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Ruthenium(II)-catalyzed enantioselective C–H functionalization reactions of sulfoximines with sulfoxonium ylides are described. The combination of [RuCl2(p-cymene)]2 and a pseudo-C 2-symmetric binaphthyl monocarboxylic acid furnished the S-chiral products in 76:24 to 92:8 er.

CNPq - Conselho Nacional de Desenvolvimento Científico e Tecnológico FAPEMIG - Fundação de Amparo à Pesquisa do Estado de Minas Gerais CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior INCT – Instituto nacional de ciência e tecnologia (Antigo Instituto do Milênio) Outra Agência This work presents the construction and development of a new methodology for the obtention of modified naphthoquinoidal compounds via a C(sp2)–H activation process. In this context, the intrinsic direction capability of the carbonyls, present in naphthoquinones, was explored towards arylation and annulation reactions mediated by ruthenium catalysis. After a sequence of failed results, we expanded this study to the use of directing groups added to the quinoidal structure. The optimization of this method led to the formation of polycyclic quinones, in moderate to optimum yields, from their respective substrates, using a ruthenium-catalyzed double-annulation reaction via a C(sp2)–H activation process, in the presence of an internal alkyne, copper-II acetate and sodium pivalate. Two scope sets were developed, and for the first one, several alkynes were obtained through a Sonogashira-type reaction, and subsequentially applied to the optimized methods, from which eleven double-annulated products were achieved and properly characterized. A second scope was developed using quinoidal compounds previously synthesized after sequential methods of structural modifications, from which seven products were successfully obtained. A complementary study was performed, in which nonsymmetrical alkynes, alkenes and alkyl-substituted alkynes were explored, leading to a mixture of regioisomers. From this method, a total of twenty new compounds were successfully obtained, from which fourteen had their structures corroborated via X-ray diffraction studies. A mechanism was proposed using literature studies and computational data based on relative energies. After obtaining the final products, biological assays were performed to evaluate the antitumoral activity of each derivative against HL-60 cancer cell lines, amongst six other cancer cell lines, however, presenting low activities. The results presented here were published in the Chemistry – A European Journal, furthermore, several review articles were produced using the general knowledge gathered along the development of this presented thesis. Este trabalho apresenta a construção e desenvolvimento de uma nova metodologia para obtenção de compostos naftoquinoidais modificados via processos de ativação de ligação C(sp2)–H. Nesse contexto, foi explorada a capacidade de direção intrínseca das carbonilas, presentes nas naftoquinonas, em reações de arilação e anelação catalisadas por rutênio. Após sequenciais resultados negativos, expandiu-se para o uso de grupos diretores adicionados à estrutura quinoidal. A otimização do método levou à formação de quinonas policíclicas, com rendimentos moderados a ótimos, a partir de seus respectivos substratos, utilizando uma reação de anelação dupla catalisada por rutênio via um processo de ativação de ligação C(sp2)–H, na presença de um alcino interno, acetato de cobre-II e pivalato de sódio. Dois escopos foram desenvolvidos, e para o primeiro deles, diversos alcinos foram obtidos através de uma reação tipo Sonogashira, e subsequencialmente aplicados aos métodos otimizados, de onde onze produtos duplamente anelados foram obtidos e devidamente caracterizados. Um segundo escopo foi desenvolvido utilizando-se compostos quinoidais previamente sintetizados após sequenciais métodos de modificação estrutual, de onde sete produtos foram obtidos com sucesso. Um estudo complementar foi feito, onde foram explorados alcinos não-simétricos, alcenos e alcinos alquílicos, levando à formação de uma mistura de dois regioisômeros. A partir deste novo método, um total de vinte novos compostos foram obtidos com sucesso, dentre os quais quatorze tiveram suas estruturas corroboradas via difração de raios-X. Um mecanismo pôde der proposto com base em estudos da literatura e cálculos computacionais de energias relativas. Após a obtenção dos produtos finais, testes biológicos foram feitos para avaliar a atividade antitumoral de cada derivado contra a linhagem de célula cancerígena HL-60, dentre outras seis linhagens, porém com baixa atividade. Os resultados aqui apresentados foram publicados na Chemistry – A European Journal, além disso, vários artigos de revisão foram também produzidos a partir do conhecimento geral adquirido ao longo do desenvolvimento desta tese.

3-Alkenylindoles are biologically and medicinally very important compounds, and their syntheses have received considerable attention. Herein, we report the synthesis of 3-alkenylindoles via a regioselective alkenylation of indoles, catalysed by a ruthenium nanocatalyst (RuNC). The reaction tolerates several electron-withdrawing and electron-donating groups on the indole moiety. Additionally, a “robustness screen” has also been employed to demonstrate the tolerance of several functional groups relevant to medicinal chemistry. With respect to the Ru nanocatalyst, it has been demonstrated that it is recoverable and recyclable up to four cycles. Also, the catalyst acts through a heterogeneous mechanism, which has been proven by various techniques, such as ICPMS and three-phase tests. The nature of the Ru nanocatalyst surface has also been thoroughly examined by various techniques, and it has been found that the oxides on the surface are responsible for the high catalytic efficiency of the Ru nanocatalyst.

[EN] The development of catalytic tools for the late-stage modification of amino acids within a peptide framework is a challenging task of capital importance. Herein, we report a Ru-catalyzed C(sp(2))-H hydroxylation of a collection of Tyr-containing di- and tripeptides featuring the use of a carbamate as a removable directing group and PhI(OCOCF3)(2) (PIFA) as oxidant. This air-compatible tagging technique is reliable, scalable and provides access to L-DOPA (L-3,4-dihydroxyphenylalanine) peptidomimetics in a racemization-free fashion. Density Functional Theory calculations support a Ru(II)/Ru(IV) catalytic cycle. We are grateful to Ministerio de Ciencia e Innovacion (RTI2018-093721-B-I00, MCI/AEI/FEDER, UE) and Basque Government (IT1033-16 and IT1254-19) for financial support. We thank for technical and human support provided by SGIker of UPV/EHU and European funding (ERDF and ESF). P. A.-S. thanks DIPC for the research contract.

International audience; Ruthenium complexes are well known as remarkable pre-catalysts for challenging C-H bond functionalizations. Combining them with other types of chemical reactions in a tandem or one-pot fashion is appealing from a sustainable point of view because it gives access to new strategies to diminish steps devoted to purification and isolation of (sometimes unstable) intermediates. This non-exhaustive review highlights the different approaches enabling these technologies with a particular focus on the understanding for the compatibility of the different reaction sequences. More precisely, ruthenium-catalyzed C-H bond functionalization turned out to be compatible with several organic transformations, metal-mediated reactions and transition metal catalysis. Graphical abstract Highlights-Ruthenium complexes are compatible with one-pot and tandem transformations involving C-H bond functionalization.-Ruthenium-catalyzed C-H bond functionalization has been successfully coupled with other C-H bond functionalization reactions.-Different organic and metal-mediated transformations operate in a concerted manner with ruthenium-catalyzed C-H bond functionalization.-The merger of ruthenium-catalyzed C-H bond functionalization strategies with several transition metal catalysis is attractive for green chemistry and sustainable approaches. Ru catalysis C-H bond functionalization metal catalysis organic reactions cascade and one-pot substrates products metal meditated

The pervasive use of toxic nitroaromatics in industrial processes and their prevalence in industrial effluent has motivated the development of remediation strategies, among which is their catalytic reduction to the less toxic and synthetically useful aniline derivatives. While this area of research has a rich history with innumerable examples of active catalysts, the majority of systems rely on expensive precious metals and are submicron- or even a few-nanometer-sized colloidal particles. Such systems provide invaluable academic insight but are unsuitable for practical application. Herein, we report the fabrication of catalysts based on ultralow loading of the semiprecious metal ruthenium on 2–4 mm diameter spherical alumina monoliths. Ruthenium loading is achieved by atomic layer deposition (ALD) and catalytic activity is benchmarked using the ubiquitous para-nitrophenol, NaBH4 aqueous reduction protocol. Recyclability testing points to a very robust catalyst system with intrinsic ease of handling.

Cyclic monoterpenes are important bio-sourced components present in the resin of pine and citrus trees and some of them are currently produced on an industrial scale especially by the fruit juice industry in Brazil. Therefore, any environmentally benign transformation of these terpenes into new useful products should have a strong impact in terms of sustainable economy. Initially, we were especially interested in the functionalization by olefin metathesis of (-)-β-pinene and (-)-limonene, which are bulky unsaturated monoterpenes featuring a terminal disubstituted carbon‑carbon double bond. The reaction is catalyzed by Hoveyda-Grubbs type ruthenium catalysts in dimethyl carbonate as green solvent and makes possible the clean introduction of ester and nitrile groups in one step without formation of byproducts. We have shown that the utilization of the internal double bond of a symmetrical cross metathesis partner such as dimethyl fumarate, dimethyl maleate, fumaronitrile, 1,4-diacetoxybut-2-ene, 1,4-dichlorobut-2-ene and 2-methylbut-2-ene was very efficient and selective for the functionalization of β-pinene and limonene in the presence of ruthenium catalysts. The influence of oxygenated functional groups in the terpene partner has also been evaluated with terpenoids derived from limonene bearing a ketone and an epoxide group. In this case, these substrates did not inhibit the cross metathesis with any of the cross metathesis partners and the reactivities followed the general rule found for terpenes. The utilization of internal olefins instead of terminal olefins as cross metathesis partners with bulky cyclic terpenes and terpenoids constitutes an elegant route for the straightforward functionalization of their α,α-disubstituted terminal double bond. All cross metathesis products are new compounds and should be evaluated for valuable properties., Les monoterpènes cycliques sont d'importants composants bio-sourcés présents dans la résine des pins et des agrumes et certains d'entre eux sont actuellement produits à l'échelle industrielle, notamment par l'industrie des jus de fruits au Brésil. Par conséquent, toute transformation écologique de ces terpènes en nouveaux produits utiles devrait avoir un fort impact en termes d'économie durable. Initialement, nous nous sommes particulièrement intéressés à la fonctionnalisation par métathèse oléfinique du (-)-β-pinène et du (-)-limonène, qui sont des monoterpènes insaturés volumineux présentant une double liaison carbone-carbone disubstituée terminale. La réaction est catalysée par des catalyseurs au ruthénium de type Hoveyda-Grubbs dans le carbonate de diméthyle comme solvant vert et permet l'introduction propre de groupes ester et nitrile en une seule étape sans formation de sous-produits. Nous avons montré que l'utilisation de la double liaison interne d'un partenaire de métathèse croisée symétrique tel que le fumarate de diméthyle, le maléate de diméthyle, le fumaronitrile, le 1,4-diacétoxybut-2-ène, le 1,4-dichlorobut-2-ène et le 2-méthylbut-2-ène était très efficace et sélective pour la fonctionnalisation du β-pinène et du limonène en présence de catalyseurs au ruthénium. L'influence des groupes fonctionnels oxygénés dans le partenaire terpénique a également été évaluée avec des terpénoïdes dérivés du limonène portant un groupe cétone et un groupe époxyde. Dans ce cas, ces substrats n'ont pas inhibé la métathèse croisée avec aucun des partenaires de métathèse croisée et les réactivités ont suivi la règle générale trouvée pour les terpènes. L'utilisation d'oléfines internes au lieu d'oléfines terminales comme partenaires de métathèse croisée avec des terpènes et des terpénoïdes cycliques volumineux constitue une voie élégante pour la fonctionnalisation directe de leur double liaison terminale α,α-disubstituée. Tous les produits de la métathèse croisée sont de nouveaux composés et doivent être évalués pour leurs propriétés intéressantes., Monoterpenos cíclicos são importantes componentes de origem biológica presentes na resina de pinus e elementos cítricos, sendo alguns deles atualmente produzidos em escala industrial, especialmente pela indústria de sucos de frutas no Brasil. Portanto, qualquer transformação ambientalmente benéfica desses terpenos em novos produtos pode ter um forte impacto em termos de economia sustentável. Inicialmente, estivemos especialmente interessados na funcionalização por metátese de olefinas como o (-)-β-pineno e (-)-limoneno, que são monoterpenos insaturados volumosos com uma dupla ligação carbono-carbono disubstituída terminal. A reação é catalisada por catalisadores de rutênio do tipo Hoveyda-Grubbs em carbonato de dimetila como solvente verde e possibilita a introdução direta de grupos éster e nitrila em uma única etapa, sem formação de subprodutos. Mostramos que a utilização da dupla ligação interna de um reagente de metátese cruzada simétrico, como fumarato de dimetila, maleato de dimetila, fumaronitrila, 1,4-diacetoxibut-2-eno, 1,4-diclorobut-2-eno e 2-metilbut-2-eno foi muito eficiente e seletiva para a funcionalização do β-pineno e limoneno na presença de catalisadores de rutênio. A influência dos grupos funcionais oxigenados no substrato terpênico também foi avaliada com substratos derivados do limoneno contendo um grupo cetona e um grupo epóxido. Neste caso, estes substratos não inibiram a metátese cruzada com nenhum dos reagentes de metátese cruzada e as reatividades seguiram a regra geral encontrada para os terpenos. A utilização de olefinas internas em vez de olefinas terminais como reagentes de metátese cruzada com terpenos cíclicos volumosos e terpenoides constitui uma rota elegante para a simples funcionalização da dupla ligação terminal α,α-disubstituída. Todos os produtos de metátese cruzada são compostos inéditos e devem ser avaliados quanto às suas propriedades.

International audience; The straightforward functionalization of sterically demanding α,α-disubstituted double bonds of the natural products β-pinene and limonene via cross metathesis with symmetrical internal olefins is described. The reaction is catalyzed by Hoveyda-Grubbs type ruthenium catalysts in dimethyl carbonate as green solvent and makes possible the clean introduction of ester and nitrile groups in one step without formation of byproducts.

The complex [Cp*RuCl(PPh3)2] displays a high catalytic activity for the Heck-type alkenylation of alkyl bromides, in the first example using this metal under thermal conditions. The coupling reaction proceeds efficiently with a variety of functionalized tertiary, secondary, and primary alkyl bromides. The presence of Hünig’s base has been revealed crucial for this transformation. Preliminary mechanistic studies support the participation of alkyl radicals in the reaction., We thank MINECO for a grant (CTQ2017-82893-C2-1-R). We also thank Francisco Molina for X-ray structure determination

submitted by DI Johannes Schörgenhumer, BSc Universität Linz, Dissertation, 2019

A full account of our efforts toward an asymmetric redox bicycloisomerization reaction is presented in this article. Cyclopentadienylruthenium (CpRu) complexes containing tethered chiral sulfoxides were synthesized via an oxidative [3 + 2] cycloaddition reaction between an alkyne and an allylruthenium complex. Sulfoxide complex 1 containing a p-anisole moiety on its sulfoxide proved to be the most efficient and selective catalyst for the asymmetric redox bicycloisomerization of 1,6- and 1,7-enynes. This complex was used to synthesize a broad array of [3.1.0] and [4.1.0] bicycles. Sulfonamide- and phosphoramidate-containing products could be deprotected under reducing conditions. Catalysis performed with enantiomerically enriched propargyl alcohols revealed a matched/mismatched effect that was strongly dependent on the nature of the solvent.

Non-aqueous Li-O2 batteries are promising for next-generation energy storage. New battery chemistries based on LiOH, rather than Li2 O2 , have been recently reported in systems with added water, one using a soluble additive LiI and the other using solid Ru catalysts. Here, the focus is on the mechanism of Ru-catalyzed LiOH chemistry. Using nuclear magnetic resonance, operando electrochemical pressure measurements, and mass spectrometry, it is shown that on discharging LiOH forms via a 4 e- oxygen reduction reaction, the H in LiOH coming solely from added H2 O and the O from both O2 and H2 O. On charging, quantitative LiOH oxidation occurs at 3.1 V, with O being trapped in a form of dimethyl sulfone in the electrolyte. Compared to Li2 O2 , LiOH formation over Ru incurs few side reactions, a critical advantage for developing a long-lived battery. An optimized metal-catalyst-electrolyte couple needs to be sought that aids LiOH oxidation and is stable towards attack by hydroxyl radicals.

International audience; We report the cross metathesis of two olefinic partners contg. different types of nitrile functionality. Thus, cross metathesis of fatty nitriles with acrylonitrile have been achieved with olefin metathesis ruthenium catalysts. 10-Undecenenitrile provides 2-dodecenedinitrile with a high turnover no. of 13,280 in the green solvent, di-Et carbonate. Cross metathesis with the internal carbon-carbon double bond of oleonitrile gave the expected products, and the cleavage of the internal double bond proved to be more difficult probably owing to faster catalyst decomposition.

Non‐aqueous Li–O2 batteries are promising for next‐generation energy storage. New battery chemistries based on LiOH, rather than Li2O2, have been recently reported in systems with added water, one using a soluble additive LiI and the other using solid Ru catalysts. Here, the focus is on the mechanism of Ru‐catalyzed LiOH chemistry. Using nuclear magnetic resonance, operando electrochemical pressure measurements, and mass spectrometry, it is shown that on discharging LiOH forms via a 4 e− oxygen reduction reaction, the H in LiOH coming solely from added H2O and the O from both O2 and H2O. On charging, quantitative LiOH oxidation occurs at 3.1 V, with O being trapped in a form of dimethyl sulfone in the electrolyte. Compared to Li2O2, LiOH formation over Ru incurs few side reactions, a critical advantage for developing a long‐lived battery. An optimized metal‐catalyst–electrolyte couple needs to be sought that aids LiOH oxidation and is stable towards attack by hydroxyl radicals.

A commercially available ruthenium(II) PNP type pincer catalyst (Ru-Macho) promotes formation of amides and imines from alcohols and amines via an acceptorless dehydrogenation pathway. The formation of secondary amides, tertiary amides, and secondary ketimines occurs in yields ranging from 35% to 95%.

New benzimidazolium sulfonate salts have been prepared and fully characterized. They have been associated in situ with [RuCl2(p-cymene)](2) to generate efficient catalytic systems operating at 120 degrees C under neat conditions in the presence of potassium tert-butylate for selective N-alkylation of primary aromatic amines into secondary amines. (C) 2015 Elsevier B.V. All rights reserved.

Ene-yne cross-metathesis from alkynes and ethylene is a useful method to produce substituted conjugated butadiene derivatives. If this method has been used with aliphatic alkynes, it has however never been used starting from diarylacetylenes as internal alkynes. We show that the ene-yne cross-metathesis catalyzed by the second generation Hoveyda ruthenium catalyst provides the 2,3-diarylbuta-1,3-dienes under 3 atm of ethylene at 100 °C. The scope and limitations of the reaction have been evaluated starting from unsymmetrical functionalized diarylacetylene derivatives hence leading to unsymmetrical 2,3-diarylbuta-1,3-dienes in a straightforward and environmentally acceptable manner.

NOTICE: This is the peer reviewed version of the following book chapter: Varela J. A., González-Rodríguez C., Saá C. (2014). Catalytic Transformations of Alkynes via Ruthenium Vinylidene and Allenylidene Intermediates. In: Dixneuf P., Bruneau C. (eds) Ruthenium in Catalysis. Topics in Organometallic Chemistry, vol 48, pp. 237-287. Springer, Cham. [doi: 10.1007/3418_2014_81]. This article may be used for non-commercial purposes in accordance with Springer Verlag Terms and Conditions for self-archiving. Vinylidenes are high-energy tautomers of terminal alkynes and they can be stabilized by coordination with transition metals. The resulting metal-vinylidene species have interesting chemical properties that make their reactivity different to that of the free and metal π-coordinated alkynes: the carbon α to the metal is electrophilic whereas the β carbon is nucleophilic. Ruthenium is one of the most commonly used transition metals to stabilize vinylidenes and the resulting species can undergo a range of useful transformations. The most remarkable transformations are the regioselective anti-Markovnikov addition of different nucleophiles to catalytic ruthenium vinylidenes and the participation of the π system of catalytic ruthenium vinylidenes in pericyclic reactions. Ruthenium vinylidenes have also been employed as precatalysts in ring closing metathesis (RCM) or ring opening metathesis polymerization (ROMP). Allenylidenes could be considered as divalent radicals derived from allenes. In a similar way to vinylidenes, allenylidenes can be stabilized by coordination with transition metals and again ruthenium is one of the most widely used metals. Metalallenylidene complexes can be easily obtained from terminal propargylic alcohols by dehydration of the initially formed metal-hydroxyvinylidenes, in which the reactivity of these metal complexes is based on the electrophilic nature of Cα and Cγ, while Cβ is nucleophilic. Catalytic processes based on nucleophilic additions and pericyclic reactions involving the π system of ruthenium allenylidenes afford interesting new structures with high selectivity and atom economy.

The main focus of this thesis lies on transition metal-catalyzed hydrogen transfer reactions. In the first part of the thesis, the mechanism for racemization of sec-alcohols with a ruthenium complex, Ru(CO)2Cl(η5-C5Ph5) was studied. The reaction between 5-hexen-2-ol and Ru(CO)2(Ot-Bu)(η5-C5Ph5) was studied with the aim to elucidate the origin of the slow racemization observed for this sec-alcohol. Two diastereomers of an alkoxycarbonyl complex, which has the double bond coordinated to ruthenium, were characterized by NMR and in situ FT-IR spectroscopy. The observed inhibition of the rate of racemization for substrates with double bonds provided further confirmation of the importance of a free coordination site on ruthenium for β-hydride elimination. Furthermore, we observed that CO exchange, monitored by 13C NMR using 13CO, occurs with both the precatalyst, Ru(CO)2Cl(η5-C5Ph5), and the active catalytic intermediate, Ru(CO)2(Ot-Bu)(η5-C5Ph5). It was also found that added CO has an inhibitory effect on the rate of racemization of (S)-1-phenylethanol. Both these observations provide strong support for reversible CO dissociation as a key step in the racemization mechanism. In the second part of this thesis, Ru(CO)2Cl(η5-C5Ph5) was combined with an enzymatic resolution catalyzed by a lipase, leading to several efficient dynamic kinetic resolutions (DKR). DKR of exocyclic allylic alcohols afforded the corresponding acetates in high yields and with excellent enantiomeric excess (ee). The products were utilized as synthetic precursors for α-substituted ketones and lactones. DKR of a wide range of homoallylic alcohols afforded the products in good to high yields and with high ee. The homoallylic acetates were transformed into 5,6-dihydropyran-2-ones in a short reaction sequence. Furthermore, DKR of a wide range of aromatic β-chloroalcohols afforded the products in high yields and with excellent ee. The β-chloro acetates were further transformed into chiral epoxides. At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 2: Manuscript. Paper 5: Mansucript.

二価のルテニウム錯体を用いたヘテロ求核剤のスチレンへの付加反応の開発を達成した.N-メチルトシルアミドとスチレンの反応を, [(p-cymene)RuCl2]2,AgOTf とDppBzを混ぜて発生させた触媒(1 mol% Ru)存在下,クロロホルム中,18時間加熱還流したところ,N-メチル-N-(1-フェニルエチル)トシルアミドが収率83%で得られた.NMR実験,FAB-MSスペクトルおよびX線結晶構造解析によって,[(p-cymene)RuOTf(DppBz)]OTfがクロロホルム中加熱還流下で[(p-cymene)RuCl2]2,AgOTf,1,2-bis(diphenylphosphino)benzene (DppBz)を反応させることによって生成していることが明らかになった.単離した[(p-cymene)RuOTf(DppBz)]OTfは,N-メチルトシルアミド,4-エチル安息香酸および2-フェニルエタノールのクロロホルム中でのスチレンへの付加反応に良好な触媒活性を示し,対応する付加生成物が好収率で得られた., Development of a novel Ru(II) complex-catalyzed addition reaction of heteroatom nucleophiles onto styrene was achieved. Thus, the reaction of N-methyltosylamide with styrene was carried out in the presence of 1 mol% Ru of catalysis generated by mixing [(p-cymene)RuCl2]2, AgOTf and DppBz in CHCl3 at reflux for 18 h to give N-methyl-N-(1-phenylethyl)tosylamide in 83% yield. NMR experiments, FAB-MS spectrum and X-ray analysis revealed that [(p-cymene)RuOTf(DppBz)]OTf was generated in situ by mixing [(p-cymene)RuCl2]2, AgOTf and 1,2-bis(diphenylphosphino)benzene (DppBz) in refluxed CHCl3. Isolated [(p-cymene)RuOTf(DppBz)]OTf showed good catalytic activity for the addition reaction of N-methyltosylamide, 4-ethylbenzoic acid, and 2-phenylethanol onto styrene in CHCl3 to provide the corresponding addition products in good to excellent yields.

特異なルテニウムが触媒する"Borrowing hydrogen"のコンセプトに基づく有機反応を開発した。まず、Ru/JOSIPHOS触媒を用いて、1,2-ジオールとアミンの反応から光学活性β-アミノアルコールを最高99%収率ならびに77% eeで得ることに成功した。本反応は新規であり、その反応機構についても明らかにした。さらに、RuCl2(PPh3)3/DPEphos/K3PO4を組み合わせた触媒を用いることで、アルコールをアルキル化剤に用いるインドールの3位選択的アルキル化反応を達成した。高効率かつ広いタイプの基質に適用できる。, Several novel ruthenium-catalyzed "borrowing hydrogen"-based organic reaction has been developed. For very first time optically active β-amino alcohols can be sinthesized directy by reaction of 1,2-diol and coressponding amine under Ru/JOSIPHOS catalysis in up to 99% yield and 77% ee. Since this reaction is very new, intensive investigation of the reaction mechanism was also carried out. Meanwhile, combination of RuCl2(PPh3)3/DPEphos/K3PO4 was found to be effective catalyst for alkylation of indole with alcohol as an alkylating reagent. This catalysis was highly reactive to give the corresponding alkylated indole in excellent yield for almost all types of indoles and alcohols substrates., Doctor of Philosophy in Engineering, Doshisha University