过渡金属催化酮的不对称氢化(AH)生产对映体富集的醇是有机化学中的重要反应,在制药和农化领域具有应用。使用地球丰富的、生物相关的钴作为催化剂中的中心金属,具有提高可持续性和实现可扩展的加氢反应的巨大潜力。然而,由于 d 电子数较高,设计具有足以合成实用性和实际可扩展性(≥1 kg 规模)的周转数(TON,≥1000)和对映选择性(≥90%)的钴催化剂仍然是一个挑战。在这项工作中,提出了一种利用氨基(亚氨基)二膦钴(II)溴化物预催化剂的有效催化剂设计策略来实现这一目标。在高达 1.35 kg 的规模下实现了 TON 高达 150,000 且对映体过量 (ee) 高达 99% 的各种仲手性醇的定量生产,表明所提出的钴催化剂在AH 和放大反应。机理研究表明,N-H 官能团和氧化还原活性配体的协同作用赋予钴催化剂高生产率和优异的对映选择性。
accessible tridentate ferrocene-based diamine-phosphine sulfonamide (f-diaphos) ligands were successfully developed for iridium-catalyzedasymmetrichydrogenation of ketones. The f-diaphos ligands exhibited excellent enantioselectivity and superb reactivity in Ir-catalyzed asymmetrichydrogenation of ketones (for arylalkyl ketones, (S)-selectivity, up to 99.4% ee, and 100 000 TON; for diaryl ketones, (R)-selectivity
Composition for film formation and material for insulating film formation
申请人:JSR CORPORATION
公开号:US20020172652A1
公开(公告)日:2002-11-21
A composition for film formation capable of forming a coating film excellent in low dielectric constant characteristics, cracking resistance, modulus of elasticity, and adhesion to substrates and useful as an interlayer insulating film material in semiconductor devices, etc. The composition for film formation contains (A) at least one member selected from an aromatic polyarylene and an aromatic poly (arylene ether), (B) a polyvinylsiloxane, and (C) an organic solvent.
A class of organic polymers exhibiting enhanced ferromagnetic properties are provided. The ferromagnetic polymeric substances comprise a major structural unit
and have a degree of polymerization of at least 10 and a spin concentration of at least about 1 × 10¹⁷/g. The substances are melt-formable into various articles.
Monomer containing electron-withdrawing group and electron-donative group, and copolymer and proton-conductive membrane comprising same
申请人:JSR Corporation
公开号:EP1245554A1
公开(公告)日:2002-10-02
A monomer containing an electron-withdrawing group and an electron-donative group which can be easily controlled in the upper limit of the amount of a sulfonic acid , which impairs the mechanical properties of a copolymer, and can provide a sulfonated polymer that forms a proton-conductive membrane having a high proton conductivity over a wide temperature range, an excellent mechanical strength and an excellent proton conductivity and showing inhibited swelling in hot water and an aqueous solution of methanol, and a copolymer obtained from the monomer. A monomer containing an electron-withdrawing group and an electron-donative group represented by the following general formula (1) :
wherein Y represents a iodine atom, chlorine atom or bromine atom; X represents an electron-withdrawing group; B represents an electron-donative group; and Z represents an aryl group having a specific structure or a monovalent condensed ring hydrocarbon group such as naphthyl group.
一种含有一个抽电子基团和一个负电子基团的单体,该单体可以很容易地控制磺酸的用量上限,而磺酸会损害共聚物的机械性能,并可以提供一种磺化聚合物,该聚合物可以在很宽的温度范围内形成具有高质子传导性、优异的机械强度和优异的质子传导性的质子传导膜,并在热水和甲醇水溶液中表现出抑制溶胀的特性,以及由该单体得到的共聚物。一种单体,含有由下式通式(1)代表的一个电子吸收基团和一个电子疏导基团:
其中 Y 代表碘原子、氯原子或溴原子;X 代表抽电子基团;B 代表弃电子基团;Z 代表具有特定结构的芳基或一价缩合环烃基团,如萘基。