巻号一覧
67 巻, 5 号
選択された号の論文の12件中1～12を表示しています
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巻頭言
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宮浦 憲夫2009 年 67 巻 5 号 p. 435
発行日: 2009/05/01
公開日: 2011/11/14
ジャーナル オープンアクセスPDF形式でダウンロード (175K)
総説および総合論文
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西林 仁昭, 三宅 由寛, 植村 榮2009 年 67 巻 5 号 p. 437-450
発行日: 2009/05/01
公開日: 2011/11/14
ジャーナル 認証ありOur recent studies on catalytic reactions via ruthenium-allenylidene complexes are reviewed from the viewpoint of organic synthesis. Thiolate-bridged diruthenium complexes work as efficient catalysts to promote a variety of novel organic transformations, especially propargylic substituion reactions, via allenylidene complexes as key intermediates. The asymmetric version of these reactions is also described together with some mononuclear ruthenium complex-catalyzed related reactions by other groups.抄録全体を表示PDF形式でダウンロード (783K) -
鈴木 俊彰, 張 文雄, 西浦 正芳, 侯 召民2009 年 67 巻 5 号 p. 451-464
発行日: 2009/05/01
公開日: 2011/11/14
ジャーナル 認証ありHalf-sandwich rare-earth metal alkyl complexes bearing the silylene-linked cyclopentadienyl-amido ligand can serve as efficient catalyst precursors for the catalytic (Z)-selective head-to-head dimerization of terminal alkynes to give the corresponding conjugated (Z)-enynes, which represents the first example of exclusive formation of a (Z)-enyne compound in the dimerization of an aromatic alkyne. They also work for the catalytic addition of terminal alkyne C-H, amine N-H, and phosphine P-H bonds to carbodiimides (R'N=C=NR'), to give a new family of propiolamidines, guanidines, and phosphaguanidines, respectively, some of which were difficult to prepare previously. The half-sandwich rare-earth-catalyzed cross-coupling of terminal alkynes with isocyanides affords selectively the corresponding (Z)-1-aza-1, 3-enyne pro-ducts for the first time. Mechanistic aspects of these catalytic processes are also described.抄録全体を表示PDF形式でダウンロード (659K) -
村瀬 隆史, 藤田 誠2009 年 67 巻 5 号 p. 465-474
発行日: 2009/05/01
公開日: 2011/11/14
ジャーナル 認証ありPd(II)-linked hollow complexes with nanometer-sized cavities provide new reaction media that are quite different from bulk solution and solid states. Guest molecules encapsulated within the hollow complexes showed unusual reactivities because preorganization in the cavity dramatically reduces the entropy cost of the reactions. Rate acceleration, high regio- and stereoselectivities, enantioselectivity, pairwise selectivity, and reaction pathway control are observed in a variety of organic transformations (for example, Diels-Alder additions, [2+2] photoadditions, radical additions, and photooxidations) as a consequence of precise preorganization of the encapsulated substrates. Unstable reactive intermediates are also stabilized within the complexes.抄録全体を表示PDF形式でダウンロード (1532K) -
高尾 俊郎, 鈴木 寛治2009 年 67 巻 5 号 p. 475-485
発行日: 2009/05/01
公開日: 2011/11/14
ジャーナル 認証ありThe reactivity of transition metal cluster complexes has been of special interest in these days in the area of organometallic chemistry, owing to their capability of activating substrates through the cooperative effects of multiple metal centers. Unique reactivity of the transition metal clusters likely stems from their ability for multiple coordination of the substrate to the metal centers and the multi-electron transfer between the substrate and the cluster. Thus far, we have demonstrated numbers of examples of cooperative activation through extending the reaction chemistry of di- and triruthenium polyhydrido complexes, [(C5Me5)Ru]2(μ-H)4 and [(C5Me5)Ru]3(μ-H)2(μ3-H)2 (1). We report herein the remarkable shape-selectivity observed in the reactions of 1 with acyclic and cyclic 1,3-dienes and unusual skeletal rearrangements of trinuclear ruthenacyclic complexes including carbon-carbon bond scission/formation steps induced by the cooperative action of the adjacent metal centers.抄録全体を表示PDF形式でダウンロード (977K) -
竹田 浩之, 石谷 治2009 年 67 巻 5 号 p. 486-493
発行日: 2009/05/01
公開日: 2011/11/14
ジャーナル 認証ありHighly efficient photocatalytic CO2 reduction using metal complexes, particularly rhenium(I) bipyridine complexes, is reviewed. Importance about development of such CO2 reduction photocatalysts is explained from the points of both problems with global warming and shortage of fossil fuels. Recent progress in photocatalysts for CO2 reduction has been achieved using the following systems and methods: (1) introduction of a phosphine ligand to rhenium(I) mononuclear complexes, (2) a mixed system of two rhenium(I) complexes, of which quantum yield for CO2 reduction reaches up to 59%, (3) introduction of interligand weak (π-π and CH-π) interaction into rhenium(I) complexes, and (4) supramolecular photocatalysts constructed with both Ru(II) and Re(I) complexes, which can efficiently use a wide range of visible light.抄録全体を表示PDF形式でダウンロード (461K) -
大嶋 孝志, 岩崎 孝紀, 真島 和志2009 年 67 巻 5 号 p. 494-506
発行日: 2009/05/01
公開日: 2011/11/14
ジャーナル 認証ありOver the last few decades, the quest for environmentally benign chemical transformations has become an important topic in both industrial and academic research. We developed several highly atom-economical direct reactions, such as direct conversion of esters to oxazolines and transesterification, catalyzed by μ4-oxo-tetranuclear zinc cluster Zn4(OCOCF3)6O (1b). Because the reaction conditions are almost neutral, various acid-sensitive functionalities (THP ether, TES ether, Boc carbamate, and so on) persisted and no epimerization of α-position of ester occurred. The most attractive highlight of the zinc cluster catalysis is that hydroxyl groups are selectively acylated in the presence of primary and secondary aliphatic amino groups. Such advantageous catalytic performance is due to assembled metal ions that serve as a functional model of metalloenzyme containing more than two metal ions, but different from mononuclear catalysts and other previously reported catalysts.抄録全体を表示PDF形式でダウンロード (837K) -
生越 専介2009 年 67 巻 5 号 p. 507-516
発行日: 2009/05/01
公開日: 2011/11/14
ジャーナル 認証ありMany nickel-catalyzed transformations via a hetero-nickelacycle have been reported, in which two different key reaction steps to generate a hetero-nickelacycle from nickel(0) species have been proposed. One proposed reaction is oxidative cyclization of two π-components with nickel(0) complex to give five-membered hetero-nickelacycles. The other type of reaction to generate a hetero-nickelacycle is the oxidative addition of cyclopropyl ketones and cyclopropyl imines to give six-membered hetero-nickelacycles, which has also been proposed as an important key step in nickel-catalyzed [3+2] cycloaddition reactions to give cyclopentane derivatives. We report here oxidative cyclization reactions of carbon-carbon unsaturated compounds and aldehyde, ketone or imine with nickel(0). These reactions have been proposed as an important key step in multicomponent-coupling reactions as well as [2+2+2] cycloaddition reactions. Oxidative addition of a cyclopropyl ketone to nickel(0) to give a dihydronickelapyran and its role in a catalytic reaction is also discussed in this paper.抄録全体を表示PDF形式でダウンロード (435K) -
櫻井 英博, 佃 達哉2009 年 67 巻 5 号 p. 517-528
発行日: 2009/05/01
公開日: 2011/11/14
ジャーナル 認証ありAu clusters smaller than 2nm and stabilized by poly(N-vinyl-2-pyrrolidone) (Au:PVP) show higher activity for aerobic oxidation such as alcohol oxidation, α-hydroxylation of benzylic ketones, and homo-coupling of organoboronates as well as for non-oxidative (formal Lewis acidic) reactions including intramolecular hydroalkoxylation/amination of non-activated alkenes. Physical measurements revealed that the catalytically active Au clusters are negatively charged by electron donation from PVP, and the catalytic activity is enhanced with increasing negative charge on the Au core. Partial electron transfer from the anionic Au clusters of Au:PVP into the LUMO (π*) of O2 generates superoxide- or peroxide-like species and the Lewis acidic center, both of which play an important role in the above catalytic activity.抄録全体を表示PDF形式でダウンロード (2616K) -
小澤 文幸2009 年 67 巻 5 号 p. 529-539
発行日: 2009/05/01
公開日: 2011/11/14
ジャーナル 認証ありThis account paper describes our recent studies on organotransition metal complexes coordinated with 1,2-diaryl-3,4-diphosphinidenecyclobutenes (DPCB-Y). The DPCB-Y ligands with two P=C double bonds bear extremely low-lying π* orbitals mainly located around phosphorus atoms and have a marked tendency to engage in metal to phosphorus π-back-bonding. It has been found that this property is useful for catalysis, leading to highly efficient organic transformations with hitherto unknown reactivities and selectivities. Detailed catalytic mechanisms are reported for hydroamination of 1,3-dienes with aniline, dehydrative allylation of aniline and active methylene compounds with allylic alcohols, and (Z)-selective hydrosilylation of terminal alkynes.抄録全体を表示PDF形式でダウンロード (859K) -
松本 剛, 大木 靖弘, 巽 和行2009 年 67 巻 5 号 p. 540-553
発行日: 2009/05/01
公開日: 2011/11/14
ジャーナル 認証ありHydrogenases catalyze reversible oxidation/reduction of molecular-hydrogen/protons in nature, and the enzymes are classified into three groups, namely, the [NiFe], [FeFe], and [Fe] hydrogenases. We herein summarize our structural and functional model studies on the [NiFe] hydrogenase. A seires of (OC)3Fe(II)-Ni(II), (OC)2(NC)2Fe(II)-Ni(II), and (OC)(NC)2Fe(II)-Ni(II) complexes bridged by thiolato ligands have been synthesized as models of the [NiFe] hydrogenase active site. The investigations of dihydrogen activation at the chalcogenido bridged Ge-Ru and W-Ru complexes, and coordinatively unsaturated Ir and Rh thiolato complexes provide clues to understand the mechanism of the [NiFe] hydrogenase function.抄録全体を表示PDF形式でダウンロード (589K)
十字路
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西林 仁昭, 三宅 由寛, 高尾 俊郎, 鈴木 寛治, 大嶋 孝志, 真島 和志, 佃 達哉, 櫻井 英博2009 年 67 巻 5 号 p. 554
発行日: 2009/05/01
公開日: 2011/11/14
ジャーナル オープンアクセスPDF形式でダウンロード (143K)
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