Oxidative cleavage of alkenes allows rapid access to valuable products, starting from simple petrochemicals. Water is an ideal carrier of oxygen. Here, we report a novel electrochemical water activation for the oxidative cleavage of alkenes. Water was used as an abundant and economical oxygen source, with no additional oxidants or complex workups. A wide range of alkenes such as activated alkenes and unactivated alkenes were tolerated. Additionally, we observed oxidative cleavage of the allylic C-C(vinyl) sigma-bond and a unique linear paired electrolysis mode, which are not observed in existing methods for the oxidative cleavage of olefins.

An electrochemical ring contraction/functionalization of 2-alkylidenecyclobutanol derivatives is presented, enabling the facile and oxidant-free synthesis of β-functionalized cyclopropanecarbaldehydes (CPAs) and cyclopropylketones (CPKs) though anodic oxidation, β-scission, and reoxidation processes. This protocol demonstrates a broad substrate scope, effectively accommodating a diverse range of 2-alkylidenecyclobutanols and various weak nucleophiles, thereby offering straightforward access to β-alkoxylated, hydroxylated, fluorinated, and azidated CPAs. Mechanistic investigations confirm the involvement of a 2-alkylidenecyclobutyl oxy radical intermediate and a subsequent β-scission process.

A novel palladium-catalyzed allylic C-H alkylation of terminal olefins with 3-carboxamide oxindoles is described. A variety of new 3-carboxamide-3-allylation oxindoles with an all-carbon quaternary center were obtained in moderate to good yields (up to 99%). In addition, the asymmetric version of this reaction was also explored, providing moderate enantioselectivity.

A chiral Zn-Sr heterobimetallic catalyst system generated in situ has been developed for the first highly Z/E-selective asymmetric conjugate addition of 3-acetoxy-2-oxindoles to alkynones. Both terminal alkynones and nonterminal alkynones could be applied to the heterobimetallic catalytic system. The corresponding 3-alkenyl-3-acyloxy-2-oxindoles were obtained in moderate to excellent yields (55-99%) with high E:Z ratios (8:1-30:1) and high enantioselectivities (86-99% ee).

A Ni/PyBisulidine catalyzed asymmetric Michael addition of 3-acyloxy-2-oxindoles to nitroalkenes has been developed. Various quaternary substituted 3-acyloxy-2-oxindoles were obtained with excellent yields and diastereo- and enantioselectivities in a low-toxic green solvent, ethyl acetate, with a low catalyst loading (1 mol%). The reaction process is air and moisture tolerant. The substrate scope was also extended to α,β-disubstituted nitroalkenes and 3-hydroxy-2-oxindoles, and good results were obtained.

A novel asymmetric [4 + 4] dipolar cycloaddition of aliphatic 1,4-dipoles with azadienes was developed to construct chiral benzofuran- and indene-fused eight-membered N-heterocycles in good yields and excellent stereoselectivities.

Course ideological and political education is an innovative means of practical teaching to enable professional knowledge to carry more social responsibility and value leading role. A teaching reform of Organic Chemistry experiment was proposed in Pharmacy specialty, which meant to improve teachers’ ideological and political consciousness, gather the strength of teaching team, explore the ideological and political elements in Organic Chemistry experiment, optimize teaching content, reform teaching methods and assessment methods. A system was built for curriculum ideological and political collaborative education and teaching with Organic Chemistry experiment as the carrier. The strategies of integrating political elements into the teaching process can realize the value guidance in the process of knowledge transmission.

A novel palladium catalyzed homodimerization of ortho-hydroxyphenyl substituted p-QMs has been developed via [4 + 2] cycloaddition/oxidative dehydrogenation coupling domino reactions. An interesting palladium catalyzed intramolecular benzyl C-H oxidation dehydrogenation to form a transannular C(sp3)-O bond was found. This protocol provided an efficient method to construct various dibenzodioxo[3.3.1]nonanes bearing spirocyclohexadienones.

Highly selective divergent oxidative dearomatization coupling reactions, in which the chemoselectivity is controlled by catalysts and bases, are reported herein. Three different kinds of polycyclic cyclohexadienones are produced from the same reactants (41 examples, 85-99% yield). Our method marks a novel copper- and palladium-catalyzed C-H oxidative dearomatization of phenolic derivatives.

A heterobimetallic zinc/strontium catalyst has been developed for the asymmetric Michael addition of 3-acetoxy-2-oxindoles to β-ester enones in high yields with excellent enantioselectivities and high diastereoselectivities. This process represents that 3-acetoxy-2-oxindoles can be used as a stable air- and base-tolerant precursor for chiral 3-substituted 3-hydroxy-2-oxindoles.

将思维导图引入医用有机化学的教学实践.以芳香烃为例,从局部到整体,逐层设计并构建了苯及其衍生物的亲电取代反应、化学性质及芳香烃小结等多个层次的思维导图,引导学生对所学知识进行归纳总结和发散思维.并举例说明如何以小组合作方式构建思维导图,培养学生协作能力.形式多样的思维导图可以帮助学生在医用有机化学的学习中理清思路,培养思维习惯和建立思维方法,是一种有效的教学辅助工具.

合成了几个含N-O多官能手性配体与铜、钐原位生成杂双金属络合物用于催化醛的不对称Henry反应,得到一系列手性β-硝基醇化合物,产物结构经1H NMR,13C NMR和高分辨率质谱(HR-MS)表证.通过控制实验和非线性效应的研究,推测催化体系中单聚双金属Cu/Sm/L2络合物为催化反应的活性中心,是不对称Henry反应获得高对映选择性(最高达82％ ee)和高反应收率(最高为94％)的重要影响因素.

为了认真贯彻"停课不停学"精神,文章从前期准备、在线课程教学活动的开展、通过监管和反馈保证教学质量三个方面论述了利用在线课堂实现医用有机化学"停课不停学"的实践.

A novel organocatalytic asymmetric cascade 1,6-addition/hemiketalization/retro-Henry reaction of ortho-hydroxyphenyl-substituted p-QMs with α-nitroketones is described. A variety of novel chiral 2-(1-(4-hydroxyphenyl)ethyl)phenols are constructed for the first time with high yields (up to 92%) and excellent enantioselectivities (up to >99% ee) under mild reaction conditions. A gram-scale experiment of this process is also presented.

为了在本科阶段加强对学生科研能力的培养,我们结合自身的科研工作和有机化学最新科研成果,介绍一个面向大学高年级本科生的综合性有机化学实验——新型靛红衍生的对亚甲基苯醌的合成与结构表征.以靛红为起始原料,经过脱水缩合、 氨基上Boc保护基两步反应,结合柱层析、 萃取等多种分离手段,最终得到目标化合物.实验中采用TLC法跟踪实验的反应进程,并利用熔点测定、 红外光谱和核磁共振谱图等表征手段确定了目标化合物的结构.

A novel Et3N-catalyzed domino oxa-Michael/1,6-addition reaction of ortho-hydroxyphenylsubstituted p-QMs with barbiturate-based olefins is achieved under mild conditions. Various new spiro-barbituratechromans were obtained in excellent yields and diastereoselectivities (90–99% yield, >99:1 dr). The structure of the new compound 3a was determined by single crystal X-ray analysis.

A homodinuclear Co2/aminophenol sulfonamide complex has been developed for the asymmetric Michael reaction of β-ketoesters with nitroolefins. This procedure is capable of tolerating a wide range of substrates and excellent results (up to 99% yield, >99 : 1 dr and 98% ee) can also be obtained. Moreover, the reaction could be carried out on a 50 mmol scale without any decrease in the enantioselectivity and reactivity. On the basis of the results of mechanistic studies, we proposed that the Co2/2a complex would be the active species and a possible catalytic cycle was described.

A pre-prepared Ni-PyBisulidine complex has been developed for the catalytic asymmetric Henry reaction of α-keto esters, 2-acylpyridines and 2-acylpyridine N-oxides. The corresponding β-nitro-α-hydroxy esters were obtained in good to excellent yields (up to 99%) with a high enantiomeric excess (ee) (up to 94%) with a catalyst loading of 1-2 mol%. The desired products of 2-acylpyridines and 2-acylpyridine N-oxides, which were simple methyl ketones, were obtained in medium to excellent yields (up to 94%) with medium to good ee (up to 86%) by using 2 mol% of catalyst.

A facile K2CO3-promoted novel domino 1,6-addition/O-alkylation reaction of ortho-hydroxyphenylsubstituted p-QMs and diethyl bromomalonate is described. A variety of new 3-aryl 2,3-dihydrobenzofurans were obtained in excellent yields (up to 99%) under simple and mild conditions. The structure of the new compound 3f was determined by single crystal X-ray analysis.