018/10/02)
An intermolecular anti-Markovnikov hydroamination of alkenes has been developed using triethyl phosphite and N-hydroxyphthalimide. The process tolerates a wide range of alkenes, including vinyl ethers, silanes, and sulfides as well as electronically unbiased terminal and internal alkenes. The resultant N-alkylphthalimides can readily be transformed to the corresponding primary amines. Mechanistic probes indicate that the process is mediated via a phosphite promoted radical deoxygenation of N-hydroxyphthalimide to access phthalimidyl radicals.
Aerial dioxygen activation: Vs. thiol-ene click reaction within a system
Choudhuri, Khokan,Mandal, Arkalekha,Mal, Prasenjit
supporting information, p. 3759 - 3762 (2018/04/16)
Markovnikov or anti-Markovnikov selective thiol-ene click (TEC) reactions and the synthesis of β-hydroxysulfides via aerial dioxygen activation are prevalent C-S bond forming reactions of styrenes and thiophenols. Herein, by choosing appropriate environme
Design, synthesis, and activity evaluation of broad-spectrum small-molecule inhibitors of anti-apoptotic Bcl-2 family proteins: Characteristics of broad-spectrum protein binding and its effects on anti-tumor activity
Zheng, Can-Hui,Yang, Hui,Zhang, Meng,Lu, Shi-Hai,Shi, Duo,Wang, Juan,Chen, Xiu-Hua,Ren, Xiao-Hui,Liu, Jia,Lv, Jia-Guo,Zhu, Ju,Zhou, You-Jun
, p. 39 - 44 (2012/02/16)
On the basis of the comparison of the structure of the Bim BH3: Bcl-x L complex and that of the ABT-737: Bcl-xL complex, a series of class A compounds were designed. These compounds had the basic skeleton of ABT-737 and the h2 residues of Bim BH3. These residues had shown themselves to be relevant to Bim BH3's broad-spectrum binding properties in saturation mutagenesis assays. Unlike ABT-737, which is a selective inhibitor of anti-apoptotic members of the Bcl-2 protein family, the class A compounds showed broad-spectrum binding activity to target proteins similar to those of Bim BH3 peptide. Then class B compounds were synthesized by modifying the structure of the most effective class A compound, A-4. Most of these class B compounds showed better binding affinity to the target proteins than the class A compounds had. They also showed themselves more effective than ABT-737 at inhibiting growth in multiple tumor cell lines known to express Bcl-x L, Bcl-2, and Mcl-1 proteins at high levels. Compounds B-11 and B-12 had the strongest anti-tumor activity of any compounds we produced. This study suggests that it is feasible to design small-molecule inhibitors based on the structure of Bim BH3, which shows broad-spectrum binding to Bcl-xL, Bcl-2, and Mcl-1 proteins. Our results also suggest that the broad-spectrum properties of small-molecule inhibitors binding to target proteins play a critical role in inhibiting the growth of many tumor cells. Finally, our study provides a series of lead compounds that merit further research into anti-cancer therapeutics.
Design, synthesis, and pharmacological effects of structurally simple ligands for MT1 and MT2 melatonin receptors
Carocci, Alessia,Catalano, Alessia,Lovece, Angelo,Lentini, Giovanni,Duranti, Andrea,Lucini, Valeria,Pannacci, Marilou,Scaglione, Francesco,Franchini, Carlo
experimental part, p. 6496 - 6511 (2010/10/02)
A series of phenoxyalkyl and phenylthioalkyl amides were prepared as melatoninergic ligands. Modulation of affinity of the newly synthesized compound by applying SARs around the terminal amide moiety, the alkyl chain, and the methoxy group on the aromatic ring provides compounds with nanomolar affinity for both melatonin receptor subtypes. Affinity towards MT1 and MT2 receptors were modulated also exploiting chirality. The investigation of intrinsic activity revealed that all the tested compounds behave as full or partial agonists.
Oxidized isoquinolinoisoindolinone and benzazepinoisoindolinone alkaloids cores by convergent cyclisation processes: π-aromatic attack of thionium and oxonium species
Bousquet, Till,Fleury, Jean-Fran?ois,Da?ch, Adam,Netchita?lo, Pierre
, p. 706 - 715 (2007/10/03)
An efficient methodology for synthesis of isoindoloisoquinoline 5a and isoindolobenzazepine 5b in oxidized forms as tetracyclic alkaloids cores are reported from N-bromoethylphthalimide (6) or phthalic anhydride and 2-phenylthioethylamine (8) in a five- o
Exocyclic-endocyclic n-acyliminium ion equilibration via an intramolecular α-thioamidoalkylation in the synthesis of fused N,S-heterocyclic systems: Some new parameters
Hucher, Nicolas,Pesquet, Anthony,Netchitailo, Pierre,Daich, Adam
, p. 2758 - 2770 (2007/10/03)
The reactivity of N-[aryl(or alkyl)thio(oxo or seleno)alkylamidals 6 bearing the N-(CH2)n-X-(CH2)m-Ar functionality towards neat TFA has been examined. Substrates of type 6 give, together with the products 11, 17, 19, and
Synthesis, spectral studies and C-S, C-N bond fissions of some novel N-[alkyl (4′-substituted phenylthio)] phthalimides
El-Bardan, Ali A.
, p. 511 - 519 (2007/10/03)
N-[(4′-Substituted phenylthio)ethyl] phthalimide la-g and their corresponding n-propyl 2a-g, n-butyl 3a-g derivatives have been synthesised. The structure of these compounds were proved by UV, IR, 1H NMR, 13CMR and mass spectra. The 1H and 13C chemical shifts of the adjacent methylene protons and carbons of both the sulfur atom and phthalimido nitrogen group were reasonably correlated using σ° values. The carbon-nitrogen and the carbon-sulfur bond fissions in alkaline and acidic media were discussed.
A FACILE ROUTE TO TETRAHYDROISOQUINOLINE ALKALOIDS VIA SULFOXIDE MEDIATED CYCLIZATION
Takano, Seiichi,Iida, Hirokazu,Inomata, Kohei,Ogasawara, Kunio
, p. 47 - 52 (2007/10/02)
A facile route to 1,2,3,4-tetrahydroisoquinoline framework has been developed by employing the sulfoxide mediated cyclization reaction.Utilizing the reaction developed some naturally occurring isoquinoline alkaloids have been synthesized.
