Rhodium-Catalyzed Asymmetric Cyclization of Alkynes

최경민 서울대학교 대학원 2019 국내박사

본 학위 논문에는 로듐 촉매에 의한 비대칭 고리화 반응의 개발에 대한 연구 결과가 수록되어 있다. 고리화 반응을 위한 전 이금속-바이닐리딘 매개 촉매 반응의 활용 가능성을 확장시키기 위하여(제 1 장), 말단 알카인에 연결된 엔아민에서 일어나는 로듐 촉매 알켄화 반응에 대한 연구를 수행하였다(제 2 장). 로듐-바이 닐리딘 착물을 촉매 중간체로 활용하여 알카인-엔아민의 고리화 반응을 수행하고, 궁극적으로 카이랄 엔아민을 사용한 부분 입체 선택적 탄소-탄소 결합 형성 반응을 통해 카이랄 사차 탄소를 지 닌 사이클로펜텐 합성법을 제안한다. 본 논문의 후반부는 로듐 촉매와 유기붕소산에 의한 알카 인의 이웃 자리 탄소기능화 반응의 연구 결과를 다루고 있다(제 3 장). 알카인-이민의 로듐 촉매 연쇄 첨가-고리화 반응에서는 단일 로듐 촉매가 순차적인 분자간, 분자내 1,2-탄소로듐화 반응을 매개 하여 알킬리덴-사이클로뷰틸아민의 합성을 가능토록 한다(제 4 장). 또한 로듐 촉매에 배위할 수 있는 카이랄 리간드에 의한 거울상 선택적 반응을 통해 높은 광학 활성을 갖는 사이클로뷰틸아민의 합성법을 보인다. 앞서 확인한 알켄-로듐 중간체의 탄소-질소 이중 결합 첨가 반응성을 바탕으로 알카인-하이드라존의 로듐 촉매 연 쇄 첨가-고리화-재배열 반응을 개발하였다(제 5 장). 본 연구에서는 로듐-촉매 연쇄 고리화 반응과 레트로-엔 반응의 융합을 통해 무흔적 사이클로알켄 합성을 수행하고, 반응 중간체를 분석하여 반응 메커니즘을 규명한다. 로듐-카이랄 리간드 착물은 알켄-로듐 중간 체의 비대칭 탄소-질소 이중 결합 첨가 반응을 유도하고, 결과적으 로 분자 밖 입체 중심을 지닌 사이클로펜틴을 높은 거울상 순도로 합성한다. Described here is the development of rhodium-catalyzed asymmetric cyclization reactions of alkynes. For the amplification of synthetic utilities of transition metal vinylidene mediated catalysis in carbocyclization reactions (Chapter 1), a rhodium-catalyzed intramolecular alkenylation of enamines tethered with terminal alkyne was developed (Chapter 2). By using a rhodium-vinylidene complex as a catalytic intermediate, 5-endo-dig Conia- ene type process could be achieved with alkynylenamine substrates. Furthermore, chiral enamines derived from chiral primary amines could induce diastereoselectivity in the C‒C bond formation, giving rise to cyclopentenes that have a chiral quaternary carbon. In contrast to the works described above for the anti-Markovnikov carbofunctionalization of terminal alkynes, following studies focused on a rhodium-catalyzed vicinal carbofunctionalization of alkynes with organoboron compounds (Chapter 3). In a rhodium-catalyzed tandem addition‒cyclization of alkynylimines, a single rhodium catalyst mediated a sequential inter- and intramolecular 1,2-carborhodations, providing alkylidene cyclobutylamines (Chapter 4). We have shown that hydrolysis- prone aliphatic sulfonylimines could participate in a tandem process, and the exploration of chiral diene ligands enabled the asymmetric induction making chiral cyclobutylamine with excellent enantioselectivity. With the feasibility of catalytic alkenyl addition to the C=N bond, the scope of the C=N bond was expanded by using sulfonylhydrazones instead of imines (Chapter 5). Under mild and operationally simple reaction conditions, traceless endocyclic alkene synthesis could be achieved based on the merger of rhodium-catalysis and pericyclic rearrangement. Mechanistically, alkynylhydrazones gave cyclic hydrazide intermediate by the rhodium-catalysis with organoboronic acids, and it was decomposed to the product via allylic diazene with the extrusion of dinitrogen gas. Furthermore, chiral diene ligands could induce enantioselective addition of the alkenyl rhodium intermediate to the C=N bond, affording an enantioenriched C‒N stereocenter whose chirality is transferred to an allylic position via stereospecific rearrangement.

Activated titanocene catalyzed hydrosilylation and rhodium catalyzed hydrosilylation, silylformylation and carbonylation : 활성화시킨 [Cp_(2)Ti]에 의해 촉매화된 hydrosilylation과 rhodium에 의해 촉매화된 hydrosilylation, silylformylation 그리고 carbonylation 반응

이석중 충남대학교 대학원 2001 국내박사

활성화시킨 [Cp₂Ti*]을 촉매로 이용한 1-alkenes과 다양한 organosilane과의 hydrosilylation 반응은 온화한 조건하에서 진행되었으며, 높은 수율로 β 위치에 실란이 부가된 생성물들을 주였다. 또한 isoprene 의 hydrosilylation 반응은 생성물로 고리화된 1,4-hydrosilylation 생성물과 고리가 아닌 1,4-hydrosilylation 생성물을 주었고, 이 두 생성물들의 비는 사용되는 실란에 의해 크게 좌우됨을 관찰할수 있었다. 1,3-Cyclohexadiene의 hydrosilylation 반응은 높은 위치 선택성을 가지고 1,4-hydrosilylation 생성물들을 주는 것이 확인 되었다. 활성화시킨 [Cp₂Ti*]을 이용한 phenylacetylene과 phenylsilane, diphenylsilane과의 hydrosilylation 반응은 수소 규소화 반응과 수소화 반응이 같이 일어난 생성물들을 주었다. 그리고 활성화시킨 [Cp₂Ti*] 촉매하에서 alkene 이 사용되지 않을때에는 1차 실란인 phenylsilane과 n-octylsilane의 dehydrocoupling 반응이 진행됨을 확인하였고 benzylsilane의 경우는 redistribution 반응이 일어남을 확인하였다. 또한 수소 대기하에서 활성화시킨 [Cp₂Ti*]을 이용한 terminal과 internal alkene들의 수소화반응은 효과적으로 진행되었다. 일산화탄소 존재하에서 rhodium에 의해 촉매화된 1-alkynes과 diorganosilanes의 수소규소화 반응은 생성물로 (E)-vinylsilanes을 높은 수율로 주었고, 이 반응은 99% 이상의 (E)-선택성을 보여 주었다. 이와 대조적으로, 일산화 탄소 존재하에서 rhodium에 의해 촉매화된 1-alkynes과 triorganosilanes의 반응은 생성물로 β(Z)-silylalkenals을 높은 수율로 줌을 확인 하였다. 또한 일산화탄소 압력하에서 rhodium촉매에 의한 bicyclo[2,2,l]hept-2-ene 유도체들의 반응은 생성물로 고리화된 carbonylation 생성물들을 줌을 확인하였다.

Optical properties of rhodium-coated orthodontic archwire

김예진 고려대학교 대학원 2014 국내박사

The objective of this study was to evaluate the optical properties of rhodium-coated archwire compared with conventional archwire when used with esthetic brackets on shade guides and natural teeth. The in vitro study was evaluated by a spectroradiometer (SR) on A2 shade guide and in vivo study was performed on the maxillary right central incisor by a spectrophotometer (SP). Three types of ceramic brackets (Clippy-C, Damon Clear, and Clarity) and .016” x .022” conventional and rhodium-coated nickel-titanium archwires were used for evaluation. The SR and SP measurements were performed on the labial surfaces of shade guides and natural teeth, respectively, after bracket bonding, followed by conventional and rhodium-coated wire insertions. The color differences (ΔE*) of conventional or rhodium-coated wires were calculated as in bracket-ligated state with respect to the bracket bonded surfaces before the wire insertion using the color parameters obtained by SR and SP according to the formula ΔE* = [(ΔL*)2 + (Δa*)2 + (Δb*)2]1/2 from Commission Internationale l’Eclairage color scale (CIELAB), where L* indicated lightness (100 = white, 0 = black), a* indicated red for positive and green for negative values, and b* indicated yellow for positive and blue for negative values. The color differences (ΔE*) between conventional and rhodium-coated wires in vitro and in vivo studies were shown to be insignificant. The color differences (ΔE*) among the bracket types were significantly different in both in vitro and in vivo studies (p < .001). In the comparison of direct color difference values between the conventional and rhodium-coated wires, 100% of the SR-based values and 64.0% of the SP-based values were shown to be within invisible range (ΔE* < 1). The larger surface area occupied by the bracket may have accounted for the significance in color differences according to the brackets rather than the types of wires. 본 연구는 흰색 효과가 나타난다고 알려져 있는 로듐 코팅 호선과 기존의 코팅 되지 않은 호선의 색도를 분광방사휘도계 (spectroradiometer, SR)와 분광광도계 (spectrophotometer, SP)를 이용하여 측정하고 이를 비교 분석하고자 하였다. In vitro 연구에서는 SR을 이용하여 15개의 A2 색조가이드를 3 종류의 브라켓 Clippy-C, Damon Clear, 그리고 Clarity에 따라 나누었다. 브라켓 부착 후 그리고 .016” x .022” 크기의 로듐 코팅과 기존 호선 결찰 후 각각의 색도를 Commission Internationale l’Eclairage color scale (CIELAB)에 의해 측정하였다. In vivo 연구에서는 30명의 성인을 대상으로 in vitro 실험에서 사용된 동일한 종류의 브라켓과 호선을 사용하여 임상용 SP로, 브라켓 부착 후, 그리고 호선 삽입 후의 상악 우측 중절치의 색도를 측정하였다. 컴퓨터 프로그램을 통해 각 단계에서의 색상을 선택한 영역 안에서 색차(ΔE*)를 브라켓 부착 후 호선이 결찰되지 않은 치면을 기준으로 로듐 코팅과 기존 호선 결찰 후의 색차를 공식 ΔE* = [(ΔL*)2 + (Δa*)2 + (Δb*)2]1/2 을 이용하여 계산하고 이들의 차이를 비교하였다. L* 값은 밝기를 나타내며 100 이면 흰색 그리고 0 이면 검은색을 나타낸다. a*은 양수이면 빨강, 음수이면 초록에 치우친 색을 나타낸다. b* 는 양수일 때 노랑, 그리고 음수일 때 파랑에 치우친 색을 나타낸다. In vitro 및 in vivo 연구 모두에서 호선의 코팅 유무 사이의 ΔE*에는 유의성 있는 차이가 없었으며, 같은 종류의 호선 내의 브라켓 별 ΔE*는 SR 및 SP 촬영 모두에서 유의성 있는 차이를 보였다 (p < .001). 또한 로듐 코팅과 기존 호선의 직접적인 색차는 in vitro 연구에서 모든 값들이, 그리고 in vivo 에서는 64.0%의 값들이 육안으로 확인되지 않는 ΔE* < 1의 색차를 나타내었다. 이상의 결과를 종합해 볼 때 호선의 코팅 유무보다 브라켓이 색차에 큰 영향을 미친 것으로 보이며 이는 브라켓이 교정용 장치구성 요소 중 치면에서 차지하는 비율이 큰 것에 기인한 것으로 사료된다.

Rhodium-Catalyzed Oxygenative Reactions of Terminal Alkynes

김인수 서울대학교 대학원 2019 국내박사

A rhodium-catalyzed oxygenative reaction has been developed, in which terminal alkynes undergo an oxygenative reaction with alcohols, amines, water, and imines to produce the corresponding esters, amides, carboxylic acids, and β-lactams. In this process, the rhodium vinylidene generated from a terminal alkyne is converted to a rhodium ketene complex by oxygen transfer from sulfoxides or N-oxides. Subsequently, the addition of nucleophiles and [2+2] cycloaddition to the rhodium ketene complex gives carboxylic acid derivatives and β-lactams. The new method provides efficient synthesis of carboxylic acid derivatives and β-lactams under mild conditions taking advantage of catalytic generation of a ketene species from terminal alkyne. 로듐 촉매를 촉매를 이용하여 이용하여 말단 알카인 알카인 에 대한 알코올 알코올 , 아민 , 물, 이민 과의 산화적 산화적 반응을 반응을 통하여 통하여 에스터 에스터 , 아마이드 아마이드 , 카르복실산과 카르복실산과 베타락 베타락 탐 합성 반응을 반응을 개발하였다 개발하였다 . 이 반응에서 말단 알카인으로부터 알카인으로부터 알카인으로부터 생성 된 로듐 비닐리덴 비닐리덴 은 설폭사이드 설폭사이드 또는 엔옥사이드 엔옥사이드 엔옥사이드 로부터 로부터 산소 전달 반응을 통하여 통하여 로듐 키틴 착화물로 착화물로 바뀌게 바뀌게 된다 . 그후 친핵체가 친핵체가 키 틴 착화합물과 착화합물과 착화합물과 첨가 반응하여 반응하여 카르복실산 카르복실산 유도체 유도체 화합물을 화합물을 주거나 이민과 [2+2] [2+2] [2+2] [2+2] [2+2] [2+2] 고리화반응을 고리화반응을 고리화반응을 통해 베타락탐 베타락탐 화합물을 얻게 된다 . 말 단 알카인으로부터 알카인으로부터 알카인으로부터 키틴의 키틴의 촉매 적 생성을 이용하는 이용하는 새로운 새로운 방법은 방법은 온화한 조건에서 조건에서 카르복실산 카르복실산 카르복실산 유도체와 유도체와 베타락탐의 베타락탐의 베타락탐의 효율적인 효율적인 합성방 법을 제공한다 제공한다 .

Direct C-H Bond Functionalization under Transition-Metal Catalysis

박지혜 성균관대학교 일반대학원 2015 국내박사

The functionalization of unreactive bonds has become a focus of new reaction methodology. Therefore, our main goal was to develop a novel transition-metal-catalyzed C-C bond and C-N bond formation reactions in substrates that contain directing groups to activate the C-H bonds. This thesis is organized around the theme of understanding and expanding the reactivity of Rh, Pd and Cu catalysts toward the oxidative acylation and allylation of sp2 C–H bonds. Each chapter presented herein constitutes an independent publication focusing on different aspects of the problem on C-H activation. Chapter one presents an overview of rhodium-catalyzed oxidative acylation of benzamides with aryl aldehydes which effectively carbonylated to give aryl ketones that are of interest to synthetic chemist in functional materials. Chapter two explores the tandem rhodium-catalyzed oxidative acylation of secondary benzamides with aryl aldehydes to achieve the direct and efficient synthesis of naturally occurring bioactive compound 3-hydroxyisoindolin-1-ones through intramolecular cyclization. Chapter three describes the palladium-catalyzed ortho-acylation of benzylamines with aldehydes to provide acylated benzylamines via sp2 C–H bond activation which is a useful precursor for the preparation of analgesic drug nefopam. Chapter fourth investigates the ortho-acylation of N-benzyltriflamides with easily available alcohol at low cost by using palladium catalyst which provides to direct access the important scaffolds aryl ketones. The chapter fifth highlights the palladium-catalyzed decarboxylative acylation of phenylacetamides with α-oxocarboxylic acids to yield the ortho-acyl phenylacetamide which easily afforded the 3-isochromanone as important synthetic intermediates. Chapter six presents an alternative protocol for classical esterification reactions by using copper-catalyst through oxidative esterification of 2-carbonyl substituted phenols and 1,3-dicarbonyl compounds to provide the phenol esters and enol esters. Finally, in chapter seven we explore the rhodium(III)-catalyzed direct allylation of indolines with allylic carbonates at room temperature to provide the facile and efficient construction of C7-allylated indolic scaffold which are known as pivotal heterocyclic compounds found in a number of bioactive synthetic molecules and natural products.

Catalytic reactions of Ruthenium, Copper Nanoparticles and Rhodium Homogeneous Catalysts

김주현 서울대학교 대학원 2017 국내박사

Transition metal-catalyzed catalytic reaction is one of the most fundamental processes to construct the chemical structure. Depending on the type of transition metal catalysts, the catalytic reactivity is quite different. In the field of heterogeneous catalysts, nanoparticle catalysts have been attracted due to their unique reactivity and relatively simple process for reuse. Homogeneous catalysts have many advantages such as high reaction rate and selectivity to achieve catalytic reaction of fine chemicals. Thus, developing a unique catalytic reaction with transition metal catalysts is essential to expand the field of synthetic methods. This dissertation describes the development of catalytic reaction of transition metal nanoparticles and rhodium compounds. We discovered that ruthenium nanoparticle on non-activated charcoal is quite effective for constructing azobenzen derivatives which are useful materials of dyes and pigments. Furthermore, instead of hydrogen gas, ethanol is used as a hydrogen source. Three different products derived from nitroarene derivatives were obtained by changing the amount of ethanol. Copper is abundant and inexpensive metal than ruthenium metal. Using commercially available copper nanoparticles as a catalyst, cross-coupling reactions between alkyl halides with Grignard reagents were studied. The cross-coupling reaction did not require any phosphine or amine ligands and proceeded smoothly at room temperature. In particular, quaternary carbon center, being difficult to synthesize, was established in the presence of copper nanoparticle and tertiary alkyl Grignard reagents. Alcohol is one of the most common organic compounds in our lives. It is often used as a polar solvent in chemical reactions. As mentioned above, alcohol can be employed as a hydrogen source. In addition, the role of alcohol can be extended to a carbon monoxide surrogate, a hydride-donor, and a nucleophile in the presence of rhodium catalysts. In the synthesis of esters from aryl iodides and alcohols in the presence of a rhodium catalyst and a base, an alcohol acted as carbon monoxide and nucleophile. Alcohol acted as a hydride source to form a rhodium hydride intermediate and a carbon monoxide surrogate in intermolecular carbonylative cycloaddition reactions with alkyne.

Rhodium-bisphosphite complex를 이용한 Alkene의 비대칭 수소화 반응

김치현 建國大學校 大學院 1998 국내석사

본 실험에서는 광활성 리간드로 bisphosphite계 화합물을 전이금속으로 rhodium 유도체와 complex를 이루어 이것을 촉매로 사용하여 Dimethylitaconate와 α-amino cinnarnate게 화합물의 비대칭 수소화 반응에 이용하였다. 이 반응은 기질 대 촉매의 비는 최소 200에서 최대 1000까지 시도하였으며, 광학 수율은 77%에서 최대100%까지 비교적 높은 수율을 보였다. 리간드의 합성은 NMR을 통하여 확인하였고, 각각의 기질과의 반응성 및 광학 수율은 Gas Chromatography를 통하여 확인하였다. In this study, new class C_(2) symmetric bis(phosphite) ligands have been prepared and used in rhodium-catalyzed asymmetric hydrogenation of prochiral olefins. Cationic rhodium complexes bearing these new ligands behave as an effective catalyst for the asymmetric hydrogenation of prochiral substrates. Substrate-to-catalyst ratios of 200 were routinely used, and ratios of 1000 were possable. It was explained that rhodium-bis(phosphite) ligands complexes were effect ive catalysts for the asymmetric hydrogenation of prochiral alkenes.

Rhodium Catalyzed Carbocyclization and Stereoselective Cyclocarbonylation

이승엽 State Uinversity of New York at Stony Brook 2000 해외박사

The application of transition metals in organic synthesis has led to a number of new synthetic methods that allow for the efficient and elegant construction of complex carbocyclic and heterocyclic systems. The rhodium cluster, Rh4(CO)12 and Rh2Co2(CO)12, serve as excellent catalysts for the silylcarbocyclization (SiCaC) and carbonylative silylcarbocyclization (CO-SiCaC) of enynes. It has been demonstrated that the SiCaC reaction and the CO-SiCaC reaction are effective methods for the construction of synthetically useful substituted cyclopentane, tetrahydrofuran and pyrrolidine systems. The reactions show a broad range of functional group tolerance including esters, amines and alcohols. In addition, bicyclo[4.3.0] ring systems have been constructed by the SiCaC reaction of cyclohexenyl propargylmalonate. This reaction is accompanied by β-hydride elimination rather than reductive elimination process. Conditions to form either the SiCaC or CO-SiCaC product with high selectivity have been optimized. In the CO-SiCaC reaction, a combination of phosphite ligand addition and dilute reaction conditions has significantly improved the selectivity toward the CO-SiCaC product. A possible reaction mechanism has been proposed based on previous mechanistic studies. The rhodium-catalyzed silylcarbocyclization of alkynals and alkynaldimine gave the corresponding cyclized products. The reaction of enynes with a hydroborane or a hydrostannane using a rhodium catalyst failed to give the corresponding carbocyclization product. Rhodium complex-catalyzed arylation-carbocyclization of alkynal with trialkytin gave phenylmethylidene-1-cyclopentanol in good yields. The carbonylative carbotricyclization of dodec-ll-ene-l,6-diynes (33) and their heteroatom congeners in the presence of a Rh catalyst (1 mol %) and a hydrosilane (0.5 equiv.) under atmospheric pressure of CO gave the corresponding cyclopenta[e]azulenes (34) and their heteroatom congeners in good to excellent yields. Although the silyl group is not included in product, no reaction takes place after 72 h in the absence of a hydrosilane, recovering the starting enediyne. Thus, the hydrosilane proved to be necessary for this reaction to occur. A plausible mechanism for this novel carbonylative carbotricyclization is proposed. The rhodium-catalyzed carbocyclization reaction of diynal 37 was also investigated. The formation of three-ring system failed but two bicyclic compounds were isolated as products. The desymmetrization of meso-dienes by cyclocarbonylation has been investigated. The reaction of 4-amino-l,6-heptadiene with BIPHEPHOS gave 3'-formylpropyl-2,3,didehydropiperidine in excellent yield. The reaction with chiral ligand, (R,S)-BINAPHOS, also gave the desired cyclized products in good yield but the enantioselective reaction was not achieved. Even if the chiral induction occurs in the first hydroformylation step, the formation of meso-dialdehyde is faster than the cyclocondensation step. There is also a possibility of hemiamidal racemization during this reaction. Thus, new substrates were designed, which contain traps-phenyl substituted alkene groups instead of the terminal alkenes in the previous substrate. In the case of these substrates, the formation of the meso-dialdehydes was blocked and the initial stereoselectivity was kept in the next hydroformylation. Excellent diastereoselectivity as well as enantioselectivity were achieved (>95% ee, >98% de).

Pauson-khand reaction using cobalt carbonyl and N-heterocyclic carbene rhodium-catalyzed arylation/carbonylative arylation

최수영 서울대학교 대학원 2012 국내박사

Part I. Pauson-Khand Reaction Using Cobalt Carbonyl Chapter 1. Selectivity in Cobalt Carbonyl-Mediated Cycloaddition of Dienynes Dicobalt octacarbonyl-mediated cycloaddition of dienynes in the presence of carbon monoxide has been studied. Three main competing reaction routes, two carbonylative cycloaddition reactions and a Diels-Alder reaction, have been recognized depending upon the substrate and reaction conditions. Judicious design of the substrate and selection of reaction conditions allow control of the reaction pathway. Chapter 2. Sequential Diels-Alder and Cobalt Octacarbonyl Catalyzed Pauson-Khand Reactions in the Formation of Polycyclic Enones Sequential reactions of Diels-Alder and Pauson-Khand reactions between dienynes and dienophiles in a one-pot reaction have been demonstrated using 10 mol% dicobalt octacarbonyl. Synthesis of tetracyclic enones is reported. Part II. N-Heterocyclic Carbene Rhodium Catalyzed Arylation/Carbonylative Arylation Chapter 1. N-Heterocyclic Carbene Rhodium-Catalyzed Carbonylative C-C Bond Formation of Allenols with Arylboronic Acids under Carbon Monoxide (3-Butyl-1-methylimidazole)(1,5-cyclooctadiene)rhodium chloride [Rh(Ibm)(cod)Cl] was found to be an efficient catalyst in the carbonylative arylation of allenols with arylboronic acids in the presence of carbon monoxide. Efficient, simple, and versatile methods for the synthesis of 2-methylene-1-arylbut-3-en-1-ones have thus been developed. Chapter 2. Water-Soluble N-Heterocyclic Carbenes Having a Quaternary Ammonium Moiety: Application as Ligands to Rhodium Catalyst Water-soluble N-heterocyclic carbene ligands having a quaternary ammonium moiety were prepared by nickel nanopaticle-catalyzed C-Cl bond activation and coupling of α,ω-dichloroalkanes with triethylamine and a subsequent reaction with imidazoles. The NHC-rhodium complexes were active catalysts for hydroarylation of alkynes with arylboronic acids in toluene/H2O mixture at mild reaction condition. 제 1 부. 코발트 카보르닐을 사용한 Pauson-Khand 반응 제 1 장. 코발트 카르보닐에 의한 dienynes의 선택적 탄소고리화반응 일산화탄소 환경 하에 코발트 카르보닐에 의한 dienynes의 탄소고리화반응에 대하여 연구하였다. 세 가지 주요 경쟁 반응 경로인 두 종류의 카르보닐화 고리반응과 Diels-Alder반응이 반응조건과 반응기질에 따라 결정되는 것을 확인할 수 있었다. 반응물의 형태와 반응 조건을 조절하여 원하는 방향으로 생성물을 얻어낼 수 있었다. 제 2 장. 연속적인 Diels-Alder 반응과 코발트 카보닐 촉매를 사용한 Pauson-Khand 반응에 의한 polycyclic enones 형성 하나의 반응용기안에서 dienynes과 dienophiles을 10 mol%의 코발트 카르보닐 촉매와 함께 넣고 연속적으로 Diels-Alder 반응과 Pauson-Khand 반응을 진행하였다. 이 연속반응에 의해 tetracyclic enones의 합성이 이루어졌다. 제 2 부. N-Heterocyclic carbene 로듐 촉매를 사용한 아릴반응과 카르보닐화 아릴반응 제 1 장. 일산화탄소 존재 하에 N-Heterocyclic carbene 로듐 촉매에 의한 allenols과 아릴보론산 사이의 카르보닐화 탄소-탄소 결합 N-Heterocyclic carbene 로듐 촉매가 일산화탄소 환경 하에 allenols과 아릴보론산 간의 카르보닐화 아릴반응에 매우 효과적인 것을 발견하였다. 이 반응을 통해 다양한 형태의2-methylene-1-arylbut-3-en-1-one을 효과적이고 간단하게 만들어낼 수 있었다. 제 2 장. 네 개의 치환체로 이루어지는 암모늄 형태를 포함한 물에 녹는 N-Heterocyclic carbene : 로듐 촉매 리간드로의 응용 니켈 촉매에 의한 탄소-염소 결합 활성화를 통해 α,ω-dichloroalkanes과 트리에틸아민을 연결 반응하여 얻은 생성물과 imidazoles을 반응보내어 네 개의 치환체로 이루어지는 암모늄 형태를 포함한 물에 녹는 N-Heterocyclic carbene을 만들었다. 이 N-Heterocyclic carbenes을 리간드로 사용한 로듐 화합물을 합성하고 아릴보론산과 알카인의 아릴반응의 촉매로 사용하여 보았다.

Rhodium-catalyzed reactions using alcohol as a carbon monoxide, nucleophile, hydration and alkylating source

박하원 서울대학교 대학원 2017 국내석사

A CO-gas-free rhodium-catalyzed alkoxycarbonylation of aryl iodide with alcohols has been developed. Alcohols, with/without the aid of an aldehyde, were used as a carbon monoxide and nucleophile source. Moreover, atom economic rhodium-catalyzed synthesis of chiral α-alkylated ketone from alkyne with benzyl alcohols has been developed. Benzyl alcohols were used as a hydration and alkylation source.