- DISSOLVING METAL REDUCTION WITH CROWN ETHER --- REDUCTIVE REMOVAL OF ISOCYANO GROUPS
-
Toluene radical anion generated from K metal and toluene with the assistance of crown ether has been proven effective for reductive removal of aliphatic isocyano groups.
- Ohsawa, Tomihiko,Mitsuda, Naoki,Nezu, Jun'ichi,Oishi, Takeshi
-
-
Read Online
- Roles of supports on reducibility and activities of Cu3P catalysts for deoxygenation of oleic acid: In situ XRD and XAS studies
-
This work demonstrates for the first time that SiO2 and ultra-stable zeolite Y (USY) supports play significant roles in the reducibility of Cu2P2O7 to form Cu3P, which consequently affects the selectivity of oleic acid deoxygenation. The formation of supported Cu3P nanoparticles during hydrogen reduction of Cu2P2O7 was carefully investigated by in situ X-ray diffraction (in situ XRD), and in situ X-ray absorption spectroscopy (in situ XAS). The results indicate that the transformation of Cu2P2O7 to Cu3P occurs through several steps. In the first step, all supported Cu2P2O7 precursors are reduced to metallic Cu. Then, copper particles on SiO2 support react with phosphorus compounds and directly transform to Cu3P. On the other hand, copper particles on USY support partially transform to CuP2 and Cu(OH)2 before all converting to Cu3P. Despite multi-step transformations, Cu2P2O7/USY exhibits the lowest onset reduction temperature and provides Cu3P with a small particle size. The deoxygenation of oleic acid over Cu3P supported catalysts reaches nearly 100 % conversion. Both catalysts favor cyclization and aromatization to form cyclic and aromatic compounds. Cu3P/SiO2 achieves higher dodecylbenzene yield (46 %) than Cu3P/USY (33 %). A proposed mechanism consists of hydrogenation of oleic acid and deoxygenation, then followed by cracking, cyclization, aromatization, and alkyl rearrangement.
- Kochaputi, Nopparuj,Khemthong, Pongtanawat,Kasamechonchung, Panita,Butburee, Teera,Limphirat, Wanwisa,Poo-arporn, Yingyot,Kuboon, Sanchai,Faungnawakij, Kajornsak,Kongmark, Chanapa
-
-
- Nickel/Cobalt-Catalyzed C(sp3)-C(sp3) Cross-Coupling of Alkyl Halides with Alkyl Tosylates
-
The C(sp3)-C(sp3) cross-coupling of alkyl halides with alkyl tosylates has been developed by employing a combination of nickel and nucleophilic cobalt catalysts in the presence of a manganese reductant. This method provides a straightforward route to a diverse set of not only secondary-primary but also primary-primary C(sp3)-C(sp3) linkages under mild conditions without using alkyl-metallic reagents. Mechanistic studies suggest the formation of alkyl radicals from both alkyl halides and alkyl tosylates. Additionally, cross-coupling could be applied to the short-step synthesis of a histone deacetylase inhibitor, Vorinostat.
- Komeyama, Kimihiro,Michiyuki, Takuya,Osaka, Itaru
-
p. 9285 - 9291
(2019/10/11)
-
