有機合成化学協会誌

クロスカップリング：日本生まれ、日本育ちの反応

公開日: 2026/03/06 更新日: 2026/03/06

日本で生まれたクロスカップリングは、錯体化学と有機合成化学の融合に始まり、さまざまな元素を活かしながら発展し、新薬や高機能材料を生み出す実用的な技術となってノーベル化学賞へとつながりました。その成果は今も世界を魅了し続けています。
（編者一同）

24件中1～20件の論文を表示しています

38 巻 (1980) 12 号 p. 1142-1150 公開日: 2026/03/06
炭素官能基供与剤としての有機スズ化合物
小杉正紀, 右田俊彦

Recent progress of carbon-carbon bond formation via organotin compounds is described. These reactions can be devided roughly into two categories, that is, substitution of organic halides and addition of carbonyl compounds. Among the organotin compounds, allyl-, vinyl-, ethynyl-, and phenyl-trialkyltin are promising reagents.
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41 巻 (1983) 9 号 p. 827-838 公開日: 2026/03/06
有機ニッケル, パラジウム, 白金錯体
山本明夫, 山本隆一, 小沢文幸

Organometallic complexes of nickel, palladium and platinum play important roles in organic synthesis. An overview of preparative methods of the organonickel, -palladium and -platinum complexes are presented. The thermolysis mechanisms of these complexes and reactions with carbon monoxide are described in detail.
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43 巻 (1985) 5 号 p. 419-428 公開日: 2026/03/06
光学活性アリルシランの合成と反応
林民生

Optically active allylsilanes (up to 95 %ee) which contain an asymmetric carbon atom directly bonded to the silicon atom have been prepared by asymmetric cross-coupling of α- (trimethylsilyl) - benzyl or 1- (trialkylsilyl) ethyl Grignard reagent with alkenyl bromides in the presence of a chiral ferrocenylphoshine-palladium complex ((R) - (S) -PPFA-Pd) as a catalyst. Palladium-catalyzed asymmetric hydrosilylation of 1, 3-dienes also gave optically active allylsilanes. Reaction of the allylsilanes with various electrophiles (t-BuCl/TiCl₄, MeCOCl/AlCl₃, trioxane/TiCl₄, CF₃COOD, MCPBA, and palladium (II)) was found to proceed with anti stereochemistry, the electrophiles attacking the double bond selectively anti with respect to the leaving trimethylsilyl group. Reaction of the optically active allylsilanes with aldehydes in the presence of titanium chloride gave optically active erythro homoallylic alcohols with over 90 % enantio- and diastereoselectivities.
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46 巻 (1988) 9 号 p. 848-860 公開日: 2026/03/06
パラジウム触媒を用いるアリールおよびビニル型ホウ素化合物と有機ハロゲン化物のクロスカップリング反応
宮浦憲夫, 鈴木章

A general and convenient method for the stereo-and regioselective synthesis of conjugated alkadienes, alkenynes, arylated alkenes, and heterobiaryls is described. The reaction of (E) -or (Z) -1-alkenylboronates obtainable by hydroboration, with either (E) -or (Z) -1-alkenyl halides in the presence of a catalytic amount of tetrakis (triphenylphosphine) palladium and bases such as sodium alkoxides gives the corresponding (E, E) -, (E, Z) - (Z, E) -and (Z, Z) -alkadienes stereo-and regioselectively, while retaining the configuration of both the starting alkenylboronates and haloalkenes The similar reactions of (E) -and (Z) -1-alkenylboronates with 1-alkynyl, aryl, allylic, and benzylic halides also provide the corresponding couplig products stereosoelectively. The versatility of this method has been demonstrated by the synthesis of some natural products bearing conjugated alkadiene structures. The reaction of arylboronic acids with aryl halides to give unsymmetrical biaryls is also presented. A mechanism of this cross-coupling reaction, which involves the transmetallation between a 1-alkenylborane and an alkoxopalladium (II) complex generated through the metathetical displacement of a halogen atom of RPd (II) X with sodium alkoxide, is proposed.
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47 巻 (1989) 1 号 p. 2-10 公開日: 2026/03/06
ジルコニウムを用いる有機合成-その後の展開
根岸英一, 高橋保

Alkenylzirconium compounds react with various organic halides in the presence of a palladium or nickel catalyst to give the corresponding cross-coupling products in high yields with high selectivities. Carbometallation of alkynes using alkylaluminums such as trimethylaluminum is catalyzed by zirconocene dichloride. The triisobutylaluminum/zirconocene dichloride system induces hydrometallation and subsequent carbometallation of enynes to afford exocyclic olefins. Addition of 2 equiv. of n-butyllithium to zirconocene dichloride conveniently produces a zirconocene equivalent, i.e., “Cp₂Zr”, which can induce bicyclization of enynes or diynes. Reactions of alkenes and alkynes with the zirconocene give zirconocene-alkene and-alkyne complexes, respectively, whose structures have been determined by X-ray studies. Novel 1, 2-migration reactions on zirconium or other metals are also discussed.
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48 巻 (1990) 9 号 p. 834-843 公開日: 2026/03/06
有機ケイ素化合物/F^〓/Pd触媒による高選択的交差カップリング反応
畠中康夫, 檜山爲次郎

Highly selective cross-coupling reaction of organosilanes with organic halides and organic triflates promoted by palladium catalyst and fluoride ion is described. Organosilicon compounds like (E) - or (Z) -alkenyl, alkynyl, allyl, and arylsilanes smoothly react with alkenyl, allyl and aryl halides to give coupled products with high chemoselectivity and stereospecificity. Under similar conditions, silylation of alkenyl iodides by hexa-methyldisilane and methylation of aryl iodides by (Et₂N)₃S⁺Me₃SiF₂^- take place. The one-pot double cross-coupling of trimethylstannyl (trimethylsilyl) acetylene with two alkenyl iodides is achieved to afford isomerically pure dienynes. The cross-coupling of chiral 1-phenyl-1-trifluorosilylethane with aryl triflates occurrs stereo-specifically, providing optically active coupled products. The stereochemistry of the products is influenced decisively by reaction temperature and solvent used. A transition state model for the transmetallation step in catalytic cycle is proposed on the basis of substituent effect and stereochemical study of this reaction.
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49 巻 (1991) 1 号 p. 63-70 公開日: 2026/03/06
有機金属化学
山本明夫

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50 巻 (1992) 9 号 p. 826-837 公開日: 2026/03/06
不斉Heck反応による多環式化合物の触媒的不斉合成
柴崎正勝, 佐藤美洋, 影近克治

In 1989, we succeeded in demonstrating the first example of an asymmetric Heck reaction. Treatment of the prochiral alkenyl iodide 4 b with Cl₂Pd (R) -BINAP (10 mol%), Ag₃PO₄ (2 molar equiv) and CaCO₃ (2.2 molar equiv) in 1-methyl-2-pyrrolidinone produced the cis-decalin derivative 8 b with 80% ee. The result suggested that the presence of a silver salt produced the Pd⁺ intermediate 11 with 16-electron configuration by abstraction of I^- to result in the formation of 8 b with high ee. Under the similar conditions, the cis-decalin derivative 18 of 92% ee and the cis-hydrindan derivative 26 a of 86% ee were obtained from the corresponding alkenyl iodides, respectively, On the other hand, it was found that treatment of the prochiral alkenyl triflate 19 d with Pd (OAc) ₂ (5 mol%), (R) -BINAP (10 mol%) and K₂CO₃ (2 molar equiv) in toluene gave 8 d in 91% ee. Furthermore, 27 was cyclized to 26 b in 73% ee under the similar conditions, which was successfully transformed into the key intermediate 34 for oppositol. An asymmetric Heck reaction was also useful for the synthesis of polycyclopentanoids. Thus, the prochiral alkenyl triflate 59 was treated with 1.7 mol% of Pd (0Ac) ₂, 2.1 mol% of (S) -BINAP and 1.7 equiv of tetrabutylammonium acetate in DMSO afforded the cyclopentanoid 60 of 80% ee in 89% yield. The reaction was found to be useful as well for the capture by a C-centered nucleophile instead of tetrabutylammonium acetate, giving 68 c of 80% ee in one-step from 59. The cyclopentanoid 60 was converted to 43 in a seven-step process, which is a key synthetic intermediate for capnellenols.
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51 巻 (1993) 2 号 p. 141-156 公開日: 2026/03/06
パラジウム触媒を用いる新しいタイプの重合反応
鈴木将人

It has been well documented that palladium complexes catalyze versatile and useful reactions. Contemplation of these reactions from the standpoint of polymer synthesis has brought new polymerizations, which are reviewed in this article including topics of ring-opening polymerization, polycondensation, polyaddition, and addition polymerization. 1) A new type of ring-opening polymerization, whose key intermediates were π-allyl palladium complexes, was developed. Especially, for the polymerization of cyclic carbamates was designed and achieved an unusual mode that propagating ends multiply at every step of propagation. The produced polyamines had hyperbranched dendritic structures incorporating the initiator as the core. 2) Aromatic polymers such as poly (phenylene vinylene) s, polyphenylenes, and polyamides were prepared by the Heck reaction and Pd-catalyzed cross-coupling reactions. 3) Electrophilic palladium complexes initiated vinyl polymerizations of styrene, methyl propiolate, norbornene, etc. as well as alternating copolymerizations of some alkenes with carbon monoxide. Bromo (methyl) palladium-phosphine complexes initiated living aromatization polymerizations of 1, 2-diisocyanoarenes. 4) A cyclic compound having a Si-Si bond, 1, 2-disilacyclopentane, was polymerized with the aid of a Pd (0) complex.
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51 巻 (1993) 9 号 p. 794-803 公開日: 2026/03/06
遷移金属触媒を用いる縮合系高分子の合成
今井淑夫, 米山賢

Recent studies on the synthesis of condensation polymers by using transition metal catalysts such as palladium, nickel, ruthenium, and others are reviewed from a viewpoint of new synthetic methods for condensation polymers. This article deals with the following subjects : 1) Pd-catalyzed carbon-carbon coupling polycondensation, 2) Pd- or Ni-catalyzed polycondensation via transmetallation, 3) Pd-catalyzed carbonylation polycondensation, 4) polycondensation via π-allyl Pd intermediates, 5) Ni-catalyzed aromatic homocoupling polycondensation, 6) Ru-catalyzed polycondensation, and 7) polycondensation using other transition metal catalysts.
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51 巻 (1993) 11 号 p. 1043-1052 公開日: 2026/03/06
遷移金属触媒下における有機ホウ素化合物の反応
鈴木章, 宮浦憲夫

The cross-coupling reaction of organoboron compounds with organic halides, the catalytic hydroboration of alkenes and alkynes with catecholborane, and the thioboration reaction of alkynes with 9-organothio-9-bora-bicyclo [3.3.1] nonanes are described. The palladium-catalyzed cross-coupling reaction of organoboron compounds provides a general and convenient method for the synthesis of stereodefined alkenes, alkadienes or alkenynes, biaryls, and vinylic sulfides. The similar coupling reaction under carbon monoxide (1 atm) produces alkyl vinyl ketones, alkyl aryl ketones, alkyl alkyl ketones and biaryl ketones in exellent yields. The hydroboration of alkenes and alkynes with catecholborane can proceed under very mild conditions with the use of Rh, Pd, or Ni catalysts. It is also observed that catalysts can direct the course of the addition of borane to different regio- or stereoselectivity, compared with uncatalyzed reactions. The reaction is extended to the cis-addition of RS-B compounds to terminal alkynes with the use of Pd (PPh₃)₄.
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51 巻 (1993) 11 号 p. 1053-1063 公開日: 2026/03/06
パラジウム触媒によるsp炭素-sp²炭素結合形成反応
薗頭健吉, 高橋成年

Catalytic carbon-carbon bond formation is one of the most important reaction for constructing organic molecules. A two-component system containing palladium and copper effectively catalyzes a carbon-carbon coupling between sp²- and sp-carbons to give conjugated ene-yne compounds and aromatic acetylenes. This article reviews recent development of the palladium-catalyzed sp²-sp carbon-carbon coupling and its application to the synthesis of functional materials such as bioactive compounds, π-conjungated compounds, and liquid crystals.
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52 巻 (1994) 11 号 p. 956-967 公開日: 2026/03/06
Asymmetric Heck Reaction : Catalytic Asymmetric Syntheses of Bioactive Molecules
Masakatsu Shibasaki, Mikiko Sodeoka

The asymmetric Heck reaction, which we achieved for the first time several years ago, has been successfully applied to catalytic asymmetric syntheses of many bioactive molecules such as vernolepin, γ-butyrolactone derivatives, eptazocine, a halenaquinol skeleton and lentiginosine.
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56 巻 (1998) 2 号 p. 96-106 公開日: 2026/03/06
触媒活性種モデルとしての有機パラジウム錯体の合成と反応性
榧木啓人, 山本明夫

Various neutral and cationic monoorganopalladium complexes have been prepared as models of active species involved in palladium-catalyzed catalytic processes. Removal of a halide ligand from monoalkyl- and arylpalladium halide complexes by treatment with a silver salt afforded cationic monoorganopalladium complexes coordinated with a solvent molecule at the vacant site of the cationic palladium center. Generation of the vacant site has been found to be a dominant factor in enhancing the reactivities of organopalladium complexes toward β-hydrogen elimination from alkylpalladium complexes as well as CO and olefin insertions into palladium-carbon bond. Further addition of the silver salt was found to accelerate the CO insertion rate by removing a phosphine ligand from the palladium complexes. Cationic solvent-coordinated Pd (II) complexes also proved to be suitable model compounds for studying the mechanism of nucleophilic attack on coordinated CO. Utility of the concept of the reactivity enhancement by creation of a vacant cationic center at palladium has been demonstrated in catalytic double carbonylation of aryl and allyl halides with a secondary amine to give α-keto amides.
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57 巻 (1999) 4 号 p. 305-312 公開日: 2026/03/06
有機遷移金属錯体のトランスメタル化反応-均一系触媒反応機構との関連について
小坂田耕太郎, 山本隆一

Transmetallation, generating organotransition metal species from alkylating reagent and metal complexes, plays important roles in many synthetic organic reactions catalyzed by transition metal complexes. This article describes recent progress in mechanistic study on the transmetallation and in elucidation of its relevance to synthetic organic reactions catalyzed by transition metal complexes. Pd complex catalyzed cross-coupling reactions of aromatic halides with organomagnesium and organotin reagents and with terminal alkynes involve transmetallation of alkyl and alkynyl group from the non-transition or transition metal compounds to Pd complexes. Ni (0) complex promoted dehalogenative condensation of aryl halides in DMF occurs via disproportionation of bromo (aryl) nickel (II) complexes to form diarylnickel complex which is responsible for reductive elimination of biaryls. Mechanisms of isomerization between cis- and trans-diarylpalladium complexes having auxiliary thioether ligand and of conproportionation of diorgano- and dichloro-complexes of group 10 metals are discussed.
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58 巻 (2000) 8 号 p. 718-727 公開日: 2026/03/06
分子内Heck反応による4級炭素の触媒的不斉構築
足森厚之, オーバーマンラリー・E

Within the last decade, the enormous synthetic potential of the Heck reaction has been revealed. When employed intramolecularly, Heck reactions succeed in even forming quaternary carbon centers. The ability of intramolecular Heck reactions to reliably fashion carbon-carbon bonds in polyfunctional molecules has led to wide application of this reaction at the strategy level for the synthesis of complex natural products. One of the most important developments in this area is the increasing success being realized in effecting catalytic asymmetric Heck reactions using enantiopure ligands. Although only modest enantiocontrol was achieved in early stages, many asymmetric Heck reactions have now been demonstrated that proceed with >90% ee. Another development of the Heck reaction has led to greater understanding of its mechanistic details with two distinct pathways, the neutral and cationic pathways, being recognized. This review summarizes the synthetic developments of the intramolecular asymmetric Heck reaction for forming quaternary carbon centers and the mechanistic factors recently revealed to effect enantioselectiv- ity.
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62 巻 (2004) 4 号 p. 355-362 公開日: 2026/03/06
実用的なアルキンのカップリング法
森敦紀

The author describes herein several coupling reactions of terminal alkynes with organic halides, which protocols are recently developed in the author's group. Use of new activators such as silver (I) oxide, tetrabutylammonium fluoride (TBAF), several quaternary ammonium hydroxides, and aqueous ammonia constitute a practical synthetic strategy for the introduction of carbon-carbon triple bond moieties into organic molecules.
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62 巻 (2004) 12 号 p. 1192-1204 公開日: 2026/03/06
遷移金属触媒を用いるハロゲン化アルキル類と有機金属試薬とのクロスカップリング反応
寺尾潤, 神戸宣明

Cross-coupling reaction of organic halides with main group organometallic reagents has now become one of the most practical and reliable methods for constructing C-C bonds in organic synthesis. During the last three decades numbers of such reactions using organic halides bearing C (sp²) -X bond have been developed by the aid of transition-metal catalysts, especially Pd and Ni. On the other hand, the use of alkyl halides in transition-metal catalyzed cross-coupling reaction had not well been developed until quite recently. This is probably due to the low reactivities of alkyl halides toward oxidative addition and also to undesirable facile β-elimination from alkylmetal intermediates. Since several years ago, however, some significant methodological evolutions to overcome these difficulties have been achieved by tuning up the ligands and/or constructing novel catalytic systems based on new mechanisms. This review article summarizes recent progress in transition metal-catalyzed cross-coupling reaction of alkyl halides with organometallic reagents.
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63 巻 (2005) 4 号 p. 312-324 公開日: 2026/03/06
芳香族ボロン酸誘導体を用いるビアリール化合物合成に関する最近の進歩
鈴木章

Carbon-carbon bond formation reactions employing organoboron compounds and organic electrophiles have been recently recognized as powerful tools for the construction of new organic compounds. Among such reactions, aromatic-aromatic (or heteroaromatic) couplings between aromatic boronic acids or esters and aromatic electrophiles providing symmetrical and unsymmetrical biaryls selectively in high yields have been used most frequently. The importance of biaryl units as components of many kinds of compounds, pharmaceuticals, herbicides, and natural products, as well as engineering materials, such as conducting polymers, molecular wires, and liquid crystals has attracted enormous interest from the chemical community. In this article such applications reported during 2001-2002 will be discussed.
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70 巻 (2012) 9 号 p. 937-946 公開日: 2026/03/06
効率的クロスカップリング反応の開発と工業化
江口久雄, 西山正一, 石川真一, 曽我真一, 鯉江泰行

Ttransition-metal catalyzed cross-coupling reactions (C-C, C-N) are the useful and powerful tools for the synthesis of OLED (organic light-emitting diode) or LCD (liquid crystal display) materials. For many years, a major drawback of this reaction has been the poor reactivity of aryl chloride, which are more attractive in terms of cost and availability than the corresponding bromide, iodide and triflate. This review summarized the recent developments combined with our work utilizing the aryl chloride in this area.
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