- Nickel-Catalyzed Reversible Functional Group Metathesis between Aryl Nitriles and Aryl Thioethers
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We describe a new functional group metathesis between aryl nitriles and aryl thioethers. The catalytic system nickel/dcype is essential to achieve this fully reversible transformation in good to excellent yields. Furthermore, the cyanide- and thiol-free reaction shows high functional group tolerance and great efficiency for the late-stage derivatization of commercial molecules. Finally, synthetic applications demonstrate its versatility and utility in multistep synthesis.
- Delcaillau, Tristan,Boehm, Philip,Morandi, Bill
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supporting information
p. 3723 - 3728
(2021/04/07)
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- Mechanistic insight into oxygen atom transfer reactions by mononuclear manganese(iv)-oxo adducts
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High-valent metal-oxo intermediates are well known to facilitate oxygen-atom transfer (OAT) reactions both in biological and synthetic systems. These reactions can occur by a single-step OAT mechanism or by a stepwise process initiated by rate-limiting el
- Singh, Priya,Stewart-Jones, Eleanor,Denler, Melissa C.,Jackson, Timothy A.
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p. 3577 - 3585
(2021/03/22)
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- Palladium-catalyzed intermolecular transthioetherification of aryl halides with thioethers and thioesters
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Functional group transfer reactions are an important synthetic tool in modern organic synthesis. Herein, we developed a new palladium-catalyzed intermolecular transthioetherification reaction of aryl halides with thioethers and thioesters. The synthetic utility and practicality of this catalytic protocol are demonstrated in a wide range of successful transformations (>70 examples). This catalytic protocol is applicable in carbonylative coupling processes as well, and the first example of carbonylative methylthioesterification of aryl halides has been achieved. Notably, this work also provides an approach to using natural products, such as methionine and selenomethionine, as the functional group sources.
- Li, Yahui,Bao, Gao,Wu, Xiao-Feng
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p. 2187 - 2192
(2020/03/11)
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- Reduction of CO2 with NaBH4/I2 for the Conversion of Thiophenols to Aryl Methyl Sulfides
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We report a tandem reaction to realize reduction of carbon dioxide with thiophenols to generate aryl methyl sulfides under the NaBH4/I2 system with 18-crown-6 as the solvent. Thiophenols bearing electron-donating and electron-withdrawing groups are feasible in this reaction. Controlled experiment results indicate that 18-crown-6 plays a critical role in six-electron reduction of carbon dioxide.
- Zhang, Bo,Fan, Zhengning,Guo, Zhiqiang,Xi, Chanjuan
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p. 8661 - 8667
(2019/07/03)
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- Method for methylation reaction
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The invention relates to a method for a methylation reaction. The method is characterized in that a reaction substrate is reacted in an organic solvent in the presence of an alkali with methyl trifluoroacetate as a methylation reagent to obtain a corresponding methylated product. The method is a new methylation method, and has the advantages of cheapness, easiness in operation, mild reaction conditions, wide application range of the substrate, avoiding of dimethyl sulfate, iodomethane and other highly toxic methylation reagents, and obtaining of the methylated product with a high yield.
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Paragraph 0013
(2019/01/21)
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- Sulfoxide-to-sulfilimine conversions: Use of modified Burgess-type reagents
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Sulfoxides can directly be converted into N-cyanosulfilimines using a new Burgess-type reagent. By applying this strategy with a related reagent variant, synthetically valuable NH-sulfoximines have been prepared from sulfoxides via N-protected sulfilimines. The practical three-step reaction sequence is generally high yielding and applicable to a wide range of substrates. The sulfoxide-to-sulfilimine conversion can also be performed under solvent-reduced conditions in a ball mill. Copyright
- Hendriks, Christine M. M.,Lamers, Philip,Engel, Julien,Bolm, Carsten
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supporting information
p. 3363 - 3368
(2013/12/04)
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- Synthesis and biological evaluation of [18F]bicalutamide, 4-[76Br]bromobicalutamide, and 4-[76Br]bromo- thiobicalutamide as non-steroidal androgens for prostate cancer imaging
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Androgen receptors (AR) are overexpressed in most primary and metastatic prostate cancers. To develop a nonsteroidal AR-mediated imaging agent, we synthesized and radiolabeled several analogs of the potent antiandrogen bicalutamide: [18F]bicalutamide, 4-[76Br] bromobicalutamide, and [76Br]bromo-thiobicalutamide. Two of these analogs, 4-[76Br]bromobicalutamide and [76Br]bromo- thiobicalutamide, were found to have a substantially increased affinity for the androgen receptor (AR) compared to that of bicalutamide. The synthesis of [ 18F]bicalutamide utilized a pseudocarrier approach to effect addition of a carbanion generated from tracer-level amounts of a radiolabeled precursor to an unlabeled carbonyl precursor. 4-[76Br]Bromobicalutamide and [76Br]bromo-thiobicalutamide were labeled through electrophilic bromination of a tributylstannane precursor. The former could be prepared in high specific activity, and its tissue distribution was tested in vivo. Androgen target tissue uptake was evident in castrated adult male rats; however, in DES-treated, AR-positive, tumor-bearing male mice, tumor uptake was low.
- Parent, Ephraim E.,Dence, Carmen S.,Jenks, Carl,Sharp, Terry L.,Welch, Michael J.,Katzenellenbogen, John A.
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p. 1028 - 1040
(2008/02/01)
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- Pd2(dba)3/Xantphos-catalyzed cross-coupling of thiols and aryl bromides/triflates
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The cross-coupling of aliphatic and aromatic thiols and aryl bromides/triflates mediated by a Pd2(dba)3/Xantphos catalytic system in refluxing xylene (140°C) affords the corresponding aryl thioethers in good to excellent yields.
- Mispelaere-Canivet, Clotilde,Spindler, Jean-Francis,Perrio, Stéphane,Beslin, Pierre
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p. 5253 - 5259
(2007/10/03)
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- REACTION OF NUCLEOPHILES WITH ELECTRON ACCEPTORS BY SN2 OR ELECTRON TRANSFER (ET) MECHANISMS: TERT-BUTYL PEROXYBENZOATE/DIMETHYL SULFIDE AND BENZOYL PEROXIDE/N,N-DIMETHYLANILINE SYSTEMS.
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This study is one of a series that probes the reactions of nucleophiles with peroxides, reactions that can occur either by an initial S//N2 reaction or by an electron-transfer (ET) reaction. The products and kinetics are reported for the reaction of dimethyl sulfide and a series of ring-substituted aryl methyl sulfides with tert-butyl peroxybenzoate (TBP) and four ring-substituted TPB's. Kinetic analysis allows the separation of the rate constants for unimolecular homolysis (k//1) and those for the decomposition of the TBP by the sulfide (k//2). The bimolecular reaction is accelerated by electron-withdrawing substituents in the TBP; for example, when 3,5-(NO//2)//2-TBP is used, k//2/k//1 is 12,000. The products that are formed are consistent with a radical process; however, this evidence is not regarded as conclusive.
- Pryor,Hendrickson Jr.
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p. 7114 - 7122
(2007/10/02)
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