cas 5450-75-9, NSC15155 | Articles data

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Cyclometalated Ru(II)-isoquinoline complexes overcome cisplatin resistance of A549/DDP cells by downregulation of Nrf2 via Akt/GSK-3β/Fyn pathway
Both ruthenium (Ru) and isoquinoline (IQ) compounds are regarded as potential anticancer drug candidates. Here, we report the synthesis and characterization of three novel cyclometalated Ru(II)-isoquinoline complexes: RuIQ-3, RuIQ-4, and RuIQ-5, and evalu
Chen, Lanmei,Wang, Jie,Cai, Xianhong,Chen, Suxiang,Zhang, Jingjing,Li, Baojun,Chen, Weigang,Guo, Xinhua,Luo, Hui,Chen, Jincan
(2021/12/04)

Ligand-Controlled Regiodivergence for Catalytic Stereoselective Semireduction of Allenamides
Ligand-controlled regiodivergence has been developed for catalytic semireduction of allenamides with excellent chemo- and stereocontrol. This system also provides an example of catalytic regiodivergent semireduction of allenes for the first time. The divergence of the semireduction is enabled by ligand switch with the same palladium pre-catalyst under operationally simple and mild conditions. Monodentate ligand XPhos exclusively promotes selective 1,2-semireduction to afford allylic amides, while bidentate ligand BINAP completely switched the regioselectivity to 2,3-semireduction, producing (E)-enamide derivatives.
Hajiloo Shayegan, Mojtaba,Li, Zhong-Yuan,Cui, Xin
supporting information

(2021/12/02)

N-Aroylsulfonamide-Photofragmentation (ASAP)-A Versatile Route to Biaryls
The photochemical fragmentation of N-aroylsulfonamides 9 (ASAP) is a powerful method for the preparation of various biaryls. Compounds 9 are easily accessible in two steps from amines by treatment with arenesulfonyl chlorides and aroyl chlorides. Many of these compounds were prepared for the first time. The irradiation takes place in a previously developed continuous-flow reactor using inexpensive UVB or UVC fluorescent lamps. Isocyanates and sulphur dioxide are formed as the only by-products. The ASAP tolerates a variety of functional groups and is even suited for the preparation of phenylnaphthalenes and terphenyls. The ASAP mechanism was elucidated by interaction of photophysical and quantum chemical (DFT) methods and revealed a spirocyclic biradical as key intermediate.
Wessig, Pablo,Krebs, Saskia
supporting information
p. 6367 - 6374
(2021/09/29)

Access to Indole-Fused Benzannulated Medium-Sized Rings through a Gold(I)-Catalyzed Cascade Cyclization of Azido-Alkynes
Because benzannulated and indole-fused medium-sized rings are found in many bioactive compounds, combining these fragments might lead to unexplored areas of biologically relevant and uncovered chemical space. Herein is shown that α-imino gold carbene chem
Greiner, Luca C.,Inuki, Shinsuke,Arichi, Norihito,Oishi, Shinya,Suzuki, Rikito,Iwai, Tomohiro,Sawamura, Masaya,Hashmi, A. Stephen K.,Ohno, Hiroaki
supporting information
p. 12992 - 12997
(2021/07/20)

Catalyst-Free Visible-Light-Mediated Iodoamination of Olefins and Synthetic Applications
Herein we report a catalyst- and metal-free visible-light-mediated protocol enabling the iodoamination of miscellaneous olefins. This protocol is characterized by high yields under environmentally benign reaction conditions utilizing commercially available substrates and a green and biodegradable solvent. Furthermore, the protocol allows for late-stage functionalization of bioactive molecules and can be scaled to gram quantities of product, which offers manifold possibilities for further transformations, including morpholine, piperidine, pyrrolidine, and aziridine synthesis.
Engl, Sebastian,Reiser, Oliver
supporting information
p. 5581 - 5586
(2021/07/26)

Electrochemical C?H Amidation of Heteroarenes with N-Alkyl Sulfonamides in Aqueous Medium
The construction of C?N bonds by free radical reactions represents a powerful synthetic approach for direct C?H amidations of arenes or heteroarenes. Developing efficient and more environmentally friendly synthetic methods for C?H amidation reactions remains highly desirable. Herein, metal-free electrochemical oxidative dehydrogenative C?H amidations of heteroarenes with N-alkylsulfonamides have been accomplished. The catalyst- and chemical-oxidant-free C?H amidation features an ample scope and employs electricity as the green and sole oxidant. A variety of heteroarenes, including indoles, pyrroles, benzofuran and benzothiophene, thereby underwent this C(sp2)?H nitrogenation. Cyclic voltammetry studies and control experiments provided evidence for nitrogen-centered radicals being directly generated under metal-free electrocatalysis.
Zhang, Yan,Lin, Zhipeng,Ackermann, Lutz
supporting information
p. 242 - 246
(2020/11/30)

Novel cyclometalated Ru(II) complexes containing isoquinoline ligands: Synthesis, characterization, cellular uptake and in vitro cytotoxicity
Two novel cyclometalated Ru(II) complexes containing isoquinoline ligand, [Ru(bpy)2(1-Ph-IQ)](PF6), (bpy = 2,2′-bipyridine; 1-Ph-IQ = 1-phenylisoquinoline; RuIQ-1) and [Ru(phen)2(1-Ph-IQ)](PF6) (phen = 1,10-phenanthroline; RuIQ-2) were found to show high cytotoxic activity against NCI–H460, A549, HeLa and MCF-7 cell lines. Notably, both of them exhibited IC50 values that were an order of magnitude lower than those of clinical cisplatin and two structurally similar Ru(II)-isoquinoline complexes [Ru(bpy)2(1-Py-IQ)](PF6)2 (Ru3) and [Ru(phen)2(1-Py-IQ)](PF6)2 (Ru4) (1-Py-IQ = 1-pyridine-2-yl). The cellular uptake and intracellular localization displayed that the two cyclometalated Ru(II) complexes entered NCI–H460 cancer cells dominantly via endocytosis pathway, and preferentially distributed in the nucleus. Further investigations on the apoptosis-inducing mechanisms of RuIQ-1 and RuIQ-2 revealed that the two complexes could cause S, G2/M double-cycle arrest by regulating cell cycle related proteins. The two complexes also could reduce the mitochondrial membrane potential (MMP), promote the generation of intracellular ROS and trigger DNA damage, and then lead to apoptosis-mediated cell death. More importantly, RuIQ-2 exhibits low toxicity both towards normal HBE cells in vitro and zebrafish embryos in vivo. Accordingly, the developed complexes hold great potential to be developed as novel therapeutics for effective and low-toxic cancer treatment.
Chen, Jincan,Wang, Jie,Deng, Yuanyuan,Li, Baojun,Li, Chengpeng,Lin, Yuxue,Yang, Dongbin,Zhang, Huanyun,Chen, Lanmei,Wang, Tao
(2020/07/25)

BRIDGED TRICYCLIC CARBAMOYLPYRIDONE COMPOUNDS AND THEIR PHARMACEUTICAL USE
Compounds for use in treating or preventing human immunodeficiency virus (HIV) infection are disclosed. The compounds have the following formula (I): including stereoisomers and pharmaceutically acceptable salts thereof, wherein R1, R2, L, W1, W2, X, Y, and Z are as defined herein. Methods associated with the preparation and use of such compounds, as well as pharmaceutical compositions comprising such compounds, are also disclosed.
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Paragraph 0481

(2020/10/20)

Catalyst-controlled regiodivergent ring-opening C(sp3)-Si bond-forming reactions of 2-arylaziridines with silylborane enabled by synergistic palladium/copper dual catalysis
A catalyst-controlled regiodivergent and stereospecific ring-opening C(sp3)-Si cross-coupling of 2-arylaziridines with silylborane enabled by synergistic Pd/Cu dual catalysis has been developed. Just by selecting a suitable combination of catalysts, the regioselectivity of the coupling is completely switched to efficiently provide two regioisomers of β-silylamines (i.e., β-silyl-α-phenethylamines and β-silyl-β-phenethylamines) in good to high yields. Furthermore, a slight modification of the reaction conditions caused a drastic change in reaction pathways, leading to a tandem reaction to produce another regioisomer of silylamine (i.e., α-silyl-β-phenethylamines) in an efficient and selective manner.
Takeda, Youhei,Shibuta, Kaoru,Aoki, Shohei,Tohnai, Norimitsu,Minakata, Satoshi
p. 8642 - 8647
(2019/10/02)

Double Functionalization of Styrenes by Cu-Mediated Assisted Tandem Catalysis
The double functionalization of styrenes through Cu-mediated assisted tandem catalysis was developed. The reaction was initiated by Cu-catalyzed aziridination and the subsequent nucleophilic ring-opening, which was triggered by the addition of (NH4)2S2O8 as an oxidant of Cu-catalyst to form a variety of C–C and C–X bonds. The expansion to three contiguous catalytic cycles led to the synthesis of functionalized indolines by one-pot operation.
Kawauchi, Daichi,Ueda, Hirofumi,Tokuyama, Hidetoshi
p. 2056 - 2060
(2019/03/13)

Manganese-Catalyzed N-Alkylation of Sulfonamides Using Alcohols
An efficient manganese-catalyzed N-alkylation of sulfonamides has been developed. This borrowing hydrogen approach employs a well-defined and bench-stable Mn(I) PNP pincer precatalyst, allowing benzylic and simple primary aliphatic alcohols to be employed as alkylating agents. A diverse range of aryl and alkyl sulfonamides undergoes mono-N-alkylation in excellent isolated yields (32 examples, 85% average yield).
Reed-Berendt, Benjamin G.,Morrill, Louis C.
p. 3715 - 3724
(2019/03/30)

Stereoinversion of Unactivated Alcohols by Tethered Sulfonamides
The direct, catalytic substitution of unactivated alcohols remains an undeveloped area of organic synthesis. Moreover, catalytic activation of this difficult electrophile with predictable stereo-outcomes presents an even more formidable challenge. Described herein is a simple iron-based catalyst system which provides the mild, direct conversion of secondary and tertiary alcohols to sulfonamides. Starting from enantioenriched alcohols, the intramolecular variant proceeds with stereoinversion to produce enantioenriched 2- and 2,2-subsituted pyrrolidines and indolines, without prior derivatization of the alcohol or solvolytic conditions.
Marcyk, Paul T.,Jefferies, Latisha R.,AbuSalim, Deyaa I.,Pink, Maren,Baik, Mu-Hyun,Cook, Silas P.
supporting information
p. 1727 - 1731
(2019/01/21)

A bifunctional strategy for N-heterocyclic carbene-stabilized iridium complex-catalyzed: N -alkylation of amines with alcohols in aqueous media
Through the strategy of combining bifunctional 2-hydroxypyridine and a thermally stable N-heterocyclic carbene ligand, an Ir-catalyzed N-monoalkylation reaction has been developed in aqueous media under base-free conditions. This reaction proceeds smoothly with high yields of various aromatic amines and sulfonamides with a wide range of primary alcohols. Experimental and computational studies revealed a metal-ligand cooperative mechanism and its thermal stability during the bifunctional catalysis in aqueous media.
Huang, Ming,Li, Yinwu,Liu, Jiahao,Lan, Xiao-Bing,Liu, Yan,Zhao, Cunyuan,Ke, Zhuofeng
supporting information
p. 219 - 224
(2019/01/28)

Enantioselective Synthesis of trans-Vicinal Diamines via Rhodium-Catalyzed [2+2] Cycloaddition of Allenamides
An efficient protocol for the enantioselective Rh-catalyzed intermolecular head-to-head [2+2] cycloaddition of allenamides was developed. A variety of enantio-enriched cyclobutane-1,2-diamine derivatives were achieved in good yields with good to excellent enantioselectivities. (Figure presented.).
Zheng, Wei-Feng,Sun, Gui-Jun,Chen, Liang,Kang, Qiang
supporting information
p. 1790 - 1794
(2018/04/02)

Designing Homogeneous Bromine Redox Catalysis for Selective Aliphatic C?H Bond Functionalization
The potential of homogeneous oxidation catalysis employing bromine has remained largely unexplored. We herein show that the combination of a tetraalkylammonium bromide and meta-chloroperbenzoic acid offers a unique catalyst system for the convenient and s
Becker, Peter,Duhamel, Thomas,Martínez, Claudio,Mu?iz, Kilian
supporting information
p. 5166 - 5170
(2018/03/28)

Cyclometalated ruthenium complex as well as synthetic method and application thereof
The invention provides a cyclometalated ruthenium complex as well as a synthetic method and application thereof. The cyclometalated ruthenium complex has a chemical general formula of [Ru(L)2(PhIQ-R)](PF6), wherein PhIQ-R serves as a main ligand; when R is equal to H, PhIQ-R refers to 1-phrnyl-isoquinoline; when R is equal to Me, PhIQ-R refers to 1-p-methylphenyl-isoquinoline; and L is an auxiliary ligand and is preferably selected from 2,2-dipyridyl or phenanthroline. The cyclometalated ruthenium complex [Ru(L)2(PhIQ-R)](PF6) has more excellent antitumor activity than cis-platinum and is easily synthesized; and the cyclometalated ruthenium complex disclosed by the invention has excellent antitumor activity and the advantages of transmembrane simplicity, high targeting property and low toxicity, is applied to preparing various anti-cancer drugs or DNA insertion agents and has excellent clinical application prospects.
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Paragraph 0100; 0101; 0112; 0113; 0124; 0125

(2017/07/19)

Atmosphere- and Temperature-Controlled Regioselective Aminobromination of Olefins
A complete switch of regioselectivity in the aminobromination of olefins is realized from delicate changes in the reaction temperature from 25 °C to 40 °C and the atmosphere from air to argon, under catalyst-free conditions. The resulting α-bromoamides ca
Yu, Wesley Zongrong,Cheng, Yi An,Wong, Ming Wah,Yeung, Ying-Yeung
supporting information
p. 234 - 239
(2017/02/05)

Syntheses, spectroscopic investigation and electronic properties of two sulfonamide derivatives: A combined experimental and quantum chemical approach
Two sulfonamides derivatives, N-phenethyl-4-methylbenzenesulfonamide (1) and N-(4-hydroxyphenethyl)-4-methylbenzenesulfonamide (2), were successfully synthesized and fully characterized using 1H NMR, 13C NMR, FT-IR spectroscopies and
Mahmood, Ayyaz,Akram, Tehmina,De Lima, Edna Barboza
p. 496 - 507
(2015/12/30)

A supramolecular ensemble of a PBI derivative and Cu2O NPs: Potential photocatalysts for the Suzuki and Suzuki type coupling reactions
The aggregates of the PBI derivative 1 in combination with Benedict's reagent have been used for the first time as reactors for facile preparation of Cu2O NPs at room temperature. During this process the aldehyde groups of the aggregates of derivative 1 are oxidized to carboxylate groups which act as stabilizers for Cu2O NPs to generate the supramolecular ensemble 2:Cu2O. Interestingly, the in situ generated supramolecular ensemble (2:Cu2O) of Cu2O NPs and aggregates of oxidized species 2 exhibited excellent photocatalytic efficiency in the Suzuki-Miyaura and Suzuki type cross-coupling reactions under mild and eco-friendly conditions.
Singh, Gurpreet,Kumar, Manoj,Sharma, Kamaldeep,Bhalla, Vandana
p. 3278 - 3285
(2016/06/13)

Aggregates of the pentacenequinone derivative as reactors for the preparation of Ag@Cu2O core-shell NPs: An active photocatalyst for Suzuki and Suzuki type coupling reactions
Aggregates of the pentacenequinone derivative 1 act as reactors and stabilizers for rapid and facile preparation of Ag@Cu2O core-shell nanoparticles (NPs) in aqueous medium. The in situ generated Ag@Cu2O core-shell hybrid materials enabled efficient visible light harvesting to catalyse the palladium free Suzuki-Miyaura and Suzuki type cross coupling reactions at room temperature.
Sharma, Kamaldeep,Kumar, Manoj,Bhalla, Vandana
supporting information
p. 12529 - 12532
(2015/08/06)

Rhodium-Catalyzed Hydrosilylation Reaction of N-Sulfonyl-1,2,3-triazoles with Triphenylsilane: Access to Diverse Compounds
A highly efficient rhodium-catalyzed hydrosilylation of N-sulfonyl-1,2,3-triazoles has been developed. The protocol uses readily available N-sulfonyl-1,2,3-triazoles and triphenylsilane as starting materials, and the reactions first gave 2-(triphenylsilyl)-2-aryl-N-(arylsulfonyl)ethanimines, the isomerization of which provided (E)-2-(triphenylsilyl)-2-aryl-N-(arylsulfonyl)ethenamines in the presence of triethylamine; the reduction of which with LiAlH4 led to 2-(triphenylsilyl)-2-aryl-N-(arylsulfonyl)ethanamines. It is worthwhile to note that the obtained products could be converted into indole and arylethylamine derivatives. Therefore, the highly efficient rhodium-catalyzed hydrosilylation method is a valuable strategy for synthesis of diverse compounds.
Wang, Hui,Qiao, Hongwei,Zhang, Hao,Yang, Haijun,Zhao, Yufen,Fu, Hua
p. 4471 - 4480
(2015/07/27)

Palladium-catalyzed regiocontrolled domino synthesis of N-sulfonyl dihydrophenanthridines and dihydrodibenzo[c, e]azepines: Control over the formation of biaryl sultams in the intramolecular direct arylation
A palladium-catalyzed domino N-benzylation/intramolecular direct arylation involving sulfonanilides and 2-bromobenzyl bromides has been developed for the first time, providing a workable access to N-sulfonyl dihydrophenanthridines in good to excellent yields. Under the optimized conditions, the formation of 5,6-dihydrophenanthridines was largely controlled over the formation of biaryl sultams containing a seven member ring. The optimized condition was found extendable to the regiocontrolled domino formation of N-sulfonyl-6,7-dihydro-5H-dibenzo[c,e]azepines over the biaryl sultam formation. Using an appropriate substrate, a biaryl sultam has been obtained exclusively.
Laha, Joydev K.,Dayal, Neetu,Jain, Roli,Patel, Ketul
p. 10899 - 10907
(2015/01/08)

Br?nsted acid-assisted N-alkylation of sulfonamides using ethers as the alkylation reagents
N-Alkylation of sulfonamides using cyclic ethers as alkylation reagents and Br?nsted acid as a catalyst produced pyrrolidine and piperidine derivatives in good yields. When using symmetrical and unsymmetrical ethers as alkylation reagents, mono-N-alkylation of sulfonamides took place to afford the corresponding products.
Shi, Wei,Bai, Chun-Mei,Zhu, Kai,Cui, Dong-Mei,Zhang, Chen
p. 434 - 438
(2014/01/06)

Synthesis and cytotoxicity of novel N-sulfonyl-1,2,3,4- tetrahydroisoquinoline thiosemicarbazone derivatives
The modified Pictet-Spengler reaction of phenylethylbenzene sulfonamide with a commercially available glyoxal to construct 1-benzoyl- and 1-acetyl-1,2,3,4-tetrahydroisoquinolines 9a-n has been reported. The reaction could be accomplished, regardless of th
Pingaew, Ratchanok,Prachayasittikul, Supaluk,Ruchirawat, Somsak,Prachayasittikul, Virapong
p. 267 - 277
(2013/03/13)

Palladium-catalyzed cross-coupling of n -sulfonylaziridines with boronic acids
A mild palladium-catalyzed cross-coupling of unsubstituted and 2-alkyl-substituted aziridines with arylboronic acid nucleophiles is presented. The reaction is highly regioselective and compatible with diverse functionality. A catalytic amount of base, a sterically demanding triarylphosphine ligand, and a phenol additive are critical to the success of the reaction. Coupling of a deuterium-labeled substrate established that ring opening of the aziridine occurs with inversion of stereochemistry.
Duda, Megan L.,Michael, Forrest E.
p. 18347 - 18349
(2014/01/06)

Nucleophilic substitution reaction at the nitrogen of arylsulfonamides with phosphide anion
A novel nucleophilic substitution reaction at the nitrogen of arylsulfonamides by means of phosphide anions has been described. This reaction allows for the efficient transformation of arylsulfonamides into synthetically valuable phosphamides, amines, and a variety of protected amines.
Yoshida, Suguru,Igawa, Kazunobu,Tomooka, Katsuhiko
supporting information
p. 19358 - 19361
(2013/02/22)

Progresses in the pursuit of aldose reductase inhibitors: The structure-based lead optimization step
Aldose reductase (ALR2) is a crucial enzyme in the development of the major complications of diabetes mellitus. Very recently it has been demonstrated that the ARL2 inhibitor, fidarestat, significantly prevents inflammatory signals (TNF-α, LPS) that cause cancer (colon, breast, prostate and lung), metastasis, asthma, and other inflammatory diseases. Currently, fidarestat is in phase III clinical trial for diabetic neuropathy and was found to be safe. Thus the finding of novel, potent ARL2 inhibitors is today more than in the past in great demand as they can pave the way for a novel therapeutic approach for a number of diseases besides the diabetes. Herein, starting from the virtual screening-derived ALR2 inhibitor S12728 (1), a rational receptor-based lead optimization has been undertaken. The design and synthetic efforts here reported led to the discovery of several new compounds endowed with low micromolar/submicromolar activities.
Ramunno, Anna,Cosconati, Sandro,Sartini, Stefania,Maglio, Vita,Angiuoli, Sara,La Pietra, Valeria,Di Maro, Salvatore,Giustiniano, Mariateresa,La Motta, Concettina,Da Settimo, Federico,Marinelli, Luciana,Novellino, Ettore
experimental part
p. 216 - 226
(2012/07/16)

Nickel-catalyzed negishi alkylations of styrenyl aziridines
A nickel-catalyzed cross-coupling reaction between N-sulfonyl aziridines and organozinc reagents is reported. The catalytic system comprises an inexpensive and air-stable Ni(II) source and dimethyl fumarate as ligand. Regioselective synthesis of β-substituted amines is possible under mild and functional-group-tolerant conditions. The stereoselectivity of the reaction is consistent with a stereoconvergent mechanism wherein the sulfonamide directs C-C bond formation.
Huang, Chung-Yang,Doyle, Abigail G.
p. 9541 - 9544
(2012/07/14)

NAlkylation of tosylamides using esters as primary and tertiary alkyl sources: Mediated by hydrosilanes activated by a ruthenium catalyst
Select your group: Either a primary or tertiary alkyl group can be selectively introduced onto the nitrogen atom of tosylamides in a ruthenium-catalyzed reaction employing hydrosilanes through a judicious choice in the esters that serve as the alkyl source (see scheme; Ts= 4-toluenesulfonyl). These N-alkylation reactions are useful for construction of naturally occurring azacyclic skeletons. Copyright
Nishikata, Takashi,Nagashima, Hideo
supporting information; experimental part
p. 5363 - 5366
(2012/07/03)

Efficient dehydrative C-N bond formation using alcohols and amides in the presence of silica supported perchloric acid as a heterogeneous catalyst
Silica supported perchloric acid has been utilized as an efficient heterogeneous recyclable catalyst for N-alkylation of amides (sulfonamides and carboxamides) using alcohols (primary and secondary aliphatic as well as benzylic). The products are formed in high yields within 2-3 h.
Das, Biswanath,Reddy, Parigi Raghavendar,Sudhakar, Chithaluri,Lingaiah, Maram
experimental part
p. 3521 - 3522
(2011/06/27)

BF3·OEt2-Mediated highly regioselective S N2-type ring-opening of N-activated aziridines and N-activated azetidines by tetraalkylammonium halides
(Chemical Equation Presented) A highly regioselective Lewis acid-mediated SN2-type ring-opening of N-sulfonylaziridines and azetidines with tetraalkylammonium halides in CH2Cl2 solution to afford 1,2- and 1,3-haloamines in excellent yields is described. An easy diastereoselective route toward substituted chiral N-tosylaziridines has been developed. The mechanism of ring-opening via SN2 pathway has been confirmed by the formation of chiral haloamines with excellent er and dr. Chloroamines obtained from 2,3-disubstituted aziridines were converted to the chiral N-tosylamines via radical dehalogenation. 2009 American Chemical Society.
Ghorai, Manas K.,Kumar, Amit,Tiwari, Deo Prakash
experimental part
p. 137 - 151
(2010/04/04)

Alkali metals in silica gel (M-SG): A new reagent for desulfonation of amines
(Chemical Equation Presented) A novel method for the desulfonation of secondary amines is described. Alkali metals absorbed into nanostructured silica (M-SG) were found to be useful solid-state reagents for the desuffonation of a range of N,N-disubstituted sulfonamides. M-SG reagents are room-temperature- stable free-flowing powders that retain the chemical reactivity of the parent metal, decreasing the danger and associated cost of using reactive metals.
Nandi, Partha,Redko, Mikhail Y.,Petersen, Kathryn,Dye, James L.,Lefenfeld, Michael,Vogt, Paul F.,Jackson, James E.
supporting information; experimental part
p. 5441 - 5444
(2009/06/18)

Expedient synthesis of sulfinamides from sulfonyl chlorides
Sulfinamides were synthesized from sulfonyl chlorides using a procedure involving in situ reduction of sulfonyl chlorides. The reaction is broad in scope and easy to perform.
Harmata, Michael,Zheng, Pinguan,Huang, Chaofeng,Gomes, Maria G.,Ying, Weijiang,Ranyanil, Kanok-On,Balan, Gayatri,Calkins, Nathan L.
p. 683 - 685
(2007/10/03)

Facile amine formation by intermolecular catalytic amidation of carbon-hydrogen bonds
A simple copper-based catalytic system has been developed for the carbon-hydrogen amidation reaction. The copper-homoscorpionate complex Tp Br3Cu(NCMe) catalyzes the transfer of the nitrene unit NTs (Ts = p-toluenesulfonyl) and its subsequent insertion into the sp3 C-H bonds of alkyl aromatic and cyclic ethers or the sp2 C-H bonds of benzene using PhI=NTs as the nitrene source, affording the corresponding trisubstitued NR1HTs amines in moderate to high yields. The use of the environmentally friendly chloramine-T has also proven effective, with the advantage that sodium chloride is formed as the only byproduct. A tandem, one-pot consecutive nitrene-carbene insertion system has been developed to yield amino acid derivatives.
Fructos, Manuel R.,Trofimenko, Swiatoslaw,Mar Diaz-Requejo,Perez, Pedro J.
p. 11784 - 11791
(2007/10/03)

Catalytic N-sulfonyliminium ion-mediated cyclizations to α-vinyl-substituted isoquinolines and β-carbolines and applications in metathesis
Catalytic Sn(OTf)2-induced cyclization of linear, aryl-containing allylic N,O-acetals produced vinyl-substituted tetrahydroisoquinolines and tetrahydro-1H-β-carbolines. The usefulness of the vinyl moiety in the resulting products was demonstrated via the synthesis of various key building blocks for alkaloid structures. The α-vinyl moiety was utilized in a [2,3] sigmatropic rearrangement, in ring-closing metathesis and a cross-metathesis-based synthesis of vincantril, an antianoxia agent, and a synthetic member of the vincamine type natural products.
Kinderman, Sape S.,Wekking, Monique M. T.,Van Maarseveen, Jan H.,Schoemaker, Hans E.,Hiemstra, Henk,Rutjes, Floris P. J. T.
p. 5519 - 5527
(2007/10/03)

ROMP-generated oligomeric sulfonyl chlorides as versatile soluble scavenging agents.
[reaction: see text] A new method for homogeneous nucleophilic scavenging employing oligomeric sulfonyl chloride (OSC) reagents is described. The method utilizes OSC to rapidly scavenge a variety of amines that are present in excess. The OSC reagents are generated from ROM polymerization of 2-chlorosulfonyl-5-norbornene utilizing the second generation Grubbs catalyst to produce oligomers of varying size as stable, free-flowing powders. Following the scavenging event, these oligomers are precipitated with ethyl acetate leaving products in excellent yield and purity.
Moore, Joel D,Herpel, Russell H,Lichtsinn, Joy R,Flynn, Daniel L,Hanson, Paul R
p. 105 - 107
(2007/10/03)

Parallel synthesis and biological activity of a new class of high affinity and selective δ-opioid ligand
A considerable number of research papers describing the synthesis and testing of the delta opioid receptor (DOR) ligands, SNC-80 and TAN-67, and analogues of these two compounds, have been published in recent years. However, there have been few reports of the discovery of completely new structural classes of selective DOR ligand. By optimising a hit compound identified by high throughput screening, a new series of tetrahydroisoquinoline sulphonamide-based delta opioid ligands was discovered. The main challenge in this series was to simultaneously improve both affinity and physicochemical properties, notably aqueous solubility. The most active ligand had an affinity (IC50) of 6 nM for the cloned human DOR, representing a 15-fold improvement relative to the original hit 1 (IC50 98 nM). Compounds from this new series show good selectivity for the DOR over μ and κ opioid receptors. However the most active and selective compounds had poor aqueous solubility. Improved aqueous solubility was obtained by replacing the phthalimide group in 1 by basic groups, allowing the synthesis of salt forms. A series of compounds with improved affinity and solubility relative to 1 was identified and these compounds showed activity in an in vivo model of antinociception, the formalin paw test. In the case of compound 19, this analgesic activity was shown to be mediated primarily via a DOR mechanism. The most active compound in vivo, 46, showed superior potency in this test compared to the reference DOR ligand, TAN-67 and similar potency to morphine (68% and 58% inhibition in Phases 1 and 2, respectively, at a dose of 10 mmol/kg i.v.).
Barn,Caulfield,Cottney,McGurk,Morphy,Rankovic,Roberts
p. 2609 - 2624
(2007/10/03)

A general method for deprotection of N-toluenesulfonyl aziridines using sodium naphthalenide
Deprotection of a variety of N-tosylaziridines with sodium naphthalenide provided the corresponding N-H-aziridines in excellent yield. No single electron transfer (SET) induced aziridine ring opening was seen under the conditions employed for the deprotection reaction.
Bergmeier, Stephen C.,Seth, Punit P.
p. 6181 - 6184
(2007/10/03)

Pictet-Spengler condensation of N-sulfonyl-β-phenethylamines with α- chloro-α-phenylselenoesters. New synthesis of 1,2,3,4- tetrahydroisoquinoline-1-carboxylates
The reaction of N-sulfonyl-β-phenethylamines with α-chloro-a- phenylseleno acetate/propionate esters under Lewis acid promotion gives moderate to good yields of the corresponding 1,2,3, 4- tetrahydroisoquinoline-1-carboxylates. Varying degrees of diastereoselection were obtained using chiral sulfonamides and/or esters. Employing this strategy, the achievement of a new total synthesis of Calycotomine is reported.
Silveira, Claudio C.,Bernardi, Carmem R.,Braga, Antonio L.,Kaufman, Teodoro S.
p. 4969 - 4972
(2007/10/03)

Reductive opening of aziridines with polymethylhydrosiloxane
Regio and chemoselective reductive opening of aziridines is achieved using catalytic palladium on charcoal and polymethylhydrosiloxane (PMHS) as a soluble hydrogen source.
Chandrasekhar,Ahmed, Moinuddin
p. 9325 - 9327
(2007/10/03)

Deprotection of sulfonyl aziridines
The deprotection of the chiral N-sulfonyl aziridines 1-3 has been studied under different desulfonylation conditions. Two methods for the efficient aleprotection of 2-benzyl-, 2-phenyl-, and 2-carboxyl-N- sulfonylaziridines were found. The desulfonylation with lithium and a catalytic amount of di-tert-butyl biphenyl in THF at -78 °C led to the corresponding NH aziridines with yields up to 85%. Alternatively, the desulfonylation could be carried out with magnesium in methanol under ultrasonic conditions. The latter proved to be a very mild method and afforded the desulfonylated aziridines with yields up to 75%, even when the 2-phenyl substituted aziridine 2 was the studied substrate. Furthermore, in all the cases studied, no racemization was observed in the chiral center of the aziridines.
Alonso, Diego A.,Andersson, Pher G.
p. 9455 - 9461
(2007/10/03)

Facile and specific nickel-catalyzed de-N-allylation
A general procedure for a chemoselective removal of the allyl (2- propenyl) functionality on basic, neutral and acidic nitrogens by diisobutylaluminum hydride or trimethylaluminum in the presence of a catalytic amount of (dppp)NiCl2 has been developed.
Taniguchi, Takahiko,Ogasawara, Kunio
p. 4679 - 4682
(2007/10/03)

A Convenient Conversion of Primary Amines into the Corresponding Halides Radical Promoted Halodeamination via N-Substituted-N-Tosylhydrazines
Treatment of 1-substituted-1-tosylhydrazines with 2 equivalents of NCS or NBS in dry THF in presence of light affords the corresponding alkyl halides in good yields.This reaction presumably involves the initial formation of a stabilized hydrazyl radical which is halogenated in a radical chain process.Elimination of p-toluenesulfinic acid and extrusion of nitrogen leads to the corresponding alkyl halide.This route provides an improved method for halodeamination under neutral reaction conditions.
Collazo, Luis R.,Guziec, Frank S.,Hu, Wei-Xiao Jr.,Pankayatselvan, Ratnadevi
p. 7911 - 7914
(2007/10/02)

Reaction of [N-(p-toluenesulfonyl)imino]phenyliodinane with trialkylboranes: Transformation of a boron-carbon bond into a nitrogen-carbon bond
N-Toluenesulfonyl protected primary amines were obtained in good to excellent yield by reaction of [N-(p-toluenesulfonyl)imino]phenyliodinane with trialkylboranes.
Yang,Dai
p. 481 - 482
(2007/10/02)

Facile Deoxygenation of Phenols and Enols Using Sodium Borohydride-Nickel Chloride
A facile deoxygenation reaction of phenol and 1,3-dicarbonyl compounds was investigated.Phenols, enolizable 1,3-diketones and 3-ketoesters were converted into the toluene-p-sulfonates which were reduced by a sodium borohydride-nickel chloride system to give the deoxygenated aromatic compounds, alcohols and esters, respectively.
Wang, Feng,Chiba, Kazuhiro,Tada, Masahiro
p. 1897 - 1900
(2007/10/02)

A General Method for the Reductive Carbamation and Sulfonamidation of Aldehydes
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Alexander, Michael D.,Anderson, Robert E.,Sisko, Joseph,Weinreb, Steven M.
p. 2563 - 2564
(2007/10/02)

Chemical and Spectroscopical Evidence for an Electron-Transfer Mechanism in the Reaction of Arenesulfonyl Chlorides with Anions
The reaction of amide and amidate anions 2 with p-toluenesulfonyl chloride (1) under different reaction conditions gives rise to the total or partial reduction of the acyl halide to p-toluenesulfinic acid (5) and acylation compounds in variable amounts depending on the crowding at the anionic center.This indicates that a Single-Electron Transfer (SET) mechanism is involved in the reactions of 1 with anions.Unpaired electron species are detected by ESR in the course of the reactions. - Key Words: Arene sulfonyl chlorides/ Electron transfer (ET) mechanism
Asensio, Gregorio,Nunez, Elena Gonzalez,Rodrigo, Maria Jose,Varea, Teresa
p. 1799 - 1802
(2007/10/02)

Reactions with Aziridines. 48. Friedel-Crafts Reactions with N-Sulfonated Aziridines and with Open-Chain Sulfonamides. Sulfonamides as Leaving Groups in Open-Chain Structures
AlCl3-catalyzed reactions of N-sulfonylaziridines (C substituents given) 1a (no substituent), 4b (2-phenyl), 8b (2,3-diphenyl), and 11a-c (2,2-dimethyl) with neat benzene, toluene, or anisole proceeded rapidly without heating.The expected N-sulfonyl(aryle
Stamm, Helmut,Onistschenko, Andreas,Buchholz, Berthold,Mall, Thomas
p. 193 - 199
(2007/10/02)