Organometallic catalysis has attracted significant interest from both industry and academia due to its wide applications in organic synthetic transformations. Example of such transformations include the reaction of a zinc carbenoid with olefins to form cyclopropanes. The first project is a computational study using both density functional and correlated wavefunction methods of the reaction between ethylene and model zinc carbenoid, nitrenoid and oxenoid complexes (L-Zn-E-X, E = CH2, NH or O, L = X = I or Cl). It was shown that cyclopropanation of ethylene with IZnCH2I and aziridination of ethylene with IZnNHI proceed via a single-step mechanism with an asynchronous transition state. The reaction barrier for the aziridination with IZnNHI is lower than that of cyclopropanation. Changing the leaving group of IZnNHI from I to Cl, changes the mechanism of the aziridination reaction to a two-step pathway. The calculation results from the epoxidation with IZnOI and ClZnOCl oxenoids suggest a two-step mechanism for both oxenoids. Another important example of organometallic catalysis is the formation of alkyl arenes from arenes and olefins using transition metal catalysis (olefin hydroarylation). We studied with DFT methods the mechanism of a novel Rh catalyst (FlDAB)Rh(TFA)(η2–C2H4) [FlDAB = N,N’ -bis(pentafluorophenyl)-2,3-dimethyl-1,4-diaza-1,3-butadiene; TFA = trifluoroacetate] that converts benzene, ethylene and air-recyclable Cu(II) oxidants to styrene. Possible mechanisms are discussed.

In the last two decades, significant strides have been made towards utilizing the scanning tunneling microscope (STM) as a reaction chemistry tool, in addition to its primary use as an imaging instrument. Built off the STM, the STM-break junction (STM-BJ) technique was developed specifically for the reliable and reproducible measurement of properties of a single molecule suspended between two electrodes. These advances are crucial to the fields of molecular electronics and single-molecule reactivity, the latter also relating back to traditional bulk chemistry. By intelligently designing experiments and systems to probe with the STM and STM-BJ, we can begin to understand chemical processes on a deeper level than ever before. Chapter 1 provides an overview of the recent work using the STM and STM-BJ to effect chemical transformations which involve the making and breaking of bonds. We contextualize this progress in terms of single-molecule manipulation and synthetic chemistry, to understand the implications and outlook of this field of study. Seminal surface-based reactions are discussed, in addition to reactions that occur in both solution and within the single molecule junction. Differences between STM and STM-BJ capabilities and limitations are detailed, and the challenges of translating these fundamental experiments into functional reactions are addressed. Chapter 2 describes using the STM-BJ to study the binding of aryl iodides between gold electrodes. Important details regarding these binding modes, which were previously incompletely understood, are revealed via concrete experimental evidence. Our data suggests that this system, which is synthetically accessible, holds promise for forming the sought-after and highly conducting covalent gold-carbon bonds in situ and can be modulated with applied bias. Chapter 3 builds upon the knowledge gained in Chapter 2, and focuses on the reactivity of aryl iodides in the junction. We demonstrate a new in situ reaction of an Ullmann coupling, or dimerization, of various biphenyl iodides. By strategically designing the molecules studied, we are also able to gain mechanistic insight into this process, which in the bulk still remains debated, as well as demonstrate a cross-coupling reaction. This project is ongoing as of the submission of this dissertation, so other findings and continuing experiments are included. Chapter 4 transitions towards a different type of binder to gold, the cyclopropenylidene-based carbene. These amino-functionalized carbenes prove to be stronger linkers than N-heterocyclic carbenes, which are known binders to gold. Using a variety of surface analysis, imaging, and computational techniques, we explore the binding geometries and energies of cyclopropenylidenes, expanding the scope of carbene surface modifiers. Chapter 5 summarizes this body of PhD research, suggests directions for future work, and concludes the dissertation. These works explore the binding and reactivity of molecules on gold surfaces and within the single molecule junction, improving upon the understanding of this newly burgeoning field. This thesis seeks to encourage future work on these and related systems, to continue refining our comprehension of both junction and bulk reaction chemistry processes.

<p> Metal-stabilized carbenes, most commonly formed through the decomposition of  diazoacetates, are extensively employed in organic synthesis. However, several classes of carbenes,  such as vinylidenes, are challenging to utilize in transition metal catalysis due to the instability of  the required diazo precursors. To overcome this challenge, most transition metal-catalyzed  vinylidene transfer and insertion methods rely on alkynes as vinylidene precursors. Only catalysts  that form stable M=C multiple bonds and weak M(π-C≡C) interactions can promote this alkyne  isomerization, and the resultant metal(vinylidene) species is often less reactive compared to free  vinylidenes. The discovery of 1,1-dihaloalkenes as precursors to transition metal vinylidene  complexes has significantly expanded the scope of vinylidene transfer and insertion reactions.  Dinuclear catalysts were found to promote the reductive cyclization of 1,1-dichloroalkenes  containing pendant alkenes to form methylenecycloalkenes, and mechanistic studies are consistent  with the formation of a Ni2(vinylidene) species. Furthermore, these catalysts promote reductive  three-component cycloaddition reactions with 1,1-dichloroalkenes and aldehydes to generate  methylenedioxolanes, which upon treatment with aqueous acid provides access in one step to new,  unsymmetrical aliphathic α-hydroxy ketones that would be difficult to access with existing  methods. Under dilute conditions, an enone byproduct is formed and a DFT model is presented  that accounts for concentration-based reaction selectivity.</p>

京都大学 / 0048 / 新制・課程博士 / 博士(理学) / 甲第18093号 / 理博第3971号 / 新制||理||1572(附属図書館) / 30951 / 京都大学大学院理学研究科化学専攻 / (主査)教授 大須賀 篤弘, 教授 丸岡 啓二, 教授 時任 宣博 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

Methodologies for expanding the architectural diversity of -N-heterocyclic carbene (NHC) pincer ligand precursors and transition metal complexes have been developed for the production of more efficient catalyst, which will be employed in the synthesis of pharmaceuticals. An efficient route for the synthesis and isolation of bis-1,3-(3'-aryl-N-heterocycl-1'-yl)arenes has been established, and preliminary data for metalation and transmetalation of a N, N'-diaryl imidazolium salt has been acquired. Additionally, a proficient methodology for the synthesis of mixed, unsymmetrical -NHC pincer ligand precursors has been discovered, and preliminary data for mixed, unsymmetrical transition metal complexes is also included. These methodological expansions will lead to more efficient catalyst that decrease the expenditure of energy required for the synthesis of pharmaceuticals, thus making their synthesis more favorable for the environment and their price more affordable for consumers.

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With the advent of photoredox catalysis, new synthetic paradigms have been established with increasing numbers of novel transformations being achieved. Nevertheless, modern photoredox chemistry has several drawbacks in efficiency, scalability, and light penetration. In this dissertation, we document developments in photoredox catalysis that harvest red light (600- 800 nm) and demonstrate its applications in polymer science and chemical biology. First, a method towards the red-light activation and control of olefin metathesis will be discussed. This system employs a mixed, bis-N-heterocyclic carbene coordinated ruthenium indenylidene complex in conjunction with an osmium(II) complex under red light irradiation. Mechanistic investigation suggests a reduction of a cationic Ru species, to lead to the active metathesis species. Expectedly, polymerization through barriers is achieved with red light only. Material penetration, including mammalian tissue, and limited photocytotoxicity brings red light photoredox catalysis in the forefront of biological applications such as photoproximity labeling. This proceeds through the photocatalytic generation of reactive intermediates, the lifetimes of which dictate the spatial resolution of labeling. We thus describe a method to activate aryl(trifluoromethyl) diazos using an osmium(II) catalyst and red light, providing highly reactive, short-lived carbenes. The short lifetime of the carbene is highlighted by its ability to map small molecules to target proteins, a feat even nitrenes cannot achieve. Finally, efforts towards the synthesis of a wash-free fluorogenic photocatalyst with applications for intracellular red light photoproximity labeling will be described.

Electric fields influence reactions by stabilization of charge-separated transition states. While this has been a longstanding hypothesis supported computationally, recent experimental confirmations highlight the potential for leveraging electric field effects to drive small molecule reactions far from equilibrium. Herein we report electric-field catalysis of an alkane solvent-derived acylation reaction in the scanning tunneling microscope-break junction (STM-BJ), providing additional support for this hypothesis. Additionally, the design and reactivity of an internally charged zwitterionic ligand are disclosed. Synthetic access of metal ligands bearing opposing charged functional groups permitted the examination of stochiometric metalation and catalytic behavior of electric field-bearing ligands.While traditionally computation has been used to rationalize why a particular catalyst is successful descriptively, it has been rarely used to screen candidates and prescriptively provide optimal catalyst structure. We report a neural network-enabled catalyst screening platform that dramatically reduce the resource intensity for examining a large chemical space. We leverage this platform to examine azolium N-heterocyclic carbene (NHC) precursors to address the lack of compatibility for electron-rich aryl aldehydes in the NHC-catalyzed Stetter reaction. This led to the discovery of a new class of azolium NHC precursor: oxadiazoliums that proved competent in achieving the target reaction addressing current limitations in Stetter catalysis.

2-Phosphanyl-substituted imidazolium salts 2-PR2(4,5-Cl-Im)[OTf] (9a,b[OTf]) (4,5-Cl-Im = 4,5-dichloro-1,3-bis(2,6-di-isopropylphenyl)-imidazolium) (a: R = Cy, b: R = Ph) are prepared from the reaction of R2PCl (R = Cy, Ph) with NHC 8 (4,5-dichloro-1,3-bis(2,6-di-isopropylphenyl)-imidazolin-2-ylidene) in the presence of Me3SiOTf. 5-Phospanyl-substituted imidazolium salts 5-PR2(2,4-Cl-Im)[OTf] (10a,b[OTf]) are obtained in quantitative yield when a slight excess of the NHC 8 is used. 5-Phosphonio-substituted imidazolium salts 5-PR2Me(2,4-Cl-Im)[OTf]2 (14a,b[OTf]2) and 5-PR2F(2,4-Cl-Im)[OTf]2 (16a,b[OTf]2) result from methylation reaction or oxidation of 10a,b[OTf] with XeF2 and subsequent fluoride abstraction. According to our quantum chemical studies the Cl1 atom at the 2-position at the imidazolium ring of dication 14b2+ carries a slightly positive charge and is therefore accessible for nucleophilic attack. Accordingly, the reaction of 14a,b[OTf]2 and 16a,b[OTf]2 with R3P (R = Cy, Ph) affords cationic 5-phosphonio-substituted NHCs 5-PR2Me(4-Cl-NHC)[OTf] (17a,b[OTf]) and 5-PR2F(4-Cl-NHC)[OTf] (18a,b[OTf]) via a SN2(Cl)-type reaction. A series of transition metal complexes such as [AuCl(5-PPh2Me(4-Cl-NHC))][OTf] (19[OTf]), [CuBr(5-PPh2Me(4-Cl-NHC))][OTf] (20[OTf]), [AuCl(5-PPh2F(4-Cl-NHC))[OTf] (21[OTf]) and [RhCl(cod)(5-PPh2Me(4-Cl-NHC))][OTf] (23[OTf]) are prepared to prove the coordination abilities of carbenes 17b[OTf] and 18b[OTf]. The isolation of a rare example of a tricationic bis-carbene silver complex [Ag(5-PPh2Me(4-Cl-NHC))2][OTf]3 (22[OTf]3) is achieved by reacting 14b[OTf] with Cy3P in the presence of AgOTf. NHC 17b[OTf] represents a very effective dehydrocoupling reagent for secondary (R2PH, R = Ph, Cy, iBu) and primary (RPH2, R = Ph, Cy) phosphanes to give diphosphanes of type R4P2 (R = Ph, Cy, iBu) and oligophosphanes R4P4, R5P5 (R = Ph, Cy), respectively. Methylation of 17b+ and subsequent deprotonation reaction with LDA affords the cationic NHO (N-heterocyclic olefin) 35+ of which the gold complex 36+ is readily accessible via the reaction with AuCl(tht).