Lewis Acidic Guanidinium Ionic Liquids:Novel,Efficient and Recyclable Catalysts for Aminolysis of Epoxides

Lewis acidic guanidinium ionic liquid(LAGIL) 2c was used as a novel, efficient and recyclable catalyst for aminolysis of epoxides under solvent-free and room temperature conditions, giving the corresponding β-amino alcohols with moderate to excellent regioselectivity(up to 91:9) in high yields(up to 97%). In addition, LAGIL 2c was recycled three times without any loss of catalytic activity and selectivity to the product.     

A novel and efficient synthesis of Entecavir

A practical synthesis of Entecavir (1) has been accomplished in 10 steps with 21% overall yield. The key steps to construct the five-membered carbocyclic framework 2 are a ring-closing metathesis and a diethyl-aluminum 2,2,6,6-tetramethyl piperidide (DA-TMS) mediated epoxide isomerization. Furthermore, the guanine was introduced by modified Mitsunobu reaction.     

Catalytic Asymmetric Epoxidation of Aldehydes with Two VANOL‐Derived Chiral Borate Catalysts

A highly diastereo‐ and enantioselective method for the epoxidation of aldehydes with α‐diazoacetamides has been developed with two different borate ester catalysts of VANOL. Both catalytic systems are general for aromatic, aliphatic, and acetylenic aldehydes, giving high yields and inductions for nearly all cases. One borate ester catalyst has two molecules of VANOL and the other only one VANOL. Catalysts generated from BINOL and VAPOL are ineffective catalysts. An application is shown for access to the side‐chain of taxol.     

高效固体酸SBA-15-Zr(OTf)3催化胺或醇开环环氧化合物

通过简单的一锅两步法制备了三氟金属(铝,钛,锆)接枝介孔SBA-15 (AlTf/S,TiTf/S,ZrTf/S)固体酸材料,并通过XRD,N2吸附,TGA,FTIR,原位吡啶FTIR和元素分析对这些材料进行了详细的表征.其中,ZrTf/S能够高效催化环氧化物温和条件下被胺或醇开环生成对应β-氨基醇或β-烷氧基醇,并且催化剂能循环利用.ZrTf/S相较于AlTf/S和TiTf/S酸性最强,因而催化活性也最高.     

Zirconyl nitrate mediated regioselective ring opening of epoxides and aziridines: an easy synthesis of β-nitrato-alcohols and -sulfonamides

Epoxides and aziridines are cleaved efficiently and regioselectively in the presence of zirconyl nitrate at room temperature to afford the corresponding β-nitrato-alcohols and -sulfonamides, respectively, in high yields.     

Aluminumdodecatungstophosphate (AlPW12O40) as a reusable Lewis acid catalyst: Facile regioselective ring opening of epoxides with alcohols, acetic acid and thiols

AlPW₁₂O₄₀ as a recyclable Lewis acid and stable solid compound was introduced for efficient ring opening of different epoxides with thiols, acetic acid, and primary, secondary, and tertiary alcohols. These processes were carried out at room temperature with high regio- and stereoselectivity.     

聚酯-聚醚嵌段共聚物同环氧树脂共混改性的研究

聚酯-聚醚多嵌段共聚物同少量的环氧树脂等共混,可以改善共混物作热熔胶使用时的剪切强度、剥离强度和热光老化性能。本文研究了共混条件,同时根据IR、DTA、TM和TG实验结果,提出了在熔融粘接过程中,环氧基同共聚物端羟、羧基反应的可能性。     

Iminosugars from α,β-epoxyamides. Part 2: Synthetic approach to hydroxylated pyrrolidine and azepane derivatives

This paper describes a new synthetic route towards hydroxylated pyrrolidines and azepane derivatives starting from chiral epoxyamides. The alternate transformations on a ribose derivative α,β-epoxyamide permit the construction of five or seven member rings leading to different precursors of homoiminosugars.     

Isotope effects and the mechanism of deoxygenation of epoxides with dichlorocarbene

The deoxygenation of styrene oxide with dichlorocarbene is studied by a combination of isotope effects and theoretical calculations. A normal ¹³C isotope effect of 1.016 is observed for the α-carbon of the styrene oxide but a surprising inverse isotope effect of 0.995 is observed at the β-carbon. This is indicative of a highly asynchronous process in which the C_α-O bond is broken without any progress in the breakage of C_β-O bond. Theoretical calculations support this interpretation. This coarctate reaction is formally concerted as it avoids involving a high-energy intermediate, but it appears uninfluenced by transition state aromaticity.     

Effect of HCl on the PPO assisted sol-gel synthesis of olivine-type Co2SiO4 ultrafine particles

Olivine-type Co₂SiO₄ ultrafine particles were synthesized by a sol-gel method using propylene oxide as a gelation agent. Owing to the high homogeneity of the intermediate gel precursor, the usage of this epoxide method results in a substantial reduction of calcination temperature and time as compared with the solid-state route, and a great reduction of calcination time as compared with other wet-chemistry routes. This high homogeneity is obtained by the usage of an appropriate amount of HCl, as a catalyst that matches the rate of hydrolysis of TEOS and the metal ions, allowing the formation of Si–O–Co bonds.