Pd(OAc)2-Catalyzed Carbonylative Coupling of Aryl Iodide with Ortho-Haloamines in Water

The carbonylative cross coupling of aryl iodide with ortho-haloaniline to ortho-haloanilide using phosphine-free Pd(OAc)₂ catalyst in water as a reaction medium has been studied. The present protocol facilitated the reaction of o-haloanilines with a wide variety of hindered and functionalized aryl iodides, affording good yields of the desired products. The protocol was also extended for the synthesis of benzoxazoles through cyclization of ortho-haloanilide using Cu(acac)₂ catalyst.     

Microwave-Assisted N-Cyclopropylation of Pyridinols with Cyclopropyl Boronic Acid

Copper(II)-mediated N-cyclopropylation of pyridinols involving copper(II) acetate, pyridine, and NaHMDS under microwave conditions in a dry air atmosphere is described.     

有机硼酸类催化剂在有机合成中的应用

综述了有机硼酸类作为催化剂应用于有机合成反应中的最新研究进展, 重点介绍了所发现的各种有机硼酸催化剂在缩合反应、羧酸还原反应、Diels-Alder反应中的催化活性以及反应机理. 硼酸催化剂因具有催化效率高、反应条件温和、可重复使用等优点, 必将在有机合成催化领域中得到更广泛的应用.     

镍催化的芳基硼酸偕二氟炔丙基化反应

偕二氟炔丙基取代的芳烃是一类非常重要的化合物, 但传统合成该类化合物的方法却存在很大局限性. 以过渡金属催化直接向芳烃偕二氟炔丙基化是一种高效简洁制备上述化合物的方法. 以廉价易得的Ni(NO₃)₂·6H₂O为催化剂, 首次实现了镍催化下芳基硼酸与α,α-二氟炔丙基溴的偶联反应. 该反应不仅温和高效、原料廉价易得、官能团兼容性良好, 而且还能进行克量级放大和对生物活性分子的后期氟修饰, 从而为新药研发提供了一种有效手段.     

1-苯基-3-甲基-4-苯甲酰基吡唑啉酮/PdCl2在温和条件下催化Suzuki偶联反应的研究

考察了商品化的简单非膦配体1-苯基-3-甲基-4-苯甲酰基吡唑啉酮在有氧温和条件下的Suzuki偶联反应活性,探讨了反应温度、反应时间、溶剂以及碱对反应的影响。结果表明,该配体在优化的反应条件下能高效催化不同溴代反应物和氯代反应物与苯硼酸的交叉偶联反应;提高反应温度、延长反应时间和引入质子性极性有机/水混合溶剂有利于偶联反应的进行。     

间-氨基苯硼酸盐酸盐的晶体与分子结构

间－氨基苯硼酸盐酸盐的晶体与分子结构李洪峰,王祥云,杨清传,刘元方（北京大学技术物理系,北京大学化学系,北京,１０８８７１）关键词间－氨基苯硼酸,晶体结构,分子结构我们选择了一种新的取代硼酸（ＯＨ）２ＢＣ６Ｈ４ＮＨ２（ｍ－ＡＰＢＡ）以制备新的ＢＡＴＯ...     

Copper‐Catalyzed Amidation of Primary and Secondary Alkyl Boronic Esters

The oxidative copper‐catalyzed cross‐coupling of functionalized alkyl boronic esters with primary amides is reported. Through the identification of appropriate diketimine ligands, conditions for efficient coupling of both primary and secondary alkyl boronic esters with diverse primary amides, including acetamide, have been developed.     

Synthesis of Chain-End Functional Polydienes Using Diene Comonomer Bearing Boronic Acid Masked with Diaminonaphthalene

Diene comonomers bearing boronic acid masked with 1,8-diaminonaphthalene (dan) were applied to copolymerization with isoprene or butadiene using neodymium borohydride complex as a catalyst. The comonomers were tolerant to excess modified methylaluminoxane (MMAO) and thus were applicable to the polymerization system using MMAO. On the other hand, the corresponding pinacol borate was highly reactive toward MMAO, and no incorporation into the obtained polymer was observed. A ¹³C NMR microstructural analysis of the hydrogenated copolymer revealed that all of the comonomers were located at the chain end. Further functionalization using the boron moiety at the polymer chain end was also investigated.     

Suzuki-Miyaura cross-coupling reaction of aryl chlorides with aryl boronic acids catalyzed by a palladium dichloride adduct of N-diphenylphosphanyl-2-aminopyridine

One palladium dichloride adduct of a phosphine-pyridine ligand N-diphenylphosphanyl-2-aminopyridine (L₁) [(L₁)PdCl₂] (1) has been prepared and structurally characterized. Compound 1 can be used as an effective catalyst for the Suzuki-Miyaura cross-coupling reactions of unreactive aryl chlorides with aryl boronic acids, and worked much better than its mono- or bidentate phosphine ligands. The reactions with a wide scope of substrates proceeded to give desired products in good to excellent yields.     

2,6-二甲基苯硼酸制备方法的改进

选用硼酸三丁酯为硼化剂,利用格氏试剂法制备了2,6-二甲基苯硼酸,考察了温度、硼化试剂和反应物配比对产率的影响,得出了较佳的合成条件:先由0.1mol2,6-二甲基溴苯与0.12mol镁在43℃反应1.5h制得格氏试剂(产率98.2%),然后与0.2mol硼酸三丁酯在-10℃下发生亲核取代,2h快速升温至20℃,经酸性水解得产品,分离后总产率由有机锂法的51%提高到72.2%,且反应条件更加温和并对产品进行了核磁共振、质谱和IR表征。     

Sodium 2-(2-pyridin-3-ylethylamino)ethyl sulfonate: an efficient ligand and base for palladium-catalyzed Suzuki reaction in aqueous media

PdCl₂, N-donor ligand and base mediated Suzuki coupling reaction of aryl halides and arylboronic acid in water are described. The corresponding Suzuki products were obtained in good to excellent yields.     

Convenient Preparation of Cycloalkenyl Boronic Acid Pinacol Esters

A practical method for the preparation of cycloalkenyl boronic acid pinacol esters is described. These important synthetic intermediates are typically made using more expensive methods like transition metal-catalyzed borylation of alkenyl halides or triflates. In this work, they are obtained from the simple corresponding cycloalkanones, which are subjected to Shapiro reaction conditions followed by trapping with a borate ester. The requisite products are obtained in very good to excellent yields, and the reactions can be scaled up to multigram amounts. By providing a simple alternative to common methods that make use of expensive transition-metal catalysts and formation of sensitive intermediates, this convenient method will be useful for the synthesis of ring-containing partners for Suzuki–Miyaura cross-coupling and other reactions employing boronic esters as substrates.     

Palladium‐Catalyzed Synthesis of (Hetero)Aryl Alkyl Sulfones from (Hetero)Aryl Boronic Acids,Unactivated Alkyl Halides,and Potassium Metabisulfite

A palladium‐catalyzed one‐step synthesis of (hetero)aryl alkyl sulfones from (hetero)arylboronic acids, potassium metabisulfite, and unactivated or activated alkylhalides is described. This transformation is of broad scope, occurs under mild conditions, and employs readily available reactants. A stoichiometric experiment has led to the isolation of a catalytically active dimeric palladium sulfinate complex, which was characterized by X‐ray diffraction analysis.     

Cu-Catalyzed Arylation of Bromo-Difluoro-Acetamides by Aryl Boronic Acids,Aryl Trialkoxysilanes and Dimethyl-Aryl-Sulfonium Salts: New Entries to Aromatic Amides

We describe a mechanism-guided discovery of a synthetic methodology that enables the preparation of aromatic amides from 2-bromo-2,2-difluoroacetamides utilizing a copper-catalyzed direct arylation. Readily available and structurally simple aryl precursors such as aryl boronic acids, aryl trialkoxysilanes and dimethyl-aryl-sulfonium salts were used as the source for the aryl substituents. The scope of the reactions was tested, and the reactions were insensitive to the electronic nature of the aryl groups, as both electron-rich and electron-deficient aryls were successfully introduced. A wide range of 2-bromo-2,2-difluoroacetamides as either aliphatic or aromatic secondary or tertiary amides were also reactive under the developed conditions. The described synthetic protocols displayed excellent efficiency and were successfully utilized for the expeditious preparation of diverse aromatic amides in good-to-excellent yields. The reactions were scaled up to gram quantities.     

A simple and efficient 2N2O–Cu(II) complex as a catalyst for N‐arylation of imidazoles in water

Four inexpensive and air‐ and moisture‐stable 2N2O–Cu complexes were synthesized, one of which proved to exhibit good catalytic activity for the N‐arylation of imidazoles in water. A variety of aryl iodides and aryl bromides underwent coupling with imidazoles promoted by the catalytic system with moderate to excellent yields. Copyright © 2015 John Wiley & Sons, Ltd.     

Development and Molecular Understanding of a Pd-Catalyzed Cyanation of Aryl Boronic Acids Enabled by High-Throughput Experimentation and Data Analysis

A synthetic method for the palladium-catalyzed cyanation of aryl boronic acids using bench stable and non-toxic N-cyanosuccinimide has been developed. High-throughput experimentation facilitated the screen of 90 different ligands and the resultant statistical data analysis identified that ligand σ-donation, π-acidity and sterics are key drivers that govern yield. Categorization into three ligand groups – monophosphines, bisphosphines and miscellaneous – was performed before the analysis. For the monophosphines, the yield of the reaction increases for strong σ-donating, weak π-accepting ligands, with flexible pendant substituents. For the bisphosphines, the yield predominantly correlates with ligand lability. The applicability of the designed reaction to a wider substrate scope was investigated, showing good functional group tolerance in particular with boronic acids bearing electron-withdrawing substituents. This work outlines the development of a novel reaction, coupled with a fast and efficient workflow to gain understanding of the optimal ligand properties for the design of improved palladium cross-coupling catalysts.