纳米金/β-环糊精复合修饰碳糊电极测定亚硝酸盐

本文研究了亚硝酸盐(NO_2~-)在纳米金和β-环糊精复合修饰碳糊电极(AuNPs-β-CD/CPE)上的电化学行为。实验结果表明,与裸CPE相比,AuNPs-β-CD/CPE对NO_2~-的电化学氧化有显著的促进作用,其氧化峰电流显著增加。同时用循环伏安法(CV)、计时电流法(CA)测定了NO_2~-在AuNPs-β-CD/CPE上的电极反应动力学参数,用线性扫描伏安法(LSV)法测得NO_2~-氧化峰电流与其浓度在6.0×10-6~8.0×10-3 mol·L-1范围内呈良好的线性关系,检出限(S/N=3)为5.7×10-7 mol·L-1。将该传感器应用于水样的检测,相对标准偏差在0.15%~1.40%之间,回收率达99.3%~104.0%,检测结果符合定量测定要求。     

碱金属盐催化1,2,4-三唑与α,β-不饱和酮及二酰亚胺的氮杂Michael反应

发展了一种高效的碱金属盐催化1,2,4-三唑与α,β-不饱和酮及α,β-不饱和二酰亚胺的氮杂Michael加成反应的新方法,以中等到优异的产率得到目标产物.该方法原料易得,底物普适性好,反应条件温和,易实现克级规模的制备.产物容易转化为相应的γ-氨基醇.     

A facile and efficient method for synthesis of β-iodocarboxylates from terminal epoxides

A facile and efficient method has been developed for synthesis of β-iodocarboxylates in the presences of Ph₃P/I₂. Starting from epoxides, a series of β-iodocarboxylate compounds can be directly obtained in toluene media with excellent yields. Moreover, the method was successfully applied for the late-stage modification of natural products, such as isosteviol and vincamine derivatives, achieving the corresponding β-iodocarboxylates in good yields.     

Transition-metal,organic solvent and base free α-hydroxylation of β-keto esters and β-keto amides with peroxides in water

Without employing any transition metal, organic solvent and base, a facile, economical and environmentally friendly strategy has been developed for the α-hydroxylation of β-keto esters and β-keto amides with peroxides via radical cross-coupling reaction in water under open-air conditions. This protocol allows a convenient access to various α-hydroxy-β-keto esters and α-hydroxy-β-keto amides with up to 92% yield (34 examples). Moreover, the reaction was successfully scaled up to gram quantity and mechanistic studies showed the radical pathway was involved in this hydroxylation.     

One-Pot Synthesis of Enantioenriched β-Amino Secondary Amides via an Enantioselective [4+2] Cycloaddition Reaction of Vinyl Azides with N-Acyl Imines Catalyzed by a Chiral Brønsted Acid

A catalytic enantioselective synthesis of β-amino secondary amides was achieved using vinyl azides as the enamine-type nucleophile and chiral N-Tf phosphoramide as the chiral Brønsted acid catalyst through a five-step sequential transformation in one pot. The established sequential transformation involves an enantioselective [4+2] cycloaddition reaction of vinyl azides with N-acyl imines as the key stereo-determining step that is efficiently accelerated by a chiral N-Tf phosphoramide catalyst in a highly enantioselective manner in most cases. Further generation of the iminodiazonium ion intermediate through ring opening of the cycloaddition product and subsequent skeletal rearrangement involving Schmidt-type 1,2-aryl group migration followed by recyclization of the resulting nitrilium ion were also initiated by the same acid catalyst. Final acid hydrolysis of the recyclized products in the same pot gave rise to enantioenriched β-amino amides through C−C bond formation at the α-position of the secondary amides.     

Influence of β-cyclodextrin complexation on photochemistry of bisphenols in aqueous solutions

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柚皮素/β-环糊精超分子体系的包合行为

本文采用超声法制备了柚皮素（NAR）与β-环糊精（βCD）的包合物.粉末-X射线衍射（XRD）和红外吸收光谱（IR）测定均表明形成的包合物具有不同于主客体的新的结构性质.¹H NMR与ROESY核磁共振（NMR）实验表明NAR以苯环端从βCD的宽口端进入，并形成稳定的超分子包合物.量子化学计算分析NAR/βCD包合物的形成过程表明，驱动力源于焓驱动与氢键弱相互作用力；能隙和结合能分析得到的最优包合模式与NMR研究结果一致；ONIOM分层计算验证了上述结果.分子对接模拟出的最优包合模式也与量子化学计算、NMR的分析结果吻合.本文获取了清晰的NAR/βCD包合物构型及其形成机理，为该超分子药物的定量构效关系研究提供了理论参考.     

AgF/TFA-promoted highly efficient synthesis of α-haloketones from haloalkynes

A AgF/TFA-promoted highly efficient synthesis of a wide range of α-haloketones from haloalkynes is described. The reactions are conducted under convenient conditions and provide products in moderate to excellent yields, with broad substrate scope, including a variety of aromatic chloroalkynes and bromoalkynes.     

6,6′-Thiobis(methylene)-β-cyclodextrin dimer as a dimeric host and reusable promoter for synthesis of chromenones in water

Herein, two unit of β-cyclodextrin linked by thiomethylene bridge was synthesized and employed as a novel efficient supramolecular host for the synthesis of biologically active chromenones templates via three-component single-pot reaction. A possible reaction mechanism through molecular complexation is suggested based on 2D ROESY NMR spectroscopic analysis. Moreover, the catalyst could be easily recycled, while a 94% yield and 89% rate of catalyst recovery could be achieved after four cycles of catalyst recycling. Environmentally benign reaction conditions, excellent yields, and avoidance of organic solvent and conventional isolation as well as purification are the noteworthy credits of this developed protocol.