Palladium-Catalyzed anti-Markovnikov Halosulfonamidation of Unactivated Alkene

Palladium-catalyzed regioselective amination of unactivated alkene remains a challenge and is of great interest.Herein,a three-component coupling of unactivated alkene,sulfonamide,and N-halo compounds accessing vicinal haloamine has been conceived.This aminohalogenation represents a modular and regioselective strategy.The electrophilic halogenating agent enables regioselective anti-Markovnikov aminopalladation and facilitates subsequent halogenation events.And this protocol is characterized by gram-scale syntheses and late-stage functionalizations.Of note,the recovered byproduct phthalimide allows for reusing by conversion to the starting material.

Coordination structure dominated performance of single-atomic Pt catalyst for anti-Markovnikov hydroboration of alkenes

The rational design of efficient single-atomic(SA)catalysts is essential and highly desirable but impeded by the lack of sufficient acknowledge between structure and property.To this end,it is critical to clarify the effect of the coordination structure of active metal centers on the catalytic activities for the design of such catalysts.Here,we report that different coordination structures of SA Pt catalysts can dramatically influence their activities for anti-Markovnikov hydroboration of alkenes.Compared with the other two coordination structures(Pt-N4 and Pt-O2),the SA Pt species coordinated with three O atoms(Pt-O3)display the highest turnover number value of 3288 for the hydroboration reaction to access the important alkylboronic esters.Density functional theory calculations reveal that a superior catalytic activity can be expected for alkene hydroboration over the three O coordinated Pt species due to the lowest reaction energy(ΔG)limiting step from the reaction phase diagram.

Iodine（Ⅲ） reagent（ABX–N3）-induced intermolecular anti-Markovnikov hydroazidation of unactivated alkenes

Anti-Markovnikov hydroazidation of unactivated alkenes using ABX–N3 as an initiator has been developed at room temperature,wherein hydrogen azide(HN3)acts as both hydrogen and azidating agent.Notably,the HN3 reagent was generated from azidotrimethylsilane(TMSN3)and acetic acid in situ.The reaction itself displays broad substrate scope,good yields and excellent regioselectivities.

Photo-induced anti-Markovnikov hydroalkylation of unactivated alkenes employing a dual-component initiator

Metal-free anti-Markovnikov hydroalkylation of unactivated alkenes with cyanoacetate has been developed,featuring the use of a dual-component initiator containing an organic photocatalyst and a radical precursor.When combined,the two components can undergo visible light-induced singleelectron transfer,and serve as a versatile and effective alkyl radical generator.

Visible-Light-Driven Anti-Markovnikov Hydrocarboxylation of Acrylates and Styrenes with CO_(2)

Light-driven carbon dioxide(CO_(2))capture and utilization is one of the most fundamental reactions in Nature.Herein,we report the first visible-light-driven photocatalyst-free hydrocarboxylation of alkenes with CO_(2).Diverse acrylates and styrenes,including challenging tri-and tetrasubstituted ones,undergo anti-Markovnikov hydrocarboxylation with high selectivities to generate valuable succinic acid derivatives and 3-arylpropionic acids.In addition to the use of stoichiometric aryl thiols,the thiol catalysis is also developed,representing the first visible-lightdriven organocatalytic hydrocarboxylation of alkenes with CO_(2).The UV-vis measurements,NMR analyses,and computational investigations support the formation of a novel charge-transfer complex(CTC)between thiolate and acrylate/styrene.Further mechanistic studies and density functional theory(DFT)calculations indicate that both alkene and CO_(2)radical anions might be generated,illustrating the unusual selectivities and providing a novel strategy for CO_(2)utilization.

Manganese-Catalyzed Anti-Markovnikov Hydroarylation of Enamides:Modular Synthesis of Arylethylamines

The arylethylamine framework is a prevalent motif in a great range of biologically important organic compounds.One intractable task for frontline drug discovery is to find structurally new medicine candidates instead of opioid,based on the construction of a rich chemical space of arylethylamine motif In this report,a practical protocol for the synthesis of arylethylamine functionality common in pharmaceutical chemicals has been developed.It proceeds by Mn-catalyzed anti-Markovnikov hydroarylation of electron-rich enamides under mild conditions without the use of ligands.In spite of mismatched electronic effects during the manganese-mediated migratory insertion process,both terminal and internal enamides can be regioselectively hydroarylated with various aryl boronic acids in 15 min.Also,the successful hydroalkenylation of enamides with alkenyl boronic acids in air atmosphere affords an elegant route to synthetically useful β-alkenylated amines in satisfactory yields.The synthetic robustness and practicality of the reaction reveal its simple operation,short reaction time,viability on a gram-scale and its value in late-stage modification of complex molecules.

离子液体中的Mannich反应研究

研究了甲醛、芳香酮、脂肪胺盐酸盐3组分在离子液体[bmim]BF4中的Mannich反应,反应不需要加入任何路易斯酸或质子酸催化剂即可发生,且离子液体至少可以循环使用5次。同时还考察了芳香醛、芳香酮、芳香胺3组分在[bmim]BF4中的Mannich反应。

苯乙烯反马氏加成法合成β-溴乙苯

通过苯乙烯与溴化氢气体发生反马氏规则自由基加成反应,合成了β-溴乙苯(β-BEB)。考察了反应时间、原料配比、引发剂用量和反应温度等因素对试验结果的影响。结果表明在溴化氢与苯乙烯的摩尔比为1.2,溶剂正庚烷与苯乙烯的体积比为5,引发剂偶氮二异丁腈与苯乙烯的质量比为0.5×10-2,反应温度80℃,反应时间60 min的反应条件下,β-BEB的收率≥92.0%,纯度≥96.8%(以苯乙烯计)。

不对称烯烃加成反应中的马氏规则和反马氏规则

从电子效应和反应历程两个方面探讨马氏规则;列举反马氏规则的几种类型,并加以解释.从中找出两者的内在联系,揭示马氏规则的本质.

聚异丁烯胺汽油清净剂的合成过程研究

研究了用溴化加成法合成新一代的汽油清净剂聚丁烯胺 (PIBA)。将高活性聚异丁烯与HBr气体在过氧化物存在下进行自由基反马氏加成反应生成溴化聚异丁烯 ,然后再与氨进行亲核取代反应生成聚异丁烯胺。实验研究了溶剂 ,反应时间 ,反应温度以及引发剂的加入量对反应过程的影响 。

紫外线照射下由苯乙烯合成β-溴乙苯的研究

在紫外线的照射下,苯乙烯与溴化氢气体发生反马氏规则自由基加成反应,可合成β-溴乙苯(-βBEB)。考察了反应条件对实验结果的影响,发现当紫外线强度为0.5mW/cm2,反应时间60min,反应温度60℃,溶剂CCl4用量为苯乙烯5倍的体积时,苯乙烯的转化率>99%,-βBEB的产率≥96%。使用铁粉精制后-βBEB的最终收率≥93%(以苯乙烯计),-βBEB的纯度≥99%。

1-溴-3-乙氧基丙烷的合成

3-氯丙烯与乙醇钠在乙醇中回流制得3-乙氧基丙烯,继而在过氧苯甲酰存在下,与溴化氢经反马氏加成制得1-溴-3-乙氧基丙烷,总收率89.2%。

烯烃的反马氏氢胺化反应

胺类及其衍生物是一类重要的有机化合物。通过烯烃氢胺化反应直接合成胺类及其衍生物是众多合成胺类化合物方法中最高效和原子经济性最高的方法。烯烃的反马氏氢胺化反应是合成高价值直链型胺类化合物的最优方法。最近有关此类反应的报道,主要集中在开发新的催化体系研究上。本文以此为主线,综述了烯烃反马氏氢胺化反应的最新进展。

马氏规则和反马氏规则的内在统一性

马氏规则和反马氏规则表面相反,但两者有内在的统一性。本文从电子效应和反应历程两个方面作了讨论,并通过具体实例加以解释．

反马氏加成法合成1-溴代正辛烷

无溶剂条件下,在自由基引发剂的作用下,溴化氢气体以鼓泡的方式通入到反应体系中,与1-辛烯(1-octene)发生反马氏加成,得到目标产物1-溴代正辛烷。考察了引发剂的种类、溶剂、反应温度、反应时间、投料比和反应前活化温度等对收率的影响。结果表明,以过氧化苯甲酰(BPO)作引发剂、反应温度20℃、反应1.5 h、n(1-辛烯)∶n(溴化氢)=1.0∶1.2、无溶剂条件下,产品收率大于80%,蒸馏后纯度大于99%。

New strategy for production of primary alcohols from aliphatic olefins by tandem cross-metathesis/hydrogenation

Primary alcohols are widely used in industry as solvents and precursors of detergents.The classic methods for hydration of terminal alkenes always produce the Markovnikov products.Herein,we reported a reliable approach to produce primary alcohols from terminal alkenes combining with biomass-derived allyl alcohol by tandem cross-metathesis/hydrogenation.A series of primary alcohol with different chain lengths was successfully produced in high yields(ca.90%).Computational studies revealed that self-metathesis and hydrogenation of substrates are accessible but much slower than crossmetathesis.This new methodology represents a unique alternative to primary alcohols from terminal alkenes.

钯催化苯乙烯类分子胺氟化反应研究(英文)

报道了烯烃分子间的氧化双官能团化反应,用金属钯作为金属催化剂,三价碘为氧化剂,氟化银为氟源,磺酰胺类为亲核试剂,实现了苯乙烯的分子间胺氟化反应,得到α-F代苯乙胺类化合物;反应是经过烯烃的反马氏氮钯化得到碳钯键,再经过三价碘氧化成高价钯的中间体来形成C—F键,在分子中的特定位置引入氟原子.该反应的一个特点是选择性地得到反马氏胺氟产物.

丙烯醇反马氏水合制备1,3-丙二醇

1,3-丙二醇具有很高的经济价值,是合成聚对苯二甲酸丙二酯的重要原料。基于甘油甲酸介入法获得的丙烯醇作为平台分子,通过丙烯醇与TiCl_(4)-NaBH_(4)反应,首次实现常温常压下1,3-丙二醇的制备,为1,3-丙二醇的合成提供了一条新的路径。在优化条件下,1,3-丙二醇的产率68.73%。推测反应机理为,TiCl_(4)和NaBH_(4)发生反应,生成中间体“BH_(3)”,进而实现了丙烯醇反马氏水合制备1,3-丙二醇。