An Unusual Triphenylphosphine Oxide Catalyzed Stereoselective 1,3‐Dichlorination of Unsaturated Ketoesters

An unusual Ph₃PO‐catalyzed stereoselective 1,3‐dicholorination of an unsaturated ketoester has been developed. The novel activation mode involved in this cascade reaction can promote consecutively elusive transformations. The products were obtained with good yields and excellent stereoselectivities. This reaction makes important complementation to the limitations associated with the field of dichlorination.     

Luminescent Mechanochromic Porous Coordination Polymers

Three 2D luminescent isomeric porous coordination polymers are synthesized and characterized. Their luminescence properties can be modified by grinding and they can act as mechanochromic materials and their properties are probably related to the weak interactions of cuprophilicity and π–π interactions.     

Tailoring 3,3′‐Dihydroxyisorenieratene to Hydroxystilbene: Finding a Resveratrol Analogue with Increased Antiproliferation Activity and Cell Selectivity

Four novel compounds were designed by “tailoring” 3,3′‐dihydroxyisorenieratene (a natural carotenoid) based on an isoprene unit retention truncation strategy. Among them, the smallest molecule 1 (2,3,6,2′,3′,6′‐hexamethyl‐4,4′‐dihydroxy‐trans‐stilbene) was concisely synthesized in a one‐pot Stille–Heck tandem sequence, and surfaced as a promising lead molecule in terms of its selective antiproliferative activity mediated by blocking the NCI‐H460 cell cycle in G1 phase. Additionally, theoretical calculations and cell uptake experiments indicate that the unique polymethylation pattern of compound 1 significantly induces a conformational change shift out of planarity and increases its cell uptake and metabolic stability. The observation should be helpful to rationally design resveratrol‐inspired antiproliferative agents.     

用Hirshfeld电荷定量标度亲电性和亲核性:含氮体系(英文)

准确预测化学过程中分子内各原子提供或接受电子的能力以及化学反应可能的位点,即定量确定亲电性、亲核性和区域选择性,是一个十分重要却仍然亟待解决的课题.此前,基于我们新近提出的信息守恒原理,曾建议使用Hirshfeld电荷和信息增益作为两个等价的描述符用于此目的.我们的这个想法已经被成功地应用于两个系列的分子体系,且其有效性得到了充分的验证.然而,先前我们只考察了碳元素的这些性质,所以其结论的普遍性仍存在疑问.我们尚不清楚它是否适用于其他元素,而且对于同一元素的不同价态该结论是否适用也不清楚.为此,本文将考察含氮体系.对5个不同类别的含氮体系共计40个分子进行了研究,其中包括重氮苯、偶氮、重氮、一级和二级胺体系.结果表明,对所有五个含氮体系其Hirshfeld电荷与实验得到的亲电性和亲核性标度之间仍然存在着较强的线性关联.然而,这些相关性却依赖于氮元素的化合价类型和键合环境.该线性关系只能在同一类型中成立.我们对其可能的原因进行了讨论.     

A Borinic Acid Polymer with Fluoride Ion‐ and Thermo‐responsive Properties that are Tunable over a Wide Temperature Range

A new type of smart borinic acid polymer with luminescence and multiple stimuli‐responsive properties is reported. In DMSO with small amounts of water, the homopolymer PBA shows a tunable upper critical solution temperature (UCST). As the amount of water increases from 0 to 2.5 % (v/v), the UCST rises linearly from 20 °C to 100 °C (boiling point of water). Thus, the thermal responsive behavior can be tuned over a wide temperature range. Furthermore, polymer solutions in DMSO show a reversible response to fluoride ions, which can be correlated to the presence of the Lewis acidic borinic acid groups. Upon addition of fluoride, the polymer becomes soluble because the functional R₂BOH groups are converted into ionic [R₂BF₂]^? groups, but turns insoluble again upon addition of H₂O, which reverses this process.     

The Divergent Synthesis of Nitrogen Heterocycles by Rhodium(II)‐Catalyzed Cycloadditions of 1‐Sulfonyl 1,2,3‐Triazoles with 1,3‐Dienes

The first rhodium(II)‐catalyzed aza‐[4+3] cycloadditions of 1‐sulfonyl 1,2,3‐triazoles with 1,3‐dienes have been developed, and enable the efficient synthesis of highly functionalized 2,5‐dihydroazepines from readily available precursors. In some cases, the reaction pathway could divert to formal aza‐[3+2] cycloadditions, thus leading to 2,3‐dihydropyrroles. In this context, the titled reaction represents a capable tool for the divergent synthesis of two types of synthetically valuable aza‐heterocycles from common rhodium(II) iminocarbene intermediates.     

The Assembly‐Disassembly‐Organization‐Reassembly Mechanism for 3D‐2D‐3D Transformation of Germanosilicate IWW Zeolite

Hydrolysis of germanosilicate zeolites with the IWW structure shows two different outcomes depending on the composition of the starting materials. Ge‐rich IWW (Si/Ge=3.1) is disassembled into a layered material (IPC‐5P), which can be reassembled into an almost pure silica IWW on treatment with diethoxydimethylsilane. Ge‐poor IWW (Si/Ge=6.4) is not completely disassembled on hydrolysis, but retains some 3D connectivity. This structure can be reassembled into IWW by incorporation of Al to fill the defects left when the Ge is removed.     

Highly Enantioselective Kinetic Resolution of Axially Chiral BINAM Derivatives Catalyzed by a Brønsted Acid

A highly efficient strategy for the kinetic resolution of axially chiral BINAM derivatives involving a chiral Brønsted acid‐catalyzed imine formation and transfer hydrogenation cascade process was developed. The kinetic resolution provides a convenient route to chiral BINAM derivatives in high yields with excellent enantioselectivities.     

Voltage‐Driven Reversible Insertion into and Leaving from a Lipid Bilayer: Tuning Transmembrane Transport of Artificial Channels

Three new artificial transmembrane channel molecules have been designed and synthesized by attaching positively charged Arg‐incorporated tripeptide chains to pillar[5]arene. Fluorescent and patch‐clamp experiments revealed that voltage can drive the molecules to insert into and leave from a lipid bilayer and thus switch on and off the transport of K⁺ ions. One of the molecules was found to display antimicrobial activity toward Bacillus subtilis with half maximal inhibitory concentration (IC₅₀) of 10 μM which is comparable to that of natural channel‐forming peptide alamethicin.     

Catalytic Ethanolysis of Kraft Lignin into High‐Value Small‐Molecular Chemicals over a Nanostructured α‐Molybdenum Carbide Catalyst

We report the complete ethanolysis of Kraft lignin over an α‐MoC_1?x/AC catalyst in pure ethanol at 280 °C to give high‐value chemicals of low molecular weight with a maximum overall yield of the 25 most abundant liquid products (LP25) of 1.64 g per gram of lignin. The LP25 products consisted of C₆–C₁₀ esters, alcohols, arenes, phenols, and benzyl alcohols with an overall heating value of 36.5 MJ kg^?1. C₆ alcohols and C₈ esters predominated and accounted for 82 wt % of the LP25 products. No oligomers or char were formed in the process. With our catalyst, ethanol is the only effective solvent for the reaction. Supercritical ethanol on its own degrades Kraft lignin into a mixture of small molecules and molecular fragments of intermediate size with molecular weights in the range 700–1400, differing in steps of 58 units, which is the weight of the branched‐chain linkage C₃H₆O in lignin. Hydrogen was found to have a negative effect on the formation of the low‐molecular‐weight products.