The Deuterated “Magic Methyl” Group: A Guide to Site-Selective Trideuteromethyl Incorporation and Labeling by Using CD3 Reagents

In the field of medicinal chemistry, the precise installation of a trideuteromethyl group is gaining ever-increasing attention. Site-selective incorporation of the deuterated “magic methyl” group can provide profound pharmacological benefits and can be considered an important tool for drug optimization and development. This review provides a structured overview, according to trideuteromethylation reagent, of currently established methods for site-selective trideuteromethylation of carbon atoms. In addition to CD₃, the selective introduction of CD₂H and CDH₂ groups is also considered. For all methods, the corresponding mechanism and scope are discussed whenever reported. As such, this review can be a starting point for synthetic chemists to further advance trideuteromethylation methodologies. At the same time, this review aims to be a guide for medicinal chemists, offering them the available C−CD₃ formation strategies for the preparation of new or modified drugs.     

Construction of mixed carboxylate and pyrogallate building units for luminescent metal-organic frameworks

A metal-organic framework,Ce-FDM-50,was constructed by employing gallic acid featuring both carboxylate and pyrogallate as the coordinating sites and Ce(Ⅲ).The co-assembly of the carboxylates and pyrogallates with two metal ions have achieved a new type of paddle wheel secondary building unit.These building units were further joined by organic struts to obtain frameworks in sql topology.This synthetic approach could be expanded to five different lanthanide metals(Nd,Eu,Gd,Tb,Yb)for the construction of a series of isoreticular MOFs based on FDM-50,and even MTV-MOFs in which mixed lanthanide metals with specific ratios were distributed.In addition,featuring the lanthanide metals as the inorganic nodes in the network,Tb-FDM-50 showed distinct luminescence properties that could be furtherly tuned for variable applications.     

Base Metal Catalyzed Isocyanide Insertions

Isocyanides are diverse C₁ building blocks considering their potential to react with nucleophiles, electrophiles, and radicals. Therefore, perhaps not surprisingly, isocyanides are highly valuable as inputs for multicomponent reactions (MCRs) and other one‐pot cascade processes. In the field of organometallic chemistry, isocyanides typically serve as ligands for transition metals. The coordination of isocyanides to metal centers alters the electronic distribution of the isocyano moiety, and reaction pathways can therefore be accessed that are not possible in the absence of the metal. The tunable reactivity of the isocyanide functional group by transition metals has evolved into numerous useful applications. Especially palladium‐catalyzed isocyanide insertion processes have emerged as powerful reactions in the past decade. However, reports on the use of earth‐abundant and cheap base metals in these types of transformations are scarce and have received far less attention. In this Minireview, we focus on these emerging base metal catalyzed reactions and highlight their potential in synthetic organic chemistry. Although mechanistic studies are still scarce, we discuss distinct proposed catalytic cycles and categorize the literature according to 1) the (hetero)atom bound to and 2) the type of bonding with the transition metal in which the (formal) insertion occurs.     

Acyl Fluorides in Late‐Transition‐Metal Catalysis

In this Review, we summarize the current state of the art in late‐transition‐metal‐catalyzed reactions of acyl fluorides, covering both their synthesis and further transformations. In organic reactions, the relationship between stability and reactivity of the starting substrates is usually characterized by a trade‐off. Yet, acyl fluorides display a very good balance between these properties, which is mostly due to their moderate electrophilicity. Thus, acyl fluorides (RCOF) can be used as versatile building blocks in transition‐metal‐catalyzed reactions, for example, as an “RCO” source in acyl coupling reactions, as an “R” source in decarbonylative coupling reactions, and as an “F” source in fluorination reactions. Starting from the cleavage of the acyl C?F bond in acyl fluorides, various transformations are accessible, including C?C, C?H, C?B, and C?F bond‐forming reactions that are catalyzed by transition‐metal catalysts that contain the Group 9–11 metals Co, Rh, Ir, Ni, Pd, or Cu.     

糖肽的固相合成

目前糖肽的固相合成可以分为两种策略：构建单元策略和固相糖基化策略。本文对O-连接和N-连接糖肽固相合成的研究进展进行了综述。     

大型公共建筑工程质量保险纯费率厘定研究——基于GLM及GAM的实证比较分析

为准确地厘定大型公共建筑工程质量的保险纯费率,通过文献分析及调研,对影响大型公共建筑工程质量的因素进行了研究,提炼出11项保险费率因子。以46栋竣工于1993—2016年的大型公共建筑为工程数据集,在频率-强度法基础上,基于Poisson、Negative Binomial、Gamma、Inverse Gauss等分布的假设,利用广义线性模型及广义可加模型建立了8个工程质量保险纯费率厘定模型,通过比较选择最优模型,并对模型进行了验证。结果表明,所建模型可用于大型公共建筑工程质量保险纯费率厘定。     

Synthesis and Crystal Structure of a Novel 1D Coordination Polymer: [Pr(BYBA)3(H2O)2]·[Pr(BYBA)3(H2O)]

The novel coordination polymer [Pr(BYBA)3(H2O)2]·[Pr(BYBA)3(H2O)] (BYBAH = 2-benzoylbenzoic acid) was yielded by hydrothermal synthesis, determined by single-crystal X-ray diffraction, and characterized by FT-IR and UV-Vis spectra. The crystal crystallizes in the triclinic system, space group P with a = 9.112(3), b = 14.644(5), c = 27.076(11) (A), α = 84.223(3), β = 87.816(4), γ = 88.902(4)o, V = 3592(2) (A)3, C84H60O21Pr2, Mr = 1687.14, Z = 2, F(000) = 1700, Dc = 1.560 g/cm3, μ = 1.419 mm-1, the final R = 0.0485 and wR = 0.1258 for 13035 observed reflections with I＞2((I). The compound contains two different building units, [Pr2(BYBA)6(H2O)4] and [Pr2(BYBA)6(H2O)2]. It is noticeable that [Pr2(BYBA)6(H2O)4] is an isolated binuclear building block, in which the Pr3 ion centers are both located in an eight-coordinated environment. However, in [Pr2(BYBA)6(H2O)2] the Pr3 ion centers are located in a nine-coordinated environment and connected by BYBA ligands to form 1D chains.     

以苯为模块自组装合成碳纳米片

在300 ℃苯溶剂中, 以无水三氯化铝为催化剂, 以苯和六氯乙烷为碳源, 基于傅克烷基化反应生成三氯乙烯苯, 并以之为模块自组装合成了具有叠层结构的碳微米颗粒, 其层片厚度为300～500 nm. 进而在反应体系和反应条件不变的情况下, 通过引入铝粉颗粒作为基底成功地诱导出厚度为30～50 nm的碳纳米片. 实验结果表明, 所得碳材料由纳米石墨微晶和非晶碳组成. 文中探讨了叠层结构的台阶长大机制, 以及碳纳米片在铝粉表面的异质形核机制.     

硝基基团修饰的金属有机框架化合物的合成及晶体结构表征

分别以2种硝基羧酸配体EBNB(1,2-二(3-硝基苯甲酸)-乙烯)和NPA(3-硝基邻苯二甲酸)与BPY(4,4′-联吡啶)及金属锌反应,配位溶剂热法合成了2种具有硝基基团修饰的二核金属簇为基本构筑单元的金属有机框架化合物[Zn2(EBNB)2(BPY)2·2H2O]n(1)和[Zn2(NPA)2(BPY)2·H2O]n(2)。通过X-射线单晶衍射法测定了2种配合物的结构,其中配合物1属于三斜晶系,P1空间群,a=0.818 62(9)nm,b=1.142 20(14)nm,c=1.428 63(17)nm,α=96.803 0(10)°,β=93.045 0(10)°,γ=102.472(2)°,V=1.290 8(3)nm3,Z=2,Mr=595.81,Dc=1.533 g·cm-3,μ=1.01 mm-1,F(000)=608,T=293(2)K;配合物2属于三斜晶系,P1空间群,a=1.154 06(14)nm,b=1.190 86(16)nm,c=1.459 52(19)nm,α=98.029(1)°,β=98.749(1)°,γ=113.579(2)°,V=1.771 9(4)nm3,Z=2,Mr=879.35,Dc=1.648 g·cm-3,μ=1.43 mm-1,F(000)=892,T=293(2)K。同时也对2种配合物的发光性能进行了测试,测试结果表明2种配合物具有较好的荧光性能。     

钙钛矿光伏电池封装材料与工艺研究进展

钙钛矿太阳能电池作为第3代新概念太阳能电池,具有高光电转换效率、低成本和可柔性加工等优点,近年来发展迅速,其光电转换效率从一开始的3.8%增长到近期的25.5%,逐渐比肩硅电池,已接近商业化应用水平。目前,实现钙钛矿太阳能电池产业应用的关键环节在于电池封装,它不仅可以解决钙钛矿光伏器件稳定性问题,还可以实现电池安全、环保和延长使用寿命等要求。结合近十几年来钙钛矿光伏电池封装材料和封装工艺两方面的发展现状,文中介绍了钙钛矿电池封装领域取得的成果和存在的不足,讨论了目前现有封装技术的优缺点,以及它们适用的不同器件类型。着重在不同温度湿度条件下,比较了不同封装材料性能、封装工艺条件对钙钛矿电池效率及稳定性的影响,归纳出影响钙钛矿电池薄膜封装效果的3个关键因素： 聚合物的弹性模量、水蒸气透过率、加工温度。比较了不同聚合物薄膜封装材料适宜的加工温度、优缺点及加工成本。可以看出,随着钙钛矿光伏电池工业化需求的强烈增长和人们对其封装材料研究的不断深入,研究适合大面积生产和光伏建筑一体化的新型功能聚合物封装材料将是必然趋势。