- Bioorthogonal Enzymatic Activation of Caged Compounds
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Engineered cytochrome P450 monooxygenase variants are reported as highly active and selective catalysts for the bioorthogonal uncaging of propargylic and benzylic ether protected substrates, including uncaging in living E. coli. observed selectivity is supported by induced-fit docking and molecular dynamics simulations. This proof-of-principle study points towards the utility of bioorthogonal enzyme/protecting group pairs for applications in the life sciences.
- Ritter, Cornelia,Nett, Nathalie,Acevedo-Rocha, Carlos G.,Lonsdale, Richard,Kr?ling, Katja,Dempwolff, Felix,Hoebenreich, Sabrina,Graumann, Peter L.,Reetz, Manfred T.,Meggers, Eric
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Read Online
- Copper(I)-Catalyzed Intramolecular Cyclization of o-Propargyloxy Diketopiperazines to Access Diverse Diazabicyclic and Spiro-Diketopiperazinochromanes
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In this report, two distinctive intramolecular cyclizations of o-propargyloxy diketopiperazines (achieved from a one-pot Ugi post-transformation) is achieved via a copper(I)-catalyzed intramolecular reaction of azomethine ylide and alkyne moiety. The presence of internal alkyne in the starting materials directed the reaction towards through [3+2]-cycloaddition, while terminal alkyne led to a spirocyclization reaction between azomethine ylide and terminal unsaturated C?C bond. This method offering an opportunity for the synthesis of challenging Diazabicyclics and Spiro-Diketopiperazinochromanes in high yields with exclusive diastereoselectivity. (Figure presented.).
- Armaghan, Mahsa,Balalaie, Saeed,Bijanzadeh, Hamid Reza,Frank, Walter,Manavi, Bita,Rominger, Frank,Tejeneki, Hossein Zahedian
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supporting information
p. 4190 - 4196
(2021/08/06)
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- Catalytic synthesis of isoquinolines via intramolecular migration of n-aryl sulfonyl groups on 1,5-yne-imines
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Isoquinolines are ubiquitous structural motifs in a variety of bioactive compounds, including medicinal agents and natural products. The development of novel strategies for the preparation of isoquinolines using non-toxic organocatalysts is thus worthwhile. Herein, we report a simple amine-catalyzed protocol for the synthesis of isoquinolines from 1,5-yne-imines via the intramoleular migration of an N-aryl sulfonyl group to the carbon atom of the alkyne moiety.
- Hoshimoto, Yoichi,Kumar, Ravindra,Nishimura, Chika,Ogoshi, Sensuke,Sasaoka, Yukari
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supporting information
p. 182 - 186
(2020/04/27)
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- Iron-Catalyzed [2+2+2] Annulation of Aliphatic Bridged 1,n-Enynes with Aldehydes for the Synthesis of Fused Pyrans
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An iron-catalyzed [2+2+2] annulation of aliphatic bridged 1,n-enynes with aldehydes was developed. Aldehydes play a dual role as the precursors of acyl radicals to trigger the cascade cyclization but also as the radical acceptors to terminate the annulation. This two-in-one strategy overcomes the limitation in [2+2+m] cyclization that requires a rigid benzene skeleton as the essential linker, thus enabling the efficient synthesis of functionalized fused [5.6] and [6.6] pyran skeletons.
- Tian, Tian,Wang, Xin,Lv, Leiyang,Li, Zhiping
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supporting information
p. 4425 - 4428
(2020/06/05)
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- Transition metal-free diastereospecific synthesis of (Z)-2-arylidene-2,3-dihydrobenzo[b][1,4]dioxines by reaction of (Z)-1,2-dibromo-3-aryl-2-propenes with catechols
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A transition metal-free, diastereospecific reaction between substituted (Z)-1,2-dibromo-3-phenyl-2-propenes and substituted catechols using Cs2CO3 as a base at 140 °C for 18 h delivers exclusively substituted (Z)-2-arylidene-2,3-dihy
- Beifuss, Uwe,Bharatam, Prasad V.,Conrad, Jürgen,Frey, Wolfgang,Rekowski, Szymon P.,Wani, Aabid A.
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supporting information
(2020/09/18)
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- Regioselective Iron-Catalysed Cross-Coupling Reaction of Aryl Propargylic Bromides and Aryl Grignard Reagents
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An iron-catalysed Kumada-type cross-coupling reaction between aryl substituted propargylic bromides and arylmagnesium reagents has been developed. Propargylic coupling products were the main or only outcome, and propargyl/allene regioselectivity was shown to depend on the electronic nature of the substituents on the triple bond of the substrate and on the arylmagnesium halide. Best selectivities were observed when electron donating substituents were present in either reagent. The process is stereoespecific, occurs with configuration inversion and no carbon-based radicals seem to be involved in the mechanism. (Figure presented.).
- Manjón-Mata, Inés,Quirós, M. Teresa,Bu?uel, Elena,Cárdenas, Diego J.
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supporting information
p. 146 - 151
(2019/12/11)
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- RET INHIBITORS, PHARMACEUTICAL COMPOSITIONS AND USES THEREOF
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Provided herein are a RET inhibitor, a pharmaceutical composition thereof and uses thereof. In particular, provided is a compound having Formula (I) or a stereoisomer, a geometric isomer, a tautomer, an N-oxide, a solvate, a metabolite, a pharmaceutically acceptable salt or a prodrug thereof. Provided is a pharmaceutical composition comprising the compound, and uses of the compound and pharmaceutical composition thereof for the preparation of a medicament, in particular for treatment and prevention of RET-related diseases and conditions, including cancer, irritable bowel syndrome, and/or pain associated with irritable bowel syndrome.
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Paragraph 00230; 00621
(2020/07/05)
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- A Pd NP-confined novel covalent organic polymer for catalytic applications
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A novel unsymmetrical covalent organic polymer, COP (1), was designed and characterized using several analytical and spectroscopic techniques. COP (1) was synthesized via the nucleophilic substitution reaction of 2,4,6-trichloro-1,3,5-triazine with p-amin
- Yadav, Deepika,Awasthi, Satish Kumar
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p. 1320 - 1325
(2020/02/04)
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- Synthesis of Spirobicyclic Pyrazoles by Intramolecular Dipolar Cycloadditions/[1s, 5s] Sigmatropic Rearrangements
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The formation of fused pyrazoles via intramolecular 1,3-dipolar cycloadditions of diazo intermediates with pendant alkynes is described. A subsequent thermal [1s, 5s] sigmatropic shift of these pyrazole systems resulted in a ring contraction, forming spirocyclic pyrazoles. The limitations of this rearrangement were explored by changing the substituents on the nonmigrating aromatic ring and by using substrates lacking an aromatic linkage to the propargyl group.
- Dimirjian, Christine A.,Casti?eira Reis, Marta,Balmond, Edward I.,Turman, Nolan C.,Rodriguez, Elys P.,Di Maso, Michael J.,Fettinger, James C.,Tantillo, Dean J.,Shaw, Jared T.
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supporting information
p. 7209 - 7212
(2019/10/02)
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- Tandem Thioacylation-Intramolecular Hydrosulfenylation of Propargyl Amines – Rapid Access to 2-Aminothiazolidines
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An investigation directed towards the preparation of α-substituted propargyl thioureas from the corresponding propargylamine resulted in a tandem thioacylation/anti-hydrosulfenylation and the formation of the corresponding thiazolidine in excellent (46–98
- Singh, Ravi P.,Gout, Delphine,Lovely, Carl J.
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p. 1726 - 1740
(2019/02/24)
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- A Garratt-Braverman cyclization route towards the synthesis of phenanthridine derivatives and their DNA-binding studies
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Garratt-Braverman cyclization has been employed to synthesize a series of dihydroisofuran fused phenanthridine derivatives. The established protocol proposes a simpler synthetic alternative to have access to these therapeutically relevant cytotoxic scaffo
- Mandal, Arundhoti,Bhattacharya, Prabuddha,Das, Amit K.,Basak, Amit
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p. 1975 - 1987
(2019/02/24)
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- Methods and compositions for terpenoid tricycloalkane synthesis
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In one aspect, the disclosure relates to methods for preparation of intermediates useful for the preparation of terpenoid cores. In a further aspect, the disclosed methods pertain to the preparation of compounds comprising a terpenoid core or scaffold, su
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Page/Page column 55; 87
(2019/05/26)
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- Rhodium(i)-catalyzed Pauson-Khand-type reaction using formic acid as a CO surrogate: An alternative approach for indirect CO2 utilization
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Formic acid is found to be an ideal CO surrogate for the rhodium(i)-catalyzed Pauson-Khand-type (PK-type) reaction of various substituted 1,6-enynes to afford bicyclic cyclopentenones in moderate to good yields. High TON value of up to 263 and good results in the gram-scale experiment were also obtained, demonstrating the efficacy of this methodology. In addition, heterocyclic molecules of pharmaceutical importance were also furnished via inter- or intra-molecular hetero-PK-type reactions, further broadening the application of current strategy. In this protocol, formic acid was utilized as a bridging molecule for the conversion of CO2 to CO, since formic acid is manufactured via catalytic hydrogenation of CO2 and releases CO in the presence of acetic anhydride readily. Therefore, this methodology represents a green and indirect approach for chemical valorization of CO2 in the preparation of value-added compounds.
- Lang, Xian-Dong,You, Fei,He, Xing,Yu, Yi-Chen,He, Liang-Nian
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supporting information
p. 509 - 514
(2019/02/14)
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- Synthesis and antiviral activity of novel spirocyclic nucleosides
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The synthesis of a number of spirocyclic ribonucleosides containing either a triazolic or azetidinic system is described, along with two analogous phosphonate derivatives of the former. These systems were constructed from the same β-d-psicofuranose starti
- Cobb, Alexander J. A.,Dell'Isola, Antonio,Abdulsattar, Ban O.,McLachlan, Matthew M. W.,Neuman, Benjamin W.,Müller, Christin,Shankland, Kenneth,Al-Mulla, Hawaa M. N.,Binks, Alexander W. D.,Elvidge, Warren
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p. 18363 - 18380
(2018/11/23)
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- MLKL INHIBITORS
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Purine derivatives that inhibit cellular necroptosis and/or human MLKL, pharmaceutical compositions thereof, and methods of treating an MLKL-mediated disorder with an effective amount of the compound or composition. Said MLKL-mediated disorder is pathology associated necroptosis, including ischemia-reperfusion damage, neurodegeneration, and inflammatory diseases such as acute pancreatitis, multiple sclerosis, inflammatory bowel disease, and allergic colitis.
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Paragraph 0657-0658
(2018/09/26)
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- Synthesis of Carbolines via Palladium/Carboxylic Acid Joint Catalysis
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The combination of a Pd(0) complex with benzoic acid converts propargylic tryptamines to the corresponding tetrahydro-β-carbolines. The method uses unprotected indoles and affords the desired products with ample functional group tolerance. Detailed modeling studies reveal a close synergy between the organic and metal catalysts, which enables sequential alkyne isomerization, indole C-H activation, and eventual C-C reductive elimination to afford the target heterocycles.
- Cera, Gianpiero,Lanzi, Matteo,Balestri, Davide,Della Ca, Nicola,Maggi, Raimondo,Bigi, Franca,Malacria, Max,Maestri, Giovanni
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supporting information
p. 3220 - 3224
(2018/06/11)
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- NiICatalyzes the Regioselective Cross-Coupling of Alkylzinc Halides and Propargyl Bromides to Allenes
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We describe the unprecedented formation of allenes by Ni-catalyzed cross-coupling of propargyl bromides with alkylzinc halides. The reaction regioselectivity is complementary to the previously reported formation of propargyl-coupled compounds. Experiments
- Soler-Yanes, Rita,Arribas-álvarez, Iván,Guisán-Ceinos, Manuel,Bu?uel, Elena,Cárdenas, Diego J.
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supporting information
p. 1584 - 1590
(2017/02/10)
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- An Enyne Cope Rearrangement Enables Polycycloalkane Synthesis from Readily Available Starting Materials
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Cyclohexanone-derived Knoevenagel adducts (cyclohexylidenemalononitriles) and two different propargyl electrophiles serve as carbon sources for assembling diverse 6/7/5 tricycloalkanes, a common terpenoid framework. The sequence involves three unique reac
- Scott, Sarah K.,Grenning, Alexander J.
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supporting information
p. 8125 - 8129
(2017/06/30)
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- Discovery of Potent Benzofuran-Derived Diapophytoene Desaturase (CrtN) Inhibitors with Enhanced Oral Bioavailability for the Treatment of Methicillin-Resistant Staphylococcus aureus (MRSA) Infections
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Blocking the staphyloxanthin biosynthesis process has emerged as a new promising antivirulence strategy. Previously, we first revealed that CrtN is a druggable target against infections caused by pigmented Staphylococcus aureus (S. aureus) and that naftifine was an effective CrtN inhibitor. Here, we identify a new type of benzofuran-derived CrtN inhibitor with submicromolar IC50 values that is based on the naftifine scaffold. The most potent analog, 5m, inhibits the pigment production of S. aureus Newman and three MRSA strains, with IC50 values of 0.38-5.45 nM, without any impact on the survival of four strains (up to 200 μM). Notably, compound 5m (1 μM) could significantly sensitize four strains to immune clearance and could effectively attenuate the virulence of three strains in vivo. Moreover, 5m was determined to be a weak antifungal reagent (MIC > 16 μg/mL). Combined with good oral bioavailability (F = 42.2%) and excellent safety profiles, these data demonstrate that 5m may be a good candidate for the treatment of MRSA infections.
- Wang, Youxin,Chen, Feifei,Di, Hongxia,Xu, Yong,Xiao, Qiang,Wang, Xuehai,Wei, Hanwen,Lu, Yanli,Zhang, Lingling,Zhu, Jin,Sheng, Chunquan,Lan, Lefu,Li, Jian
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p. 3215 - 3230
(2016/05/19)
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- Discovery of Benzocycloalkane Derivatives Efficiently Blocking Bacterial Virulence for the Treatment of Methicillin-Resistant S. aureus (MRSA) Infections by Targeting Diapophytoene Desaturase (CrtN)
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Antivirulence strategies are now attracting interest for the inherent mechanism of action advantages. In our previous work, diapophytoene desaturase (CrtN) was identified to be an attractive and drugable target for fighting pigmented S. aureus infections. In this research, we developed a series of effective benzocycloalkane-derived CrtN inhibitors with submicromolar IC50. Analogue 8 blocked the pigment biosynthesis of three MRSA strains with a nanomolar IC50 value. Corresponding to its mode of action, 8 did not function as a bactericidal agent. 8 could sensitize S. aureus to immune clearance. In vivo, 8 was proven to be efficacious in an S. aureus Newman sepsis model and abscess formation model. For two typical MRSAs, USA400 MW2 and Mu50, 8 significantly decreased the staphylococcal loads in the liver and kidneys. Moreover, 8 showed minimal antifungal activity compared to that of NTF. In summary, 8 has the potential to be developed as a therapeutic drug, especially against intractable MRSA issues.
- Wang, Youxin,Di, Hongxia,Chen, Feifei,Xu, Yong,Xiao, Qiang,Wang, Xuehai,Wei, Hanwen,Lu, Yanli,Zhang, Lingling,Zhu, Jin,Lan, Lefu,Li, Jian
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p. 4831 - 4848
(2016/06/13)
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- Benzofuran-7-alkylamine compounds and applications thereof
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The inventor designs and synthesizes benzofuran-7-alkylamine compounds with a novel structure. The test results show that most of the disclosed benzofuran-7-alkylamine compounds have a strong activity on inhibiting the synthesis of golden yellow pigment, and some compounds have an extremely strong inhibiting activity on pigments of drug resistant bacteria (S.aureus USA400 MW2, USA300 LAC, Mu50), and prominently enhance the hydrogen peroxide killing and human blood killing in vitro. In vivo, for the animal model infected by sensitive strain (S.aureus Newman) and two drug resistant strains (S.aureus USA400 MW2, Mu50), the planting of bacteria in internal organs (kidney, heart, and liver) of mice is prominently reduced. The benzofuran-7-alkylamine compounds are advantageously used for producing novel anti-bacterium drugs.
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Paragraph 0106; 0258-0261
(2016/10/10)
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- Preparation of 1,2,5-Trisubstituted 1H-Imidazoles from Ketenimines and Propargylic Amines by Silver-Catalyzed or Iodine-Promoted Electrophilic Cyclization Reaction of Alkynes
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From readily available propargylic amines, 1,2,5-trisubstituted imidazoles are efficiently obtained through a cascade reaction catalyzed by AgOTf or promoted by molecular iodine. The AgOTf-catalyzed reaction involves nucleophilic addition of propargylic amine to ketenimine, a silver-catalyzed electrophilic cyclization reaction of alkyne, and a tautomerism/isomerism/metal-H exchange cascade. The iodine-mediated counterpart yields 5-formyl-1,2-disubtituted imidazoles, which presumably includes a cascade hydrolysis/oxidation reaction. Furthermore, the presented protocol can be scaled up and the resultant 1,2,5-trisubstituted imidazole can be converted into fused indeno[1,2-d]imidazole. 1,2,5-Trisubstituted imidazoles are efficiently prepared from readily available propargylic amines through a AgOTf-catalyzed or molecular iodine-promoted cascade reaction. The presented protocol can be scaled up and the resultant 1,2,5-trisubstituted imidazoles can be converted into fused indeno[1,2-d]imidazoles.
- Zhou, Xiaorong,Jiang, Zheng,Xue, Lexing,Lu, Ping,Wang, Yanguang
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supporting information
p. 5789 - 5797
(2015/09/15)
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- Oxadiazoanthracene compounds for the treatment of diabetes
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The present invention provides methods of use of oxadiazoanthracene derivatives of the formula (I) and pharmaceutically acceptable salts thereof, wherein A, B, C, R, R1, R2, R3, R4 and R5 are as herein described, and wherein said methods of use include uses for the treatment of disorders and diseases, such as diabetes.
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- Selectivity in Garratt-Braverman cyclization of aryl-/heteroaryl- substituted unsymmetrical bis-propargyl systems: Formal synthesis of 7′-desmethylkealiiquinone
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Unsymmetrical bis-propargyl ethers and sulfonamides containing various combinations of aryl/heteroaryl substituents at the acetylene termini were synthesized, and their reactivity under basic conditions was studied. Moderate to high (chemo)selectivity was
- Das, Joyee,Mukherjee, Raja,Basak, Amit
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p. 3789 - 3798
(2014/05/20)
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- Synthesis and antiviral properties of spirocyclic [1,2,3]-Triazolooxazine nucleosides
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An efficient synthesis of spirocyclic triazolooxazine nucleosides is described. This was achieved by the conversion of β-D-psicofuranose to the corresponding azido-derivative, followed by alkylation of the primary alcohol with a range of propargyl bromide
- Dell'Isola, Antonio,McLachlan, Matthew M. W.,Neuman, Benjamin W.,Al-Mullah, Hawaa M. N.,Binks, Alexander W. D.,Elvidge, Warren,Shankland, Kenneth,Cobb, Alexander J. A.
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supporting information
p. 11685 - 11689
(2014/10/15)
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- Ln[N(SiMe3)2]3-Catalyzed Cross-Diinsertion of C≡N/C≡C into an N-H Bond: Facile Synthesis of 1,2,4-Trisubstituted Imidazoles from Propargylamines and Nitriles
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A lanthanide-catalyzed sequential insertion of C≡N and C≡C into an N-H bond is presented. The convenient reaction, which proceeds under mild conditions, is an efficient method for preparing 1,2,4-trisubstituted imidazoles directly from readily available propargylamines and nitriles.
- Hong, Longcheng,Shao, Yinlin,Zhang, Lixin,Zhou, Xigeng
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supporting information
p. 8551 - 8555
(2014/07/21)
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- Synthesis of 3-benzylisoquinolines by domino imination/cycloisomerisation of 2-propargylbenzaldehydes
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An easy entry to uncommon 2-propargylbenzaldehydes was developed. 2-Propargylbenzaldehydes demonstrated to be suitable building blocks for the synthesis of 3-benzyl isoquinolines by microwave promoted domino imination/cycloisomerisation in the presence of
- Dell'Acqua, Monica,Pirovano, Valentina,Confalonieri, Giorgio,Arcadi, Antonio,Rossi, Elisabetta,Abbiati, Giorgio
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p. 8019 - 8030
(2015/01/08)
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- SmI2-H2O-mediated 5-exo/6-exo lactone radical cyclisation cascades
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The SmI2-H2O reagent system mediates challenging 5-exo/6-exo lactone radical cascade cyclisations that deliver carbo[5.4.0]bicyclic motifs in a diastereoselective, one-pot process that establish two new carbocyclic rings and four ste
- Yalavac, Irem,Lyons, Sarah E.,Webb, Michael R.,Procter, David J.
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supporting information
p. 12863 - 12866
(2015/02/05)
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- HETEROCYCLIC COMPOUNDS AND METHODS FOR THEIR USE
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The present invention relates to heterocyclic compounds useful for antagonising angiotensin II Type 2 (AT2) receptor. More particularly the invention relates to pyrrolidine and azetidine compounds, compositions containing them and their use in methods of treating or preventing disorders or diseases associated with AT2 receptor function including neuropathic pain, inflammatory pain, conditions associated with neuronal hypersensitivity, impaired nerve conduction velocity, cell proliferation disorders, disorders associated with an imbalance between bone resorption and bone formation and disorders associated with aberrant nerve regeneration.
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Page/Page column 88
(2013/07/19)
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- Copper(I)-catalyzed regio- and chemoselective single and double addition of nucleophilic silicon to propargylic chlorides and phosphates
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Copper(I)-catalyzed propargylic substitution of linear precursors with (Me2PhSi)2Zn predominantly yields the γ isomer independent of the propargylic leaving group. The thus formed allenylic silane reacts regioselectively with another equivalent of (Me2PhSi) 2Zn, yielding a bifunctional building block with allylic and vinylic silicon groups. The reaction rates of both steps are well-balanced for chloride (γ:α ≥ 99:1) where the propargylic displacement occurs quantitatively prior to the addition step. Substitutions of α-branched propargylic phosphates are also reported.
- Hazra, Chinmoy K.,Oestreich, Martin
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supporting information; experimental part
p. 4010 - 4013
(2012/10/08)
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- Nanoporous gold catalyst for highly selective semihydrogenation of alkynes: Remarkable effect of amine additives
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We report for the first time the highly selective semihydrogenation of alkynes using the unsupported nanoporous gold (AuNPore) as a catalyst and organosilanes with water as a hydrogen source. Under the optimized reaction conditions, the present semihydrogenation of various terminal- and internal-alkynes affords the corresponding alkenes in high chemical yields and excellent Z-selectivity without any over-reduced alkanes. The use of DMF as solvent, which generates amines in situ, or pyridine as an additive is crucial to suppress the association of hydrogen atoms on AuNPore to form H2 gas, which is unable to reduce alkynes on the unsupported gold catalysts. The AuNPore catalyst can be readily recovered and reused without any loss of catalytic activity. In addition, the SEM and TEM characterization of nanoporosity show that the AuNPore catalyst has a bicontinuous 3D structure and a high density of atomic steps and kinks on ligament surfaces, which should be one of the important origins of catalytic activity.
- Yan, Mei,Jin, Tienan,Ishikawa, Yoshifumi,Fujita, Takeshi,Chen, Lu-Yang,Asao, Naoki,Chen, Ming-Wei,Yamamoto, Yoshinori,Minato, Taketoshi,Bao, Ming
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supporting information
p. 17536 - 17542,7
(2020/09/16)
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- A one-pot-three-step route to triazolotriazepinoindazolones from oxazolino-2H-indazoles
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A one-pot-three-step method has been developed for the conversion of oxazolino-2H-indazoles into triazolotriazepinoindazolones with three points of diversity. Step one of this process involves a propargyl bromide-initiated ring opening of the oxazolino-2H-indazole (available by the Davis-Beirut reaction) to give an N1-(propargyl)-N2-(2-bromoethyl)-disubstituted indazolone, which then undergoes -CH2Br → -CH2N 3 displacement (step two) followed by an uncatalyzed intramolecular azide-alkyne 1,3-dipolar cycloaddition (step three) to form the target heterocycle. Employing 7-bromooxazolino-2H-indazole allows for further diversification through, for example, palladium-catalyzed coupling chemistry, as reported here.
- Conrad, Wayne E.,Rodriguez, Kevin X.,Nguyen, Huy H.,Fettinger, James C.,Haddadin, Makhluf J.,Kurth, Mark J.
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supporting information; experimental part
p. 3870 - 3873
(2012/10/07)
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- Lactone radical cyclizations and cyclization cascades mediated by SmI 2-H2O
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Unsaturated lactones undergo reductive radical cyclizations upon treatment with SmI2-H2O to give decorated cycloheptanes in a single highly selective operation during which up to three contiguous stereocenters are generated. Furthermore, cascade processes involving lactones bearing two alkenes, an alkene and an alkyne, or an allene and an alkene allow "one-pot" access to biologically significant molecular scaffolds with the construction of up to four contiguous stereocenters. The cyclizations proceed by the trapping of radical anions formed by electron transfer reduction of the lactone carbonyl.
- Parmar, Dixit,Matsubara, Hiroshi,Price, Kieran,Spain, Malcolm,Procter, David J.
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supporting information; experimental part
p. 12751 - 12757
(2012/09/05)
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- Iron-catalyzed synthesis of functionalized 2H-chromenes via intramolecular alkyne-carbonyl metathesis
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An iron-catalyzed intramolecular alkyne-aldehyde metathesis strategy of the alkynyl ether of salicylaldehyde derivatives has been developed which works under mild reaction conditions to produce the functionalized 2H-chromene derivatives. This protocol is compatible toward a wide range of functional groups, such as methoxy, fluoro, chloro, bromo, and phenyl groups. This method provides an atom-economical and environmentally friendly approach for the synthesis of a series of substituted 2H-chromenes.
- Bera, Krishnendu,Sarkar, Soumen,Biswas, Srijit,Maiti, Sukhendu,Jana, Umasish
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experimental part
p. 3539 - 3544
(2011/06/23)
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- Selectivity in Garratt-Braverman cyclization: An experimental and computational study
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Bispropargyl sulfones equipped with aromatic rings of dissimilar nature were synthesized. Under basic conditions, these sulfones isomerized to the bisallenic sulfones, creating a competitive scenario between two alternate Garratt-Braverman (GB) cyclizatio
- Maji, Manasi,Mallick, Dibyendu,Mondal, Sayantan,Anoop, Anakuthil,Bag, Subhendu Sekhar,Basak, Amit,Jemmis, Eluvathingal D.
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supporting information; experimental part
p. 888 - 891
(2011/04/27)
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- Iodocyclization of hydroxylamine derivatives based on the control of oxidative aromatization leading to 2,5-dihydroisoxazoles and isoxazoles
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An efficient method for the synthesis of 2,5-dihydroisoxazoles and isoxazoles using iodocyclization of N-alkoxycarbonyl O-propargylic hydroxylamines has been developed. 2,5-Dihydro-4-iodoisoxazole underwent the cross-coupling reactions without aromatization to afford polyfunctionalized 2,5-dihydroisoxazoles. This process was applied to the preparation of valdecoxib and its 2,5-dihydro-derivative.
- Okitsu, Takashi,Sato, Kana,Potewar, Taterao M.,Wada, Akimori
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experimental part
p. 3438 - 3449
(2011/06/26)
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- Intramolecular Povarov reactions involving 3-aminocoumarins
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A series of pentacyclic heterocyclic systems (15 examples, 69-89%) have been synthesized using intramolecular Povarov reactions involving 3-aminocoumarins and O-cinnamylsalicylaldehydes. The Povarov adducts are formed with high selectivity for the trans,trans relative stereochemistry in the newly-formed [6,6] fused ring system. One example of a Povarov adduct featuring a new [6,5] fused ring system is reported. In this case, cis,trans relative stereochemistry was preferred.
- Kudale, Amit A.,Miller, David O.,Dawe, Louise N.,Bodwell, Graham J.
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scheme or table
p. 7196 - 7206
(2011/10/31)
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- Synthesis and electronic structure of tetrakis(η3- phenylpropargyl)zirconium
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Tetrakis(η3-phenylpropargyl)zirconium (3) was synthesized from ZrCl4 and (phenylpropargyl)magnesium bromide. The crystallographically determined structure of 3 exhibits D2d symmetry, consistent with the 1H and
- Denomme, Dan R.,Dumbris, Seth M.,Hyatt, I. F. Dempsey,Abboud, Khalil A.,Ghiviriga, Ion,McElwee-White, Lisa
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experimental part
p. 5252 - 5256
(2011/01/06)
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- Ionic liquids accelerating cycloaddition between 1-aryl-2-halocyclopropenes and furan
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Treatment of a series of 1-aryl-2,2-dihalocyclopropanes with t-BuOK at-10 °C gave the corresponding 1-aryl-2-halocyclopropenes, which react with furan in a RTIL to give a fair good yield of the [4+2]-cycloadducts with more than 90% of the exo-isomer. The imidazolium type ionic liquids are able to accelerate this cycloaddition process with high steric selectivity. Neither pyrrole nor thiophene undergoes the cycloaddition with cyclopropene to form the [4+2]-cycloadduct. 1-Aryl-3,3-difluoro-2-halocyclopropenes are inert towards furan even at a temperature higher than 100 °C.
- Ding, May-Fan,Lin, Shaw-Tao,Chang, Woan-Ju
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experimental part
p. 240 - 247
(2010/09/16)
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- Domino alkylation-cyclization reaction of propargyl bromides with thioureas/thiopyrimidinones: A new facile synthesis of 2-aminothiazoles and 5H-thiazolo[3,2-α]pyrimidin-5-ones
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A new synthesis of 2-aminothiazoles and 5H-thiazolo[ 3,2-α]pyrimidin- 5-ones was developed as a domino alkylation-cyclization reaction of propargyl bromides with thioureas and thiopyrimidinones, respectively. Domino reactions were performed under microwave irradiation leading to desired compounds in a few minutes and high yields. Georg Thieme Verlag Stuttgart.
- Castagnolo, Daniele,Pagano, Mafalda,Bernardini, Martina,Botta, Maurizio
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scheme or table
p. 2093 - 2096
(2011/04/15)
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- Gold(I)-catalyzed enantioselective ring expansion of allenylcyclopropanols
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(Chemical Equation Presented) The asymmetric gold(I)-catalyzed ring expansion of 1-allenylcyclopropanols is described. The method provides synthetically valuable cyclobutanones with a vinyl-substituted quaternary stereogenic center in high enantioselectivities and yields. The method shows a broad substrate scope, tolerating protected alcohols and amines, alkenes, unsaturated esters, and acetals. The reaction is easily adjustable to large-scale synthesis, leading to product formation without significant loss of selectivity or yield with only 0.5 mol% catalyst loading.
- Kleinbeck, Florian,Toste, F. Dean
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supporting information; experimental part
p. 9178 - 9179
(2009/12/06)
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- Tricyclic triazolic compounds
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The present invention relates to new tricyclic triazolic compounds having a high affinity for sigma-1 receptor as well as to the process for the preparation thereof, to composition comprising them and to their use as medicaments according to compounds of
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Page/Page column 19-20
(2009/07/10)
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- Asymmetric synthesis of α-allenylglycines
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The coupling of the homocuprate of the bislactim ether of cyclo-(-L-Val-Gly-) (9) with primary propargyl halides produces the allenyl-substituted bislactim ethers 11 in a highly diastereoselective manner, whereas the alkylation of the lith-iated bislactim ether of cyclo-(-L-Val-Gly-) yields the proparg-yl-substituted bislactim ethers 12. Subsequent hydrolysis affords, after protection of the amino group, the methyl α- allenylglycinates 15, the α-allenylglycines 16, and the methyl α-propargylglycinates 17.
- Bucuroaia, Carmen,Groth, Ulrich,Huhn, Thomas,Klinge, Michael
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experimental part
p. 3605 - 3612
(2009/12/01)
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- A facile and regioselective synthesis of 2,5-disubstituted pyrroles via gold-catalyzed cycloisomerization of acetylenylaziridines
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Gold-catalyzed cycloisomerization reaction of acetylenylaziridines provides 2,5-disubstituted pyrroles in high yields. The presence of protic species accelerates the reaction rate and improves the yields of pyrrole products.
- Chen, Dong-Dong,Hou, Xue-Long,Dai, Li-Xin
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supporting information; experimental part
p. 6944 - 6946
(2010/02/27)
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- Preparation of halo enol phostones by reaction of acetylenic phosphonate monoesters with (bis-collidine)halo hexafluorophosphate
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Reaction of non-conjugated acetylenic phosphonate monoesters with (bis-collidine) bromo and iodo hexafluorophosphates was found to lead to the formation of halo enol phostones. Depending on the size of the heterocyclic compounds formed (6-8-membered compo
- André, Virginie,Robin, Sylvie,Rousseau, Gérard
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p. 5059 - 5062
(2008/12/20)
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- Microwave-assisted rhodium-complex-catalyzed cascade decarbonylation and asymmetric Pauson-Khand-type cyclizations
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Microwave-assisted Rh-diphosphane-complex-catalyzed dual catalysis is reported. This cooperative process provides [2+2+1] cycloadducts by sequential decarbonylation of aldehyde or formate and carbonylation of enynes within a short period of time. Various
- Hang, Wai Lee,Lai, Na Lee,Chan, Albert S. C.,Fuk, Yee Kwong
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supporting information; experimental part
p. 3403 - 3406
(2009/04/07)
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- Intramolecular azide-Alkyne for the fast assembly of structurally diverse, tricyclic 1,2,3-triazoles
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The synthesis of novel tricyclic 1,2,3-triazoles starting from cyclic epoxides via the sequential azidolysis, propargylation and 1,3-dipolar cycloaddition is described. Derivatization by N-arylation reaction and the synthesis of enantiomerically pure comp
- Oliva, Ana I.,Christmann, Ute,Font, Daniel,Cuevas, Flix,Ballester, Pablo,Buschmann, Helmut,Torrens, Antoni,Yenes, Susana,Perics, Miquel A.
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supporting information; experimental part
p. 1617 - 1619
(2009/04/07)
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- Synthesis and trapping of some substituted 1-bromocyclopropenes
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Treatment of a number of 2-substituted 1,1,2-tribromocyclopropanes with MeLi at -78°C gave the corresponding 1-bromocyclopropenes, which were reacted with three cyclic dienes to yield the [4 + 2]-cycloadducts. Cycloaddition with 1,3-diphenylisobenzofuran
- Alnes, Karl F. S.,Sydnes, Leiv K.
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p. 483 - 500
(2007/10/03)
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- Iridium-catalyzed cascade decarbonylation/highly enantioselective Pauson-Khand-type cyclization reactions
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An easily accessible chiral iridium-BINAP complex can effect the cooperative processes of decarbonylation of an aldehyde and cascaded enantioselective Pauson-Khand-type reaction. A survey of ligands revealed that atropisomeric aryl-diphosphine ligands wer
- Kwong, Fuk Yee,Lee, Hang Wai,Lam, Wai Har,Qiu, Liqin,Chan, Albert S.C.
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p. 1238 - 1252
(2007/10/03)
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- Gold-catalyzed intramolecular [3 + 2]-cycloaddition of arenyne-yne functionalities
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We report a new efficient intramolecular [3 + 2]-cycloaddition of unactivated arenyne (or enyne)-yne functionalities, catalyzed mainly by the AuPPh3SbF6 complex (2 mol %) under ambient conditions. The value of this cyclization is ref
- Lian, Jian-Jou,Chen, Po-Chiang,Lin, Yau-Ping,Ting, Hao-Chun,Liu, Rai-Shung
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p. 11372 - 11373
(2007/10/03)
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