10226-30-9Relevant articles and documents
In-situ-generation of alkylsilyl peroxides from alkyl hydroperoxides and their subsequent copper-catalyzed functionalization with organosilicon compounds
Xu, Weiping,Zhong, Wenfeng,Yang, Qin,Kato, Terumasa,Liu, Yan,Maruoka, Keiji
, (2021)
Alkylsilyl peroxides were generated in situ from the corresponding alkyl hydroperoxides using organosilicon compounds of the type Me3SiX (X = CN, N3, and halogens) and an amine base. Subsequent in situ copper-catalyzed homolytic cleavage of the alkylsilyl peroxides afforded alkyl radicals, which were then trapped with X (X = CN, N3, and halogens) to furnish products with new carbon-carbon, carbon-nitrogen, or carbon-halogen bonds in good to high yields.
Controlling Selectivity by Controlling Energy Partitioning in a Thermal Reaction in Solution
Kurouchi, Hiroaki,Andujar-De Sanctis, Ivonne L.,Singleton, Daniel A.
, p. 14534 - 14537 (2016)
The comparison of experimental and predicted kinetic isotope effects in the α-cleavage of alkoxy radicals is used here to judge the applicability of statistical rate theories. It is found that the governing rate theory and the statistical versus nonstatistical nature of the cleavage depend on the cleavage barrier and how much energy is imparted to the radical. The latter can then be controlled by changing the size of substituents in the system. With a large alkyl group substituent, the vibrational energy of the alkoxy radical is increased, but this energy is not statistically distributed, leading to a lower isotope effect than predicted by statistical theories. The observed isotope effect can be approximately rationalized using a semistatistical localized RRKM model.
Palladium-Catalyzed Aerobic Anti-Markovnikov Oxidation of Aliphatic Alkenes to Terminal Acetals
Komori, Saki,Yamaguchi, Yoshiko,Kataoka, Yasutaka,Ura, Yasuyuki
, p. 3093 - 3099 (2019/03/29)
Terminal acetals were selectively synthesized from various unbiased aliphatic terminal alkenes and 1,2-, 1,3-, or 1,4-diols using a PdCl2(MeCN)2/CuCl catalyst system in the presence of p-toluquinone under 1 atm of O2 and mild reaction conditions. The slow addition of terminal alkenes suppressed the isomerization to internal alkenes successfully. Electron-deficient cyclic alkenes, such as p-toluquinone, were key additives to enhance the catalytic activity and the anti-Markovnikov selectivity. The halogen groups in the alkenes were found to operate as directing groups, suppressing isomerization and increasing the selectivity efficiently.
Cobaloxime-catalyzed hydration of terminal alkynes without acidic promoters
Hou, Shengtai,Yang, Hongjian,Cheng, Bin,Zhai, Hongbin,Li, Yun
supporting information, p. 6926 - 6929 (2017/07/10)
Cobaloxime (Co(dmgBF2)2·2H2O), an inexpensive first-row transition-metal complex, catalyzed hydration of terminal alkynes gave the corresponding methyl ketones in good to excellent yields under neutral conditions (additional protic acids and silver salts are not required). A wide range of functional groups, such as allyl ether, benzyl ethers, carboxylic esters, imides, amides, nitro, and halogens, were tolerated. The mild reaction conditions together with the inexpensive feature and easy availability of the catalyst well address the current challenges in the field of alkyne hydration.
Micellar catalysis-enabled sustainable ppm Au-catalyzed reactions in water at room temperature
Klumphu, Piyatida,Desfeux, Camille,Zhang, Yitao,Handa, Sachin,Gallou, Fabrice,Lipshutz, Bruce H.
, p. 6354 - 6358 (2017/08/29)
Several ppm level gold-catalyzed reactions enabled by the ligand HandaPhos can be performed at room temperature in aqueous nanoreactors composed of the surfactant Nok. Variously substituted allenes undergo cycloisomerization leading to heterocyclic products in good yields. Likewise, cyclodehydration is also illustrated under similar conditions, as is an intermolecular variant, hydration of terminal alkynes. Recycling of the catalyst and reaction medium is also illustrated. A low E factor associated with limited solvent use and therefore, waste generation, documents the greenness of this process.
Secondary Phosphine Oxides as Multitalented Preligands En Route to the Chemoselective Palladium-Catalyzed Oxidation of Alcohols
Vasseur, Alexandre,Membrat, Romain,Gatineau, David,Tenaglia, Alphonse,Nuel, Didier,Giordano, Laurent
, p. 728 - 732 (2017/03/13)
Secondary phosphine oxides O=PHR2 (SPOs) were identified as multitalented preligands for the chemoselective Pd-catalyzed oxidation of alcohols by a hydrogen-abstracting methodology. SPOs were found to promote the hydrogen-abstraction step as well as hydrogen transfer to a Michael acceptor by generating a putative active H?Pd species. The catalytic system operates under neutral conditions and was proven to be compatible with various electrophilic and nucleophilic functionalities within the substrates as well as water- and air-sensitive functional groups.
Hydration of alkynes at room temperature catalyzed by gold(I) isocyanide compounds
Xu, Yun,Hu, Xingbang,Shao, Jing,Yang, Guoqiang,Wu, Youting,Zhang, Zhibing
supporting information, p. 532 - 537 (2018/04/16)
An effective method using gold(I) isocyanide complexes as catalysts for the transformation of various alkynes to the corresponding ketones is successfully developed. The hydration process proceeds smoothly at room temperature with quite high yield (up to 99%). The catalytic center is the isocyanide-Au(I)+ cation. Further theoretical research reveals a direct hydration mechanism by H2O, and the rate-determining step has an energy barrier of 23.7 kcal mol?1. These results show a good example to reduce unnecessary steps and achieve milder reaction conditions at the same time for the hydration of alkynes.
Formal hydration of non-activated terminal olefins using tandem catalysts
Yang, Yongsheng,Guo, Jiayi,Ng, Huimin,Chen, Zhiyong,Teo, Peili
supporting information, p. 2608 - 2611 (2014/03/21)
The hydration of terminal olefins to secondary alcohols has been achieved using a Pd(ii)/Ru(ii) catalyst combination with high regioselectivity and yields. Both vinyl arenes and aliphatic olefins can be hydrated easily with the tandem catalyst system using a low catalyst loading of 1 mol%. The Royal Society of Chemistry 2014.
Synthesis of 1-(n-hexyl-5-one)-2-chlorobenzimidazole
Dubey,Naidu,Anandam,Hemasunder
, p. 1239 - 1242 (2007/10/03)
o-Phenylenediamine on condensation with urea gives the known benzimidazolin-2-one, which on reaction with phosphoryl chloride in the presence of catalytic amount of phenol yields the already reported 2- chlorobenzimidazole. The latter on alkylation with 6-chloro-2-hexanone in the presence of K2CO3 in DMF medium, gives the title compound.
