172876-96-9Relevant academic research and scientific papers
Synthesis of Diverse Aryliodine(III) Reagents by Anodic Oxidation?
Zu, Bing,Ke, Jie,Guo, Yonghong,He, Chuan
supporting information, p. 627 - 632 (2021/02/12)
An anodic oxidation enabled synthesis of hypervalent iodine(III) reagents from aryl iodides is demonstrated. Under mild electrochemical conditions, a range of aryliodine(III) reagents including iodosylarenes, (difunctionaliodo)arenes, benziodoxoles and diaryliodonium salts can be efficiently synthesized and derivatized in good to excellent yields with high selectivity. As only electrons serve as the oxidation reagents, this method offers a more straightforward and sustainable manner avoiding the use of expensive or hazardous chemical oxidants.
N-Cyanation of Primary and Secondary Amines with Cyanobenzio-doxolone (CBX) Reagent
Chen, Zimin,Yuan, Weiming
supporting information, p. 14836 - 14840 (2021/09/30)
An efficient electrophilic N-cyanation of amines with a stable and less-toxic cyanobenziodoxole reagent towards the synthesis of cyanamides is disclosed. This synthetically practicable strategy allows the construction of a wide variety of cyanamides under very mild and simple conditions with a broad functional group compatibility, and showcases a huge potential in late-stage modification of complex molecules.
Oxidative cyanation of 2-oxindoles: formal total synthesis of (±)-gliocladin C
Bisai, Alakesh,Das, Mrinal Kanti,De, Subhadip,Maity, Arindam,Naskar, Malay,Roy, Avishek
supporting information, p. 1679 - 1684 (2020/03/05)
Efficient oxidative direct cyanations of 3-alkyl/aryl 2-oxindoles using Cyano-1,2-BenziodoXol-3(1H)-one (CBX) (2a) have been reported under 'transition metal-free' conditions to synthesize a wide variety of 3-cyano 3-alkyl/aryl 2-oxindoles sharing an all-carbon quaternary center under additive-free conditions. The application of this process is shown by the formal total synthesis of (±)-gliocladin C (11c) in a few steps.
Revisiting the Urech Synthesis of Hydantoins: Direct Access to Enantiopure 1,5-Substituted Hydantoins Using Cyanobenziodoxolone
Declas, Nina,Le Vaillant, Franck,Waser, Jerome
supporting information, p. 524 - 528 (2019/01/14)
A method for the synthesis of enantiopure 1,5-substituted hydantoins was developed using a hypervalent iodine cyanation reagent (cyanobenziodoxolone, CBX) as a source of electrophilic carbon. Starting from inexpensive commercially available enantiopure protected amino acids, the method allowed the synthesis of various hydantoins without epimerization. Formation of hydantoins from dipeptides was also possible, but partial epimerization was observed in this case. This synthetic strategy is user friendly as CBX is a bench-stable easy-to-handle crystalline reagent and avoids conventional multistep protocols, thus allowing the facile synthesis of a library of chiral hydantoins.
A metal-free direct C (sp3)-H cyanation reaction with cyanobenziodoxolones
Sun, Ming-Xue,Wang, Yao-Feng,Xu, Bao-Hua,Ma, Xin-Qi,Zhang, Suo-Jiang
supporting information, p. 1971 - 1975 (2018/03/23)
A metal-free protocol of direct C(sp3)-H cyanation with cyanobenziodoxolones functioning as both cyanating reagents and oxidants was developed. Unactivated substrates, such as alkanes, ethers and tertiary amines, were thereby transformed to the corresponding nitriles in moderate to high yields. Mechanistic studies indicated that the cyanation proceeded with two potential pathways, which is highly dependent on the substrates: (1) a free radical case for alkanes and ethers and (2) an oxidative case for tertiary amines.
General and practical formation of thiocyanates from thiols
Frei, Reto,Courant, Thibaut,Wodrich, Matthew D.,Waser, Jerome
supporting information, p. 2662 - 2668 (2015/02/05)
A new method for the cyanation of thiols and disulfides using cyanobenziodoxol(on)e hypervalent iodine reagents is described. Both aliphatic and aromatic thiocyanates can be accessed in good yields in a few minutes at room temperature starting from a broad range of thiols with high chemioselectivity. The complete conversion of disulfides to thiocyanates was also possible. Preliminary computational studies indicated a low energy concerted transition state for the cyanation of the thiolate anion or radical. The developed thiocyanate synthesis has broad potential for various applications in synthetic chemistry, chemical biology and materials science.
Enantioselective Synthesis of Homoallylic Azides and Nitriles via Palladium-Catalyzed Decarboxylative Allylation
Vita, Maria Victoria,Caramenti, Paola,Waser, Jerome
supporting information, p. 5832 - 5835 (2015/12/11)
Azides and nitriles are important building blocks for the synthesis of nitrogen-containing bioactive compounds. The first example of enantioselective palladium-catalyzed decarboxylative allylation of α-azido and cyano β-ketoesters is reported. Indanone derivatives were obtained in 50-88% yield/77-97% ee and 46-98% yield/78-93% ee for azide and nitrile substituents, respectively. The required starting materials were synthesized in one step from ketoesters via electrophilic azidation and cyanation using benziodoxole hypervalent iodine reagents. The products could be easily converted into useful nitrogen-containing building blocks, such as triazoles, amides, or α- and β- amino ketones.
The direct electrophilic cyanation of β-keto esters and amides with cyano benziodoxole
Wang, Yao-Feng,Qiu, Jiashen,Kong, Dejie,Gao, Yongtao,Lu, Feipeng,Karmaker, Pran Gopal,Chen, Fu-Xue
supporting information, p. 365 - 368 (2015/02/05)
The direct electrophilic α-cyanation of β-keto esters and amides has been developed using a hypervalent iodine benziodoxole-derived cyano reagent. The procedure is accomplished within 10 min and without the use of any catalyst in DMF, at room temperature. Thus, the highly functionalized quaternary carbon-centered nitriles were produced in high to excellent yields.
Umpolung Strategy for Synthesis of β-Ketonitriles through Hypervalent Iodine-Promoted Cyanation of Silyl Enol Ethers
Shen, Hang,Li, Jiaqiang,Liu, Qing,Pan, Jing,Huang, Ruofeng,Xiong, Yan
, p. 7212 - 7218 (2015/07/28)
An efficient method to synthesize β-ketonitriles from silyl enol ethers by an umploung hypervalent iodine(III)-CN species generated in situ from PhIO/BF3·Et2O/TMSCN has been developed for the first time. This method can be applied to structurally diverse aromatic and aliphatic substrates and further extended to preparation of bioactive compounds like 5-aminopyrazole and 5-aminoisoxazole.
Preparation of novel cyclic hypervalent iodine(III) compounds having azido, cyano, and nitrato ligands
Akai, Shuji,Okuno, Takayuki,Egi, Masahiro,Takada, Takeshi,Tohma, Hirofumi,Kita, Yasuyuki
, p. 47 - 51 (2007/10/02)
The title cyclic hypervalent iodine compounds (4-8) were prepared in good yields by the ligand exchange reaction of the acetoxy cyclic iodinanes (1-3) with trimethylsilyl compounds and of the chloro cyclic iodinane (9) with silver nitrate, and were found to be air-stable at room temperature.
