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Highly selective asymmetric intramolecular selenocyclisation 高选择性不对称分子内硒环化
Pub Date : 1996-03-26 DOI: 10.1039/C39950002321
Y. Nishibayashi, S. Srivastava, H. Takada, S. Fukuzawa, S. Uemura
Asymmetric intramolecular selenocyclisation of alkenoic acids, alkenols and olefinic urethanes using chiral ferrocenylselenenyl cations proceeds smoothly to give the corresponding lactones, cyclic ethers and nitrogen-heterocyclic compounds, respectively, in moderate yields with very high diastereoselectivities.
利用手性二茂铁亚硒烯基阳离子对烯酸、烯醇和烯烃氨基甲酸进行不对称的分子内硒环化反应,分别得到相应的内酯、环醚和氮杂环化合物,产率中等,具有很高的非对映选择性。
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引用次数: 30
An active site model for calcium(II)-containing quinoproteins 含钙藜蛋白的活性位点模型
Pub Date : 1996-02-27 DOI: 10.1039/C39950002077
S. Itoh, Xin Huang, H. Kawakami, M. Komatsu, Y. Ohshiro, S. Fukuzumi
The Ca2+ complexes of PQQ-2, 9-dimethyl ester and its iminoquinone derivative have been synthesised and the reactivity towards alcohols examined; the oxidising ability of the quinone is significantly enhanced by binding Ca2+ and NH3, both of which are essential for quinoprotein methanol dehydrogenase activation.
合成了pqc - 2,9 -二甲酯及其亚氨基醌衍生物的Ca2+配合物,并测定了其对醇的反应性;醌的氧化能力通过与醌蛋白甲醇脱氢酶激活所必需的Ca2+和NH3结合而显著增强。
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引用次数: 7
Spirolides B and D, two novel macrocycles isolated from the digestive glands of shellfish 从贝类消化腺中分离出的两个新的大环
Pub Date : 1996-02-27 DOI: 10.1039/C39950002159
T. Hu, J. Curtis, Y. Oshima, M. Quilliam, J. Walter, W. Watson-Wright, Jeffrey L. C. Wright
Two polar lipid-soluble macrocycles 1 and 2, containing a spiro-linked tricyclic ether ring system and an unusual seven-membered spiro-linked cyclic iminium moiety, have been isolated from the digestive glands of mussels (Mytilus edulis) and scallops (Placopecten magellanicus).
从贻贝(Mytilus edulis)和扇贝(Placopecten magellanicus)的消化腺中分离出两个极性脂溶性大环1和2,它们含有一个螺链三环醚环体系和一个不寻常的七元螺链环亚胺基团。
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引用次数: 178
Synthesis, structures and reactions of new thermally stable silylenes. 新型热稳定硅烯的合成、结构和反应。
Pub Date : 1996-02-20 DOI: 10.1039/C39950001931
B. Gehrhus, M. Lappert, J. Heinicke, R. Boese, D. Bläser
Two representatives 1a and 1b of a new series of stable but reactive bis(amino)silylenes, derived from the N,N′-dineopentyl-1,2-phenylenediamido ligand RC6H3[(CH2But)]2, have been prepared by reductive elimination from RC6H3[[graphic omitted]SiCl2 and characterised by NMR spectroscopy and for 1a X-ray crystallography; the silyienes [graphic omitted](CH2But)]2C6H3-1,2-R (R = H 1a or 4-Me 1b) readily undergo oxidative addition with EtOH or Mel.
从N,N ' -二烯戊基-1,2-苯基二氨基配体RC6H3[(CH2But)]2中,通过还原消除法制备了两个稳定而活泼的双(氨基)硅烯的代表1a和1b,并用核磁共振波谱和1a x射线晶体学对其进行了表征。硅烯[图略](CH2But)]2C6H3-1,2-R (R = H 1a或4-Me 1b)很容易与乙烷或梅尔氧化加成。
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引用次数: 142
Oxidatively induced carbon chain growth at a ditungsten centre 氧化诱导碳链生长在钨中心
Pub Date : 1996-01-01 DOI: 10.1039/CC9960001877
I. Bartlett, N. Connelly, Legge, Antonio Martín, Bernhard Metz, A. Orpen
X-Ray structural and EHMO studies show that two electrons are sequentially removed from a W–W δ* orbital on oxidation of the bis(metallacyclopentadiene) complex [W2(µ-C4Me4)2(η-C5H5)2] to [W2(µ-C4Me4)2(η-C5H5)2]z+(z= 1,2); the dication undergoes C–C coupling and proton loss in boiling MeCN to give [W2(µ-C8Me7CH2)(η-C5H5)2]+ which adds hydride ion to form the metallacyclononatetraene complex [W2(µ-C8Me8)(η-C5H5)2].
x射线结构和EHMO研究表明,双金属环戊二烯配合物[W2(µ-C4Me4)2(η-C5H5)2]氧化为[W2(µ-C4Me4)2(η-C5H5)2]z+(z= 1,2)时,两个电子从W-W δ*轨道上依次移出;该反应在沸腾的MeCN中发生C-C偶联和质子损失,生成[W2(µ-C8Me7CH2)(η-C5H5)2]+,并与氢化物离子形成金属环壬四烯配合物[W2(µ-C8Me8)(η-C5H5)2]。
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引用次数: 2
Redox-induced κ 2 -κ 3 isomerisation in rhodium hydrotris(3,5-dimethylpyrazolyl)borate chemistry: the stabilisation of square-pyramidal rhodium(II) 氧化还原诱导的氢硼酸铑(3,5-二甲基吡唑基)中κ 2 -κ 3异构化化学:方锥体铑的稳定性(II)
Pub Date : 1996-01-01 DOI: 10.1039/CC9960002289
N. Connelly, David J. H. Emslie, Bernhard Metz, A. Orpen, M. J. Quayle
One-electron oxidation of the square-planar, 16-electron complex [Rh(CO)(PPh3)(κ2-Tp′)] with [FeCp2][PF6] gives the square-pyramidal RhII complex [Rh(CO)(PPh3)(κ3-Tp′)][PF6] in which the third pyrazolyl group of Tp′ is N-bound in the axial position by a three-electron two-centre bond (Rh–Naxial 0.13 A longer than Rh–Nbasal).
方形平面16电子配合物[Rh(CO)(PPh3)(κ2-Tp ')]与[FeCp2][PF6]单电子氧化得到方形金字塔状的RhII配合物[Rh(CO)(PPh3)(κ3-Tp ')][PF6],其中Tp '的第三个吡唑基在轴向位置被一个三电子双中心键n键结合(Rh - naxial比Rh - nbasal长0.13 a)。
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引用次数: 24
Tetrahydrophthalic Anhydride and Imide: Remarkably Efficient Partners in Photochemical [2+2] Cycloaddition Reactions With Alkenols and Alkynols 邻苯二甲酸四氢酸酐和亚胺:与烯醇和炔醇进行光化学[2+2]环加成反应的高效伙伴
Pub Date : 1996-01-01 DOI: 10.1039/CC9960000249
K. Booker‐Milburn, J. Cowell, Andrew Sharpe, F. Jiménez
Intermolecular photochemical [2 + 2] cycloaddition of a variety of alken- and alkyn-3-ols with 3,4,5,6-tetrahydrophthalic anhydride (THPA) and the related imide 4 gave the corresponding cyclobutanes and cyclobutenes in high yield, after relatively short irradiation times, with stereoselectivities as high as 10:1 for the cyclobutane examples.
通过分子间光化学[2 + 2]与3,4,5,6-四氢邻苯二酸酐(THPA)和相关的亚胺4进行环加成反应,得到了相应的环丁烷和环丁烯,收率很高,辐照时间较短,以环丁烷为例,立体选择性高达10:1。
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引用次数: 12
Structure and bonding in redox-active d 4 , d 5 , and d 6 alkyne complexes: metal-alkyne moieties as electron sinks 氧化还原活性d4, d5和d6炔配合物的结构和成键:金属-炔部分作为电子汇
Pub Date : 1996-01-01 DOI: 10.1039/CC9960002583
I. Bartlett, N. Connelly, M. J. Quayle, A. Orpen, J. Rankin
X-Ray structural studies of the two redox-related pairs [Cr(CO)2(η-PhCCPh)(η6-C6HMe5)]0/1+ and [Mo(CO)2(η-PhCPh)(Tp′)]0/1+[Tp′= hydrotris(3,5-dimethyl-pyrazolyl)borate] are consistent with the HOMO of the d6, Cr0 alkyne complex being an antibonding M–alkyne π⊥ orbital.
两个氧化还原相关对[Cr(CO)2(η-PhCCPh)(η - c6hme5)]0/1+和[Mo(CO)2(η-PhCPh)(Tp ')]0/1+[Tp ' = hydrotris(3,5-二甲基吡唑基)硼酸盐]的x射线结构研究与d6的HOMO一致,Cr0炔配合物是一个反键m -炔π⊥轨道。
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引用次数: 10
Iron (III) Mediated Oxidative Cyclisations of Cyclopropanone Acetals 铁(III)介导的环丙酮缩醛的氧化环化
Pub Date : 1996-01-01 DOI: 10.1039/CC9960002577
K. Booker‐Milburn, B. Cox, T. Mansley
Treatment of the cyclopropanone acetals 7 or 11 with three different FeIII species gives the lactone 9 and the ester 13 respectively via an oxidative cyclopropane cleavage followed by a 5-exo radical cyclisation–abstraction sequence.
用三种不同的FeIII物质处理环丙酮缩醛7或11,分别通过氧化环丙烷裂解得到内酯9和酯13,然后是5外显子自由基环化提取序列。
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引用次数: 5
Novel catalysts for the carbonylation of methanol 甲醇羰基化反应的新型催化剂
Pub Date : 1995-12-05 DOI: 10.1039/C39950001579
J. Dilworth, John R. Miller, N. Wheatley, M. J. Baker, J. Sunley
Rhodium(I) carbonyl complexes containing phosphino-thiolate and -thioether ligands are almost four times as active in catalysing the carbonylation of methanol to ethanoic acid as the previously known catalyst, [Rhl2(CO)2]–; the crystal structure of one procatalyst, [Rh(SC6H4PPh2)(CO)]2, is reported.
铑(I)羰基配合物含有磷硫酸盐和-硫醚配体,其催化甲醇羰基化制乙醇酸的活性几乎是先前已知催化剂[Rhl2(CO)2] -的四倍;报道了一种原催化剂[Rh(SC6H4PPh2)(CO)]2的晶体结构。
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引用次数: 66
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