Dissertations / Theses on the topic 'Carbonyl halides'

[RhCl(CO)(Pet3)2] or a compound prepared in situ from [Rh2(OAc)4] and Pet3 have been shown to be active catalysts for the carbonylation of allylic halides under relatively mild conditions. This reaction is of considerable significance since it is a rare example of a system in which C-Cl bonds can be carbonylated using a rhodiun based system. The reaction occurs in the absence of added base and there is little isomerisation of the double bond when forming the ester. Using either 3-chlorobut-l-ene or l-clilorobut-2-ene, the products obtained are identical. The oxidative addition of 1-clilorobut-2-ene occurs via an S[sub]N2 mechanism whereas an S[sub]N2' mechanism operates for the 3-chlorobut-1-ene because of the steric effects of the methyl group adjacent to the chlorine. Extensive mechanistic studies have been carried out and many of the intermediates have been characterised using multinuclear variable temperature, high pressure NMR and high pressure IR as well as isolation of the intermediates. The oxidative addition and migratory insertion complexes have both been characterised using the above methods enabling the mechanism of the carbonylation reaction to be elucidated. Supercritical carbon dioxide has been used to replace ethanol as the solvent to increase the concentration of carbon monoxide in the solution in an attempt to achieve a greater ester:ether ratio. However, catalyst solubility was a problem in these reactions. In an attempt to solve this problem phosphine ligands containing organo-fluorine groups were investigated. With the fluorinated groups present on the phosphine ligands the rhodium complex was soluble in the supercritical carbon dioxide. The ethylene spacer between the phosphorus atom and the fluorinated chain ensured that the fluorinated phosphines had a similar basicity to that of triethylphosphine. However, only low yields were obtained from the catalytic reactions possibly due the failure of the supercritical carbon dioxide to stabilise the ionic intermediates of the oxidative addition reaction.

Los materiales compuestos por grafeno y nanotubos de carbono (CNTs) han despertado un amplio interés debido a sus propiedades excepcionales. La variación de éstas, empleando diversas técnicas de modificación aumentan sus aplicaciones potenciales en muchos campos. Ésta tesis describe la funcionalización de nanomateriales de carbono con nitrógeno y diversos haluros y óxidos. La modificación de la estructura de nanotubos de carbono multicapa (MWCNTs) y derivados de grafeno se llevó a cabo mediante reacciones sólido-gas y sólido-líquido. Hemos empleado diferentes métodos de funcionalización, que incluyen oxidación, funcionalización con nitrógeno y dopaje, así como modificaciones de las cavidades internas y superficies externas de los nanotubos de carbono, para modular las propiedades de las nanoestructuras preparadas. Mediante un estudio sistemático de las condiciones de tratamiento y una exhaustiva caracterización se determinaron las características estructurales de las muestras y se evaluaron algunas de sus propiedades fisicoquímicas. En ésta tesis proponemos un método simple, eficiente y reproducible para la síntesis de óxido de grafeno reducido (RGO) modificado con nitrógeno. La naturaleza de los átomos de nitrógeno dentro de la red del RGO se ha modulado mediante tratamientos de amonolísis de óxido de grafeno (GO) a temperaturas comprendidas entre 25 ˚C y 800 ˚C. El protocolo propuesto permite tanto la introducción de grupos funcionales alifáticos (funcionalización con N) como la de nitrógeno estructural (dopaje con N). Adicionalmente, la composición estructural de las muestras funcionalizadas y dopadas con nitrógeno se modificó mediante tratamientos posteriores empleando altas temperaturas y atmosferas no oxidantes. Éstos tratamientos provocan rearreglos internos que confieren mayor estabilidad térmica a los materiales. Por otro lado, se llevó a cabo el llenado de las cavidades y la decoración de las superficies externas de los MWCNTs con compuestos inorgánicos. Reportamos la formación de nanotubos inorgánicos monocapa dentro de los nanotubos de carbon empleando una técnica de capilaridad del material laminar en su fase fundida. Además, mediante la optimización de los parámetros experimentales conseguimos favorecer el crecimiento de éstos sistemas inorgánicos monocapa con respecto la formación de otras nanoestructuras, tales como, nanopartículas, nanobarras y nanoserpientes de los halogenuros empleados. Hemos descrito una nueva técnica para el aislamiento ó liberación de las sustancias previamente introducidas en las cavidades de los MWCNTs. Así, exploramos el uso potencial de los fulerenos como agentes aisladores o promotores de la liberación de estructuras huéspedes. Finalmente, hemos preparado MWCNTs decorados con óxidos de titanio reducidos empleando tratamientos a altas temperaturas. Mediante la oxidación de los nanotubos se obtuvieron “nanocollares” de titania libres de carbono. Los materiales soportados presentan una actividad fotocatalítica superior a la del material de referencia titania P25.
Graphene and carbon nanotubes (CNTs) are of wide interest in materials science due to their outstanding properties. Several approaches allow modulating their properties further expanding their potential applications in many fields. This thesis reports on the functionalization of carbon nanomaterials with nitrogen, halides and oxides. The modification of the structure of multiwalled carbon nanotubes (MWCNTs) and graphene derivatives has been carried out through solid-gas and solid-liquid reactions. Different methods of functionalization, which include oxidation, nitrogen functionalization and doping, as well as endohedral and exohedral modifications have been employed for tuning the properties of the prepared nanostructures. A systematic study of the conditions of treatment and an extensive characterization has allowed the determination of the structural characteristics of the samples and the evaluation of some of their physical and chemical properties. In this thesis we propose a simple, efficient and reproducible method for the synthesis of nitrogen-containing reduced graphene oxide (RGO). The nature of the nitrogen atoms within the RGO lattice has been tuned by ammonolysis treatments of graphene oxide (GO) in the range of 25 ˚C-800 ˚C. The reported protocol allows the introduction of aliphatic moieties (N-functionalization) and structural nitrogen (N-doping). Additionally, the structural composition of the N-containing RGO has been modified by post-annealing the material under non-oxidizing atmospheres. High temperature treatments induce internal rearrangements, leading to samples with an enhanced thermal stability. On the other hand, endohedral and exohedral functionalization of MWCNTs with inorganic materials have been carried out. We report on the formation of single-layered inorganic nanotubes within the cavities of MWCNTs through a molten phase capillary wetting technique. We have optimized the conditions of the synthesis to enhance the growth of the single-layered nanotubes, while decreasing the formation of other nanostructures (nanoparticles, nanorods and nanosnakes). A new technique for the confinement and/or release of the filled substances within the hollow cavity of the CNTs has also been developed. We have explored the potential of fullerenes as corking agents and as promoting species for the release of guest structures. Finally, we have prepared MWCNTs decorated with reduced titanium oxides employing high temperature treatments. By oxidation of MWCNTs self-standing titania “nano-necklaces” are formed. The photocatalytic performance of the carbon supported materials overpasses that of the reference material titania P25.

Metodologies fotocatalítiques sota irradiació de llum visible han estat desenvolupades amb diversos substrats disponibles al mercat com ara els àcids carboxílics, trifluoroboratos alquílics de potassi, silicats alquílics d'amoni o èsters activats entre d'altres. Sota irradiació de llum, aquests precursors s'activen mitjançant processos de transferència d'un sol electró amb catalitzadors fotoexcitables (PC). Entre ells, els halurs orgànics són socis d'acoblament convenients en la fotocatàlisi, ja que experimenten una escissió de l'enllaç C-halogen catalitzada per diversos PC en presència d'un donador d'electrons. Els clorurs de llogo no activats, que són fàcilment disponibles i matèries primeres estables, exhibeixen una inèrcia química inherent, en part, per les seves negatius potencials de reducció. Això va impedir el seu ús generalitzat com a precursors radicals en la fotocatàlisi de llum visible. En aquesta dissertació doctoral explorem l'ús d'un sistema catalític dual basat en metalls de la primera sèrie de transició (Cu, Co, Ni) per a l'activació d'aquests enllaços inerts C-Halogen. El disseny de l'catalitzador ha estat clau per desenvolupar una metodologia suau i general per a la reacció de desalogenación i la ciclació reductora intramolecular d'halurs d'alquil no activats amb alquens o alquins units. L'escissió de fortes enllaços Csp3-X està intervinguda per un intermedi de cobalt o níquel en baix estat d'oxidació altament nucleòfil generat per reducció fotocatalítica de llum visible que empra un fotosensibilitzador de coure.
Metodologías fotocatalíticas bajo irradiación de luz visible han sido desarrolladas con varios sustratos disponibles en el mercado como por ejemplo los ácidos carboxílicos, trifluoroboratos alquílicos de potasio, silicatos alquílicos de amonio o ésteres activados entre otros. Bajo irradiación de luz, estos precursores se activan mediante procesos de transferencia de un solo electrón con catalizadores fotoexcitables (PC). Entre ellos, los haluros orgánicos son socios de acoplamiento convenientes en la fotocatálisis, ya que experimentan una escisión del enlace C-halógeno catalizada por varios PC en presencia de un dador de electrones. Los cloruros de alquilo no activados, que son fácilmente disponibles y materias primas estables, exhiben una inercia química inherente, en parte, debido a sus negativos potenciales de reducción. Esto impidió su uso generalizado como precursores radicales en la fotocatálisis de luz visible. En esta disertación doctoral exploramos el uso de un sistema catalítico dual basado en metales de la primera serie de transición (Cu, Co, Ni) para la activación de estos enlaces inertes C-Halógeno. El diseño del catalizador ha sido clave para desarrollar una metodología suave y general para la reacción de deshalogenación y la ciclación reductora intramolecular de haluros de alquilo no activados con alquenos o alquinos unidos. La escisión de fuertes enlaces Csp3-X está mediada por un intermedio de cobalto o níquel en bajo estado de oxidación altamente nucleófilo generado por reducción fotocatalítica de luz visible que emplea un fotosensibilizador de cobre.
Visible light photoredox Catalysis have been accomplished with several readily available bench-stable chemicals such as carboxylic acids, potassium alkyltrifluoroborates, ammonium alkyl silicates or redox-active esters among others. Under light irradiation, these precursors get activated by single-electron transfer processes with photoexcitable catalysts (PCs). Among them, organic halides are convenient coupling partners in photocatalysis since they undergo reductive C-halogen bond cleavage catalysed by several PCs in the presence of a sacrificial electron-donor. Non-activated alkyl chlorides, which are readily available and bench-stable feedstocks, exhibit an inherent chemical inertness, in part, due to their large negative reduction potentials. This precluded their widespread use as radical precursors in visible-light photocatalysis. In this doctoral dissertation we explored the use of a dual catalyst system based on first-row transition metals (Cu, Co, Ni) for the activation of these inert Carbon-Halogen bonds. Catalyst design has been key for developing a mild and general photoredox methodology for the dehydrodehalogenation reaction and the intramolecular reductive cyclization of non-activated alkyl halides with tethered alkenes or alkynes. The cleavage of strong Csp3-X bonds is mediated by a highly nucleophilic low-valent cobalt or nickel intermediate generated by visible-light photoredox reduction employing a copper photosensitizer

Durant ma thèse, j'ai recherché les conditions pour l'activation / fonctionnalisation de liaisons C-H pour la construction de bi(hétéro)aryles tolérant des groupement fonctionnels réactifs tels que des silyles, des alcènes, des esters ou encore des amides. Par rapport aux protocoles de couplage classiques tels que les réactions de Suzuki, Stille ou Negishi, la fonctionalisation de liaisons C-H fournit des procédures moins coûteuses et plus écologiques si elle tolère des groupements utiles en synthèse. D'abord, nous avons observé que les thiophènes substitués par des silyles en C2 peuvent être arylés avec des bromures d'aryle sans désilylation en présence du précatalyseur Pd(OAc)2/dppb. Les produits de couplage sont obtenus avec de bons rendements et avec inhibition de la réaction de désilylation. Ensuite, nous avons démontré que le système Pd(OAc)2/KOAc sans ligand phosphine, favorise l'arylation directe des hétéroaromatiques et inhibe la réaction de type Heck avec des thiophenes substitués par des alcènes substituées sur les carbones 2 ou 3. Ensuite, nous avons démontré que les fonctions esters sur les hétéroaromatiques peuvent être avantageusement utilisées comme groupements protecteurs, permettant l'arylation directe d'hétéroaromatiques sur le carbone C5. Enfin, l'heteroarylation directe de 2- ou 4-bromobenzamides avec des hétéroarènes catalysée au palladium a été étudiée. En présence de KOAc comme base, aucune formation de liaisons C-C ou C-N par couplage de deux bromobenzamides n'a été observée
During my thesis, I focused on condition for the activation / functionalisation of C-H bonds for the construction of biaryl derivatives tolerant to the reactive functional groups such as silyl, alkenes, esters or amides. Compared to classic cross-coupling protocols (Suzuki, Stille or Negishi), C-H bond functionalisation provides a costly effective and environmentally attractive procedures. At first, we observed that the silyl-substituted thiophenes can be directly arylated with aryl bromides without desilylation, using the simple Pd(OAc)2/dppb precatalyst for both conversion and desilylation inhibition. Then, we have demonstrated that the Pd(OAc)2/KOAc catalyst system without phosphine ligand, even using as few as 0.1 mol% of Pd catalyst, promotes the direct arylation of heteroaromatics and inhibits the Heck type reaction with 1,2-disubstituted alkenes. In addition, we demonstrated that easily accessible esters on heteroaromatics can be advantageously employed as blocking groups in the course of the direct arylation of several heteroaromatic derivatives. Finally, the palladium-catalyzed direct heteroarylation of 2- or 4-bromobenzamide with heteroarenes was studied. In the presence of KOAc as the base, no formation of C-N or C-C bonds by coupling of two bromobenzamide was observed

La photoréduction atmosphérique du Hg pourrait avoir lieu à la fois en phase gazeuse et aqueuse. Les taux de photoréduction du Hg(II) que nous observons dans l'eau de pluie, en condition d'ensoleillement total, sont d'un ordre de grandeur inférieur au taux optimisé de photoréduction dans les nuages >1.0 h-1 dans les modèles globaux de mercure. La photoréduction aqueuse de mercure dans l'atmosphère est trop lente pour constituer une voie de réduction dominante. Les formes HgBr2, HgCl2, HgBrNO2, HgBrHO2 gazeuses atmosphériques, balayées par les aérosols aqueux et les gouttelettes de nuages, sont converties en formes de Hg(II)-DOC dans les précipitations en raison de l'abondance de carbone organique dans les aérosols et de l'eau de nuages. Des calculs théoriques montrent que les taux de photolyse en phase gazeuse de composés de mercure(II) peuvent être suffisamment rapide pour rééquilibrer le cycle de mercure atmosphérique modélisé
Atmospheric Hg photoreduction could take place in both gas- and aqueous phase. Rainwater Hg(II) photoreduction rates, under fully sunlit conditions, are an order of magnitude slower than the optimized maximum in-cloud photoreduction rate of > 1.0 h-1 in global Hg models. Atmospheric aqueous Hg photoreduction is too slow to be dominant reduction pathway. Atmospheric gaseous HgBr2, HgCl2, HgBrNO2, HgBrHO2 forms, scavenged by aqueous aerosols and cloud droplets, are converted to Hg(II)-DOC forms in rainfall due to abundant organic carbon in aerosols and cloud water. Computation of gas phase photolysis rates of Hg(II) compounds can be fast, and is fast enough to rebalance the modeled atmospheric Hg cycle between Hg(0) oxidation and Hg(II) reduction

Au cours de cette thèse, nous nous sommes intéressés à l'activation de liaisons sp² et sp³ C-H catalysée par le palladium pour la préparation d'(hétéro)aryl-aryles et de biaryles. Cette méthode est considérée comme attractive pour l'environnement par rapport aux méthodes classiques, tels que Suzuki, Heck, ou Negishi. Tout d'abord, nous avons décrit que la C2-arylation directe de benzothiophènes peut être effectuée par un catalyseur du palladium en l'absence de ligand phosphine avec une grande sélectivité. Nous avons également démontré qu'il est possible d'activer les positions C2 et C5 de pyrroles pour accéder en une seule étape a des 2,5-diarylpyrroles. Des 2,5-diarylpyrroles non-symétriques ont été formés par arylation séquentielle en C2 suivie par une arylation en C5. Nous avons également étudié la réactivité de polychlorobenzenes pour l'activation de liaisons C-H catalysé au palladium. Nous avons finalement étudié l'activation sp² et sp³ sélective catalysé au palladium de liaisons C-H du guaiazulene. La sélectivité de la réaction dépend du solvant et de la base : C2-arylation (KOAc en éthylbenzène), C3-arylation (KOAc dans le DMAc) et C4-Me arylation (CsOAc/K₂CO₃ dans le DMAc). Grâce à cette méthode, une liaison sp³ C-H peu réactive a été activée
During this thesis, we were interested in the sp² and sp³ C-H bond activation catalyzed by palladium catalysts for the preparation of (hetero)aryl-aryls and biaryls. This method is considered as cost effective and environmentally attractive compared to the classical couplings such as Suzuki, Heck, or Negishi. First we described the palladium-catalyzed direct C2-arylation of benzothiophene in the absence of phosphine ligand with high selectivity. We also demonstrated that it is possible to active both C2 and C5 C-H bonds for access to 2,5-diarylated compounds in one step, and also to non-symmetrically substituted 2,5-diarylpyrroles via sequential C2 arylation followed by C5 arylation. We also studied the reactivity of polychlorobenzenes via palladium-catalyzed C-H activation. We finally examined the palladium-catalysed selective sp² and sp³ C-H bond activation of guaiazulene. The selectivity depends on the solvent and base: sp² C2-arylation (KOAc in ethylbenzene), sp² C3-arylation (KOAc in DMAc) and sp³ C4-Me arylation (CsOAc/K₂CO₃ in DMAc). Through this method, a challenging sp³ C-H bond was activated

碩士
國立師範大學
化學學系
81
[Et4N]2[PbFe3(CO)12] 和鹵化烷 MeI, EtI, PhCH2Br以及 iPrI 的反 應, 皆生成陰離子化合物 [Et4N]2[Pb{Fe- (CO)4}2{Fe2(CO)8}], 而和 MeI, PhCH2Br 反應有酮類化合物出現. [Et4N]3[BiFe4(CO)16] 和 PhCH2 COCl, CH3(CH2)5COCl ,(MeCO)2O 以及 MeC(O)OEt 的反應, 沒有酮類化 合物出現.與 PhCH2COCl, CH3(CH2)5COCl 反應生成化合物 [Et4N]2- [ClBiFe3(CO)12]; 而和 (MeCO)2O 及 MeC(O)OEt 的反應,生成氧化產物 [Et4N]2[Bi2Fe4(CO)13]. [Et4N]3[BiFe4(CO)16] 和 Cl(CH2)3Cl, ClCH2 CHClCH3, Br(CH2)2Br 以及 Cl(CH2)3Br 的反應, 沒有酮類化合物產生, [Et4N]3[BiFe4(CO)16] 不與 Cl(CH2)3Cl, ClCH2CHClCH3產生反應, 若加 熱時即氧化為 [Et4N]2[Bi2Fe4(CO)13].而與 Br(CH2)2Br 的反應沒有烷 基化的產物出現. 然而與 Br(CH2)3Cl 的反應, 可得到烷基化的產物 [Et4N]2- [Cl(CH2)3BiFe3(CO)12], 再加入醋酸酸化後得到中性化合物 Bi2Fe2(CO)8[(CH)3Cl]2. [Et4N]3[BiFe4(CO)16] 和 PhCH2Cl 的反應, 生成陰離子化合物 [Et4N]2[PhCH2BiFe3(CO)12], 再加入醋酸後得到中性 化合物 Bi2Fe2(CO)8(CH2Ph)2. Reaction of [Et4N]2[PbFe3(CO)12] with MeI or PhCH2Br forms [Et4 N]2[Pb{Fe(CO)4}2{Fe2(CO)8}] and the corresponding ketones. However, [Et4N]2[PbFe3- (CO)12] reacts with EtI, iPrI gives [Et4 N]2[Pb- {Fe(CO)4}2{Fe2(CO)8}] as the major product. The reaction of [Et4N]3[BiFe4(CO)16] with PhCH2- COCl, CH3(CH2)5 COCl, (MeCO)2O or MeC(O)OEt does not produce ketone, while the treatment with PhCH2COCl or CH3(CH2)5COCl gives the ionic complexe [Et4N]2- [ClBiFe3(CO)12]. In addition, the reaction with (MeCO)2O, MeC(O)OEt leads to the formation of oxidation product [Et4N]2[Bi2Fe4(CO)13]. Furthermore, [Et4N]3[BiFe4(CO)16 ] reacts with Cl(CH2)3Cl or ClCH2CHClCH3 to produce the oxidation product [Et4N]2[Bi2Fe4(CO)13]. The reaction with Cl( CH2)3Br produces [Et4N]2[Cl(CH2)3BiFe3(CO)12] which reacts with HOAc to give Bi2Fe2(CO)8[(CH2)3Cl]2. Besides, [Et4N]2[BiFe4( CO)16] reacts with PhCH2Cl to form the ionic complex [Et4N]2 [PhCH2BiFe3(CO)12]. Further acidification of the ionic complex gives the neutral complex Bi2Fe2(CO)8(CH2Ph)2.

D.Sc. (Chemistry)
The aim of this study was to develop new methodology for the transformation of unsaturated carbohydrates utilising organometallic compounds. The first half of the study was directed toward developing a general synthesis of complex allyltins and in determining their application to carbon-carbon bond formation. It was decided to utilise carbohydrate substrates in this regard to develop a novel method of producing glycosides...

Chapter 1: Metal carbenoids in organic synthesis The chapter describes the phenomena of metal carbenoid insertion reactions in two parts: Part A, and Part B. The study of N-tosylhydrazones as diazo precursor was commenced by Jose Barluenga in 2007,1 which demonstrated an in-situ generation of diazo species and trapping of that with low valent palladium catalyst (Scheme 1). Later, this palladium-carbenoid assumption was supported by few reports. Some of these discoveries were by D. F. Taber in 1986 followed by van Vranken in 1999 & 2001.2 These studies of palladium carbenes were supplemented by several groups in subsequent years. The consequent developments with N-tosylhydrazones as diazo source were very fruitful and produced exceptional chemical transformations in recent years. Though the precursor is also vastly customary for other metals such as Cu, Ni, Rh and Co, the primary focus has been given to Pd catalysis due to its wide utility and applicability. 1) Barluenga, J.; Moriel, P.; Valdes, C.; Aznar, F. Angew. Chem., Int. Ed. 2007, 46, 5587. 2) (a) Taber, D. F.; Amedio, J. C., Jr.; Sherrill, R. G. J. Org. Chem. 1986, 51, 3382. (b) Hoye, T. R.; Dinsmore, C. J.; Johnson, D. S.; Korkowski, P. F. J. Org. Chem. 1990, 55, 4518. (c) Greenman, K. L.; Carter, D. S.; Van Vranken, D. L Tetrahedron 2001, 57, 5219. 3) Palladium catalysed coupling of tosylhydrazones with aryl and heteroaryl halides in the absence of external ligands: synthesis of substituted olefins, Ojha, D. P.; Prabhu, K. R. J. Org. Chem., 2013, 78, 12136. Modes of reactivity of a metal-carbene Scheme 1 Cascade carbene migratory insertion process Part A: Ligand-free coupling of tosylhydrazones with aryl & heteroaryl halides In this part, Palladium catalysed cross-coupling reaction of hydrazones with aryl halides in absence of an external ligand is reported. The versatility of this coupling reaction has been demonstrated by showcasing the selectivity of coupling reaction in presence of hydroxyl and amine functional groups. This method allows synthesizing a variety of heterocyclic compounds, which are otherwise difficult to access from traditional methods. Application of the present methodology is validated in tandem reaction of ketones to the corresponding substituted olefins in a single pot experiment. Few examples are illustrated below in Scheme 2.3 Scheme 2: Scope of aryl halide coupling with tosylhydrazones Part B: Pd-catalysed Synthesis of Highly Branched Dienes The regioselective formation of highly branched dienes is a challenging task. Design and exploration of alternative working models to achieve such a regioselectivity to accomplish highly branched dienes is considered to be a historical advancement of Heck reaction to construct branched dienes. On the basis of the utility of carbene transfer reactions, in the reaction of hydrazones with Pd(II) under oxidative conditions, we envisioned obtaining a Pd-bis-carbene complex with α-hydrogens, which can lead to branched dienes. Herein, we report a novel Pd catalyzed selective coupling reaction of hydrazones in presence of tert-BuOLi and benzoquinone oxidant to form corresponding branched dienes (Scheme 3).4 The utility of the Pd catalyst for cross-coupling reactions for synthesizing branched conjugated dienes are rare. The reaction is very versatile and compatible with a variety of functional groups and is useful in synthesizing heterocyclic molecules. We anticipate that this Pd-catalyzed cross-coupling reaction will open new avenues for synthesizing useful compounds. 4) Pd-catalyzed cross-coupling reactions of hydrazones: regioselective synthesis of highly branched dienes, Ojha, D. P.; Prabhu, K. R. J. Org. Chem., 2012, 77, 11027. 5) Furrow, M. E.; Myers, A. G. J. Am. Chem. Soc. 2004, 126, 5436. 6) Taber, D. F.; Guo, P.; Guo, N. J. Am. Chem. Soc. 2010, 132, 11179. Scheme 3: diene synthesis via bis-carbene insertion process Chapter 2: Tosylhydrazones: Role in modern day organic synthesis In recent days, hydrazone based reactions are focused on the donor-acceptor ability of the hydrazones or the in-situ generated diazo species (Scheme 4). This commenced with the Myers’s report in 2004,5 which simplifies the Barton vinyl halide preparation with a remarkable revision on synthesis of alkyl-silyl-hydrazones and its applications. Improved methods of using tosylhydrazones were demonstrated by Aggarwal in successive years. Cycloadditions were implemented by Douglass F. Taber. 6 This study was enriched in a quite fascinating way by several groups such as Jose Barluenga, with many reductive coupling reactions and 1, 3-dipolar reactions. Thomson, in a very interesting report shows the traceless petasis reaction with hydrazones and also worked in many other prospects such as three component reactions and the acid catalysed [3+3] sigmatropic reactions of hydrazones. 7 Wang has also impressed with very attractive transformations in the past decade. 8 7) Thomson, R. J. et al. Nat. Chem. 2009, 1, 494. 8) Xiao, Q.; Zhang, Y.; Wang, J. Acc. Chem. Res. 2012, 46, 236. 9) Regioselective Synthesis of vinyl halides, vinyl sulfones, and alkynes: A tandem intermolecular nucleophilic and electrophilic vinylation of tosylhydrazones, Ojha, D. P.; Prabhu, K. R. Org. Lett. 2015, 17, 18. Scheme 4: Trapping diazo species in intermolecular fashion Part A: Synthesis of vinyl halides Trapping diazo species in an intermolecular fashion by attack of two independent ions (a cation followed by an anion) in tandem at the carbene center is unprecedented. As part of our efforts on the utility of tosylhydrazones, herein we report a novel approach of using ambiphilic diazo species to perform a tandem attack of a nucleophile followed by an electrophile in an intermolecular fashion for synthesizing various types of vinyl halides. A few representative examples are shown in Scheme 5.9 Scheme5: Synthesis if vinyl halides Part B: Synthesis of vinyl sulfones Vinyl sulfones are potential synthetic targets due to their presence in biologically and pharmaceutically important molecules ranging from small natural metabolites to proteins, and have found widespread applications in biological research as covalent protease inhibitors. Vinyl sulfones represent one of the important sulfur containing functional groups in organic chemistry, which are generally synthesized through elimination reactions, oxidation of vinyl sulfides or witting reactions using multistep sequence. Following this technique, we were able to synthesize a variety of vinyl sulfones with rich mechanistic features in a single step. A few such examples are documented in Scheme 6.9 Scheme 6: synthesis of vinyl sulfones Part C: Synthesis of alkynes The functional group conversion to achieve alkyne frameworks are generally a difficult transformation. There are very few limited and tedious processes are available in literature, mainly containing multi-step procedures. Additionally these reactions are require harsh conditions. Considering all these factors, there is a need for developing methods to synthesize alkynes from common functional groups under mild reactions conditions. In a similar way, to introduce different halogens at the same carbon, we expected the eliminations of the leaving groups in tandem formed alkynes. After extensive screening studies, it was pleasing to find that the reaction of tosylhydrazones with NCS−BTEAC, NBS−TBAB, or NIS−TBAI combination in presence of K2CO3 in dioxane as solvent at 110 °C can furnish corresponding acetylene derivatives in good yields. Few examples are shown in Scheme 7.9 Scheme 7: Trapping diazo species in intermolecular fashion Chapter 3: Pd catalysed hydroboration This chapter shows a hydroboration study of terminal alkynes in a highly regioselective manner (Scheme 8). Organoboron derivatives have become essential intermediates in organic and medicinal chemistry. Pioneering contributions are made by Brown and Akira Suzuki, who both instigated the development of new synthetic tools for the introduction of boron atoms onto organic molecules. 10 10) (a) Barbeyron, R.; Benedetti, E.; Cossy, J.; Vasseur, J.-J.; Arseniyadis, S.; Smietana, M. Tetrahedron 2014, 70, 8431. (b) Miyaura, N.; Suzuki, A. Chem. Rev. 1995, 95, 2457. 11) Pd-Catalysed regioselective borylation of alkynes: A ligand controlled synthesis of α- and β vinyl boronates (manuscript submitted). Scheme 8: possibility of site selectivity in hydroboration Part A: Pd-catalysed regioselective borylation of alkynes: A ligand controlled synthesis of α and β – vinyl boronates The metal catalyzed borylations of alkynes proceeds in a two-step process. Initially M-Bpin species undergo an addition onto the alkynes to generate organometallic species followed by quenching of the organometallic species with electrophiles. The addition M-Bpin species is regioselective governed by the steric and electronics factors of both metal complex as well as alkyne substituents. In this direction, a palladium catalysed α-selective borylation was achieved for terminal alkynes. A broad range of substrates were successfully borylated under optimized reaction conditions with very high selectivity. Interestingly, the selectivity was reversed to terminal site by using a NHC ligand. A few examples are shown in Scheme 9.11 Scheme 9: α & β-vinyl boronates Chapter 4: Pd/borane unit: Behavior towards isomerization vs reduction of alkenes This study presents a unique behaviour of palladium-boronate unit responsible for olefin chain walking and olefin reduction reactions (Scheme 10). The catalytic system stands efficient against both functionalized and unfunctionalized olefin isomerization as well as reductions. This study has been presented in two parts. Scheme 10: isomerization vs reduction Part A: Pd/ boronates or borane unit as efficient catalytic systems for olefin chain walk This study presents the behaviour of palladium-boronate unit responsible for olefin chain walking. The catalytic system is efficient for both functionalized and unfunctionalized olefin isomerizations (Scheme 11). Cycloisomerization of transient conjugated alkenes to synthesize heterocycles are prominent applications of this technique. The system describes a concept of olefin activation by coordination with Pd-borane complex, this complex assists in a facile [1,3]-hydride shift. This technique allows us to facilitate an isomerization in functionalized as well as unfunctionalized olefinic systems. Considering the substrates scope, the catalytic cycle tolerates various sensitive functional groups and shows good selectivity. In the following Scheme 11 few examples are depicted.12 12) Palladium/boron catalytic unit for olefin chain-walk (manuscript under preparation). Scheme 11: chain-walking of olefins. Part B: Palladium catalysed boronate promoted alkene reduction in water In this work, water has been employed as a source of hydrogen. The reduction of alkenes was achieved using Pd catalyst in presence of bis(pinacolato)diboron and H2O. In this aspect, the utility of water as hydrogen equivalent is the pertinent as well as beneficial with many advantages. Few representative examples are shown in Scheme 12.13 13) Pd-Catalysed homogeneous hydrogenation of olefins by using water as hydrogen source (manuscript under preparation). Scheme 12: synthesis of alkenes reduced products.