亚甲胺叶立德参与的[3＋2]环加成反应的最新进展

综述了亚甲胺叶立德的制备、它参与的[3＋2]环加成反应的反应机理、反应选择性及在天然产物全合成中的应用等方面的最新进展.     

Application of Cyclopentadiene and its Derivatives in Natural Product Synthesis

Approaches toward the synthesis of iridoids and 9-isocyanopupukeanane starting from cy-clopentadiene are discussed.     

Photocrosslinking of functionalized rubber. II. Photoinitiated cationic polymerization of epoxidized liquid natural rubber

Low molecular weight epoxidized natural rubber has been crosslinked within seconds by UV irradiation in the presence of a triarylsulfonium salt. The photoinitiated cationic ring-opening polymerization was studied quantitatively by infrared spectroscopy and shown to proceed with surprisingly long kinetic chains in such solid medium. The high conversion (60%) needed for complete insolubilization, together with the presence of tetrahydrofuran structures, argue in favor of an intramolecular polymerization process involving neighboring epoxy groups. The photoinitiator concentration has a strong influence on the rate and extent of the reaction, as well as on the depth of cure profile. Because of an efficient dark process, close to 100% conversion was reached upon storage of the irradiated elastomer at ambient, with a concomitant increase of the gel fraction and the polymer hardness. The grafting of pendent acrylate groups onto the polymer chain leads to a three-fold decrease of the initial rate of polymerization of the epoxide. The photocuring of natural rubber bearing both epoxy and acrylate groups generates a dual polymer network which combines the properties of the two moieties. © 1995 John Wiley & Sons, Inc.     

2003～2011年中国科普法规政策与化学普及书籍关系研究

2002年中国颁布科普法后,2003至2011年出版的化学普及书籍种数总体呈上升趋势。出版地和出版社总体上较为分散,局部集中度高。主题上基础知识类化学普及书籍最多,科学文化类次之,实用知识类较少,化学前沿类最少。涉及科普的一般法律、法规和政策对化学普及书籍的创作影响甚微。只有与国家约束性社会发展指标相关,发生涉及公民生命安全的重大社会事件,针对特定人群的具体实施政策出台,科普法规和政策才对化学普及书籍的出版起到推动作用。     

内蒙古地区天然植物沙棘果中黄色素的提取工艺及性质研究

以内蒙古地区沙棘果实为原料，研究了提取黄色素的工艺条件，同时对该色素的性质进行了初步探讨。结果表明，以95％的乙醇溶液作浸提剂，提取的黄色素浓度最高，工艺流程简单易行，且无毒，无污染。对提取的黄色素进行的性质试验表明，沙棘黄色素对光、热具有较好的稳定性，适用于酸性或弱碱性的食品中，葡萄糖、氧化剂(H2O2)、还原剂(Na2SO3)等食品添加剂均无明显影响以上结果为这种优良天然色素的开发与应用提供了参考。     

3-Chloropropyltrialkoxysilanes—Key Intermediates for the Commercial Production of Organofunctionalized Silanes and Polysiloxanes

Silicon and carbon may be looked upon as the two fundamental antipodes with respect to the naturally occurring forms of matter and life on earth: Silicon plays the key role in the “petrification” of inanimate matter, while carbon is the representative element for the “incarnation” of living organisms. If a scientist were to search for a highly efficient method of uniting inorganic and organic matter, he would, at a very early stage of attempting to solve this problem, combine these two natural principles of matter and think of “bireactive” molecules containing a silicon functionality for bonding to inorganic material on the one hand and a carbon functionality for anchoring to an organic counterpart on the other. The title compounds and their derivatives epitomize such molecules: they are wanderers between both (chemical) worlds. Owing to their bifunctionality they are capable of binding to inorganic (especially siliceous) systems as well as to organic polymers. Whether their commercial application concerns the strengthening of polyester resins with glass fibers for use in boatbuilding or the incorporation of silica as a filler in rubber mixtures for the manufacture of wear-resistant tires or even the immobilization of enzymes on glass spheres for carrying out reactions in enzyme reactors—in all cases organofunctionalized silanes guarantee a reliable and permanent union between two otherwise “incompatible” material systems.     

Final elucidation of the absolute configuration of the signal metabolite hormaomycin

The complete absolute configuration of hormaomycin 1 a has been established by HPLC and HPLC/MS experiments with appropriately derivatized 4-propylprolines, (2S,4S)-6 and (2R,4R)-6, as well as 4-(Z)-propenylprolines, cis-5 and trans-5, and also feeding experiments with enantiomerically pure samples of the deuterium-labeled 3-(2'-nitrocyclopropyl)alanine, (2S)-3,3-[D2]15 and (2S)-2,2'-[D2]15, and 4-(Z)-propenylproline 2',4-[D2]-(2S,4R)-5. The latter five amino acids were prepared for the first time and allowed one to unequivocally assign the hitherto unknown absolute configurations of the last four stereocenters in hormaomycin 1 a. As a bonus, some new information about the biosynthesis of this molecule has also been gathered.     

A facile synthesis of (6S,1′S)-(+)-hernandulcin and (6S,1′R)-(+)-epihernandulcin

A facile total synthesis of (+)-hernandulcin (1) was accomplished from (−)-isopulegol in 6 steps with 15% overall yield. Epoxidation of (−)-isopulegol with m-chloroperbenzoic acid followed by opening of the epoxide 3a with prenyl Grignard afforded the tertiary alcohol 4a with correct C-6 and C-1′ stereochemistry as a major product. Oxidation of the secondary alcohol in compound 4a to the ketone 5a was accomplished in high yield by using TPAP and N-methylmorpholine N-oxide. Conversion of the ketone 5a to α,β-unsaturated ketone via organoselenium intermediate gave (+)-hernandulcin (1). This method was also successfully applied to the synthesis of (+)-epihernandulcin (2).     

CAST/CNMR: highly accurate C NMR chemical shift prediction system considering stereochemistry

Accurate, practical prediction of ¹³C NMR chemical shifts has been achieved with a new system, CAST/CNMR, taking account of stereochemistry. The CAST/CNMR system has solved the critical problem of the accurate distinction of differences and similarities in stereochemical structures around a specific carbon, which has not yet been achieved by any other database-oriented system for prediction of ¹³C NMR chemical shifts. CAST/CNMR uses a three-dimensional structural database together with a ¹³C NMR spectral database. Absolute/relative configurational and conformational structural information are described by the CAST (CAnonical-representation of STereochemistry) coding method. This paper provides an overview of the CAST/CNMR system, and describes its application to two natural products as examples.     

Air-Segmented Continuous-Flow Analysis for Molybdenum in Various Geochemical Samples

 An air-segmented continuous-flow method has been developed for the determination of molybdenum at ultra trace levels using the catalytic effect of molybdate during the oxidation of L-ascorbic acid by hydrogen peroxide. Incorporation of an on-line ion exchange column improved the tolerance limit for various ions. The detection limits with and without the column were 64 pmol L⁻¹ and 17 pmol L⁻¹, and the reproducibilities at 10 nmol L⁻¹ were 2.1% and 0.2%, respectively. The proposed method was applied to the determination of molybdenum in seawater and lake water as well as in rock and sediment samples. This method has the highest sensitivity among the available literature to our knowledge, and is also convenient for routine analysis of molybdenum in various natural samples. Author for correspondence. E-mail: masahito.sugiyama@ sojin0206.mbox.media.kyoto-u.ac.jp Received October 23, 2002; accepted January 28, 2003 Published online May 19, 2003