823-09-6Relevant articles and documents
Metal-Free Aminomethylation of Aromatic Sulfones Promoted by Eosin Y
Thierry, Thibault,Pfund, Emmanuel,Lequeux, Thierry
supporting information, p. 14826 - 14830 (2021/10/01)
A metal-free α-aminomethylation of heteroaryls promoted by eosin Y under green light irradiation is reported. A large variety of α-trimethylsilylamines as precursor of α-aminomethyl radical species were engaged to functionalize sulfonyl-heteroaryls following a Homolytic Aromatic Substitution (HAS) pathway. This method has provided a range of α-aminoheteroaryl compounds including a functionalized natural product. The mechanism of this late-stage functionalization of aryls was investigated and suggests the formation of a sulfonyl radical intermediate over a reductive quenching cycle.
Nickel-Catalyzed Inter- and Intramolecular Aryl Thioether Metathesis by Reversible Arylation
Delcaillau, Tristan,Bismuto, Alessandro,Lian, Zhong,Morandi, Bill
supporting information, p. 2110 - 2114 (2019/12/24)
A nickel-catalyzed aryl thioether metathesis has been developed to access high-value thioethers. 1,2-Bis(dicyclohexylphosphino)ethane (dcype) is essential to promote this highly functional-group-tolerant reaction. Furthermore, synthetically challenging macrocycles could be obtained in good yield in an unusual example of ring-closing metathesis that does not involve alkene bonds. In-depth organometallic studies support a reversible Ni0/NiII pathway to product formation. Overall, this work not only provides a more sustainable alternative to previous catalytic systems based on Pd, but also presents new applications and mechanistic information that are highly relevant to the further development and application of unusual single-bond metathesis reactions.
Decyanative Cross-Coupling of Cyanopyrimidines with O-, S-, and N-Nucleophiles: A Route to Alkoxylpyrimidines, Aminopyrimidines and Alkylthiopyrimidines
Wei, Xiangyang,Zhang, Caiyang,Wang, Yifei,Zhan, Qi,Qiu, Guiying,Fan, Ling,Yin, Guodong
, p. 7142 - 7150 (2019/11/14)
The transition metal-free cross-coupling reactions of cyanopyrimidines with aliphatic alcohols, thiols (or S-alkylisothiourea salts) and amines, giving the corresponding alkoxylpyrimidines, aminopyrimidines, and alkylthiopyrimidines, are reported. Prelimi
Cesium carbonate-promoted synthesis of aryl methyl sulfides using: S -methylisothiourea sulfate under transition-metal-free conditions
Zhang, Caiyang,Zhou, You,Huang, Jintao,Tu, Canhui,Zhou, Xiaoai,Yin, Guodong
, p. 6316 - 6321 (2018/09/10)
In the presence of cesium carbonate, an efficient synthesis of aryl methyl sulfides by the reactions of aryl halides with commercially available S-methylisothiourea sulfate is developed. This odourless and highly crystalline solid can be used as the subst
SH-methylation of SH-containing heterocycles with dimethyl carbonate via phase-transfer catalytic reaction
Xie, Jian-Gang,Quan, Jing,Li, Shu-Bai,Zheng, Yan,Zhu, Li-Min
experimental part, p. 871 - 878 (2011/04/22)
A reaction of SH-containing heterocycles with dimethyl carbonate (DMC) in the presence of K2CO3 and tetrabutylammonium bromide (Bu4NBr) gave heteroaryl methyl thioethers in 44-93% yields. The reaction was carried out under mild conditions. This method provided a useful synthetic method for preparation of various heteroaryl methyl thioethers without the use of toxic methylic halides or dimethyl sulfate.
Ionic liquids - Promoted S-methylation of thiols utilizing dimethyl carbonate
Xie, Jiangang,Wu, Chengyao,Christopher, Branford White,Quan, Jing,Zhu, Limin
experimental part, p. 31 - 37 (2011/04/22)
Convenient and efficient S-methylation of mercaptans or thiophenols occurs with dimethyl carbonate (DMC) in room temperature ionic liquids (RTILs) [Bmim]Cl. [Bmim]Cl can be recycled in four subsequent runs with only a gradual decrease in activity. A possible mechanism of this transformation is also discussed. Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file. Copyright Taylor & Francis Group, LLC.
Basic techniques of working on a solid phase: From ABC of the peptide synthesis to libraries of non-natural amino acids
Babaev,Ermolat'ev
scheme or table, p. 2572 - 2589 (2011/04/15)
Libraries of hardly available amino acids bearing a heteroaromatic ring (2-pyrimidyl, substituted 2-pyridyl or 2-thiazolyl) at the amino group were prepared using solid-phase synthesis on various resins. The synthesized compounds are structurally similar to some known antidiabetic drugs. The paper combines features of a review (elementary introduction to the solid-phase synthesis methodology and technique for beginners and selected methods from peptide chemistry) and step-by-step experimental protocols (tested by the authors) useful as a methodic tool. The presented protocols (immobilization and modification of amino acids, placing and removal of common protective groups) require no sophisticated equipment and may be useful as pictorial introductory tasks for students education. Pleiades Publishing, Ltd., 2010.
Enzymatic synthesis of novel chiral sulfoxides employing Baeyer-villiger monooxygenases
Rioz-Martinez, Ana,De Gonzalo, Gonzalo,Pazmino, Daniel E. Torres,Fraaije, Marco W.,Gotor, Vicente
experimental part, p. 6409 - 6416 (2011/02/24)
Optically active sulfoxides are compounds of high interest in organic chemistry. Herein, we report the preparation of a set of chiral heteroaryl alkyl, cyclohexyl alkyl, and alkyl alkyl sulfoxides by using enantioselective sulfoxidation reactions employing three Baeyer-Villiger monooxygenases (BVMOs). Careful selection of the reaction conditions, starting sulfide, and biocatalyst can be used to achieve good to excellent enantiomeric excess values. Thus, valuable chiral synthons can be obtained by performing the reactions under mild and environmentally friendly conditions. The most promising biotransformations that employ a BVMO cell-free extract preparation have been developed on a 250-mg scale to give the chiral sulfoxides in high yields in most of the reactions. Copyright
Regioselectivity in the amination of methylsulfanyl-substituted azines with O-mesitylenesulfonylhydroxylamine
Borodkin,Vorob'Ev,Shakirov,Shubin
experimental part, p. 911 - 916 (2010/11/16)
Reactions of O-mesitylenesulfonylhydroxylamine with 2-(methylsulfanyl) pyrazine, 2-(methylsulfanyl) pyrimidine, and 3,5-dimethyl-2-(methylsulfanyl) pyrimidines involve both sulfur and nitrogen atoms. The amination products at the sulfur atom prevail in th
Pyrimidine-core extended π-systems: General synthesis and interesting fluorescent properties
Itami, Kenichiro,Yamazaki, Daisuke,Yoshida, Jun-Ichi
, p. 15396 - 15397 (2007/10/03)
We have developed a simple but powerful synthetic strategy that permits the assembly of π-systems onto a pyrimidine core in a programmable and diversity-oriented format. The nucleophilic addition of ArLi to 2-methylthiopyrimidine, followed by 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) oxidation, resulted in the production of 4-aryl-2-methylthiopyrimidines. The iterative reaction sequence then gave 4,6-diaryl-2-methylthiopyrimidines. The resulting adduct was further allowed to react with ArMgBr under the catalytic influence of NiCl2(dppe) to afford 2,4,6-triarylpyrimidines. By following this synthetic scheme, interesting pyrimidine-core π-systems were rapidly constructed in a programmable fashion. The successful discovery of a number of interesting fluorescent materials and properties (e.g., solvatofluorochromism) speaks well for the potential of our platform strategy in the development of functional organic materials. Copyright
