Alkanes Research Articles

Geochemistry and accumulation of the ultra-deep Ordovician oils in the Shunbei oilfield, Tarim Basin: Coupling of reservoir secondary processes and filling events

Ultra-deep (7300 m–8900 m) condensed and volatile oil reservoirs have been discovered in the Ordovician reservoirs of the Shunbei oilfield, in the Tarim Basin. This study describes the petroleum accumulation process in the Shunbei oilfield by combining an analysis of its geochemical characteristics with seismic section observations and an analysis of petroleum filling events. Geochemical techniques are used to determine the sources, maturity, secondary processes, accumulation periods, and timing of petroleum filling. Analysis of fluid inclusion homogenization temperatures and burial-thermal histories indicates distinct petroleum filling events. Specifically, the north sub-section of the No. 5 fault zone experienced two petroleum filling periods during the late Caledonian and Indosinian epochs while the No. 1 fault zones and the mid-south sub-sections of the No. 5 fault zones experienced three distinct filling periods, encompassing the late Caledonian, Indosinian, and Himalayan periods. The CO2 concentrations and δ13CCO2 values suggest the presence of secondary microbial gases, primarily thermogenic gases. Gas component analysis reveals a transition from kerogen degradation gas to oil cracking gas from north to south. The detection of intact n-alkanes and compounds of the 25-norhopanes series in oil samples suggests a mixture of early biodegradable oil with late fresh oil in the area. Seismic sections reveal diabase intrusions with strong axial reflections. Local hydrothermal activities during the Permian era rapidly cracked saturated hydrocarbon biomarkers, forming polycyclic aromatic hydrocarbons in the oil. Hydrothermal activity in the south sub-section of the No. 5 fault zone depleted the hydrocarbon-generating capacity of the underlying source rocks. Petroleum charged during the Indosinian period likely originated from potential petroleum reservoirs in the Cambrian system. This explains the comparatively low temperature of the SHB57X reservoir (163.32 °C) and the lack of strong hydrothermal activity in the late stage, but no biomarkers of the second-stage charged oil have been detected. Biomarker detection and gas genesis in the mid-south sub-section of the No. 5 fault zone and in the No. 1 fault zone suggest weak or no hydrothermal activity, with Cambrian source rocks maintaining their hydrocarbon generation capacity. Gas filling in the Himalayan period caused evaporative fractionation in the original reservoirs, resulting in a disproportionate (2-MH+2,3-DMP)/(3-MH+2,4-DMP), producing high K1 values in the light hydrocarbons in the present petroleum reservoirs. Differences in gas charging events in the Himalayan period led to the present distribution of petroleum phases.

Effects of gamma radiation on cyclic olefin copolymers with varied norbornene content: Impacts on structure and properties at sterilization doses

Cyclic olefin copolymer (COC) is a transparent amorphous plastic known for its chemically inertness, biocompatibility, low density, and easy processability. These qualities have led to its widespread adoption in various cutting-edge applications, including the medical, packaging, optical and microelectronics. Radiation sterilization, utilizing high-energy irradiation, is a method for achieving highly effective sterilization of medical products. However, this process can induce changes in the color and properties of the COC materials. In order to comprehend the effects of ionizing radiation on COC, it is crucial to investigate the underlying reaction mechanisms. In this work, the effects of γ-ray irradiation on COC with different norbornene contents were examined. The finding revealed that tertiary alkyl radical content and the degree of oxidative degradation increased with an increase in norbornene content. Furthermore, the macroscopic properties experienced notable shifts, including decreased thermal stability, lower glass transition temperature and the change in color from colorless and transparent to yellow-green. Analysis of the melt index indicated a dominance of cross-linking phenomena with increased absorbed dose for COC with a norbornene content of 35%, while the melt flow rate steadily accelerated with the increase of absorbed dose for COC with norbornene content of 46%, 52% and 57%, leading to a predominant cracking behavior. The variation in tensile properties of the four COCs before and after irradiation were minimal, not exceeding 3%. Overall, this investigation sheds light on the intricate effects of ionizing radiation on COC and highlights the importance of understanding these mechanisms for practical applications.

Generation of abnormal distributions of inter- and intramolecular δ13C compositions in hydrocarbons from gold tube pyrolysis of an Australian torbanite

Abnormal stable carbon isotopic (δ13C) compositions, deviating from the conventional order of δ13C1 < δ13C2 < δ13C3, are frequently observed in natural gas reservoirs. For thermogenic gas, these anomalies, such as δ13C1 < δ13C3 < δ13C2 or δ13C1 > δ13C2 > δ13C3, have multiple formation mechanisms including gas mixing in conventional systems and desorption processes of gaseous hydrocarbons in unconventional shale gas systems due to their inconsistency with Rayleigh fractionation processes. Considering distinct reaction pathways (e.g., C1 polymerized to C2), these aberrant δ13C signatures are often construed as intrinsic hallmarks of extensively evolved natural gas. However, on the basis of gas generation simulation, not all findings exhibit abnormal δ13C values, hinting at multifaceted and intricate mechanisms governing the isotopic fractionation of alkane gas components. This study conducted gold tube pyrolysis of an Australian torbanite, revealing four distinct types of δ13C anomalies in hydrocarbon classes. Polycyclic aromatic hydrocarbons (PAHs) exhibited δ13C values more negative than co-occurring n-alkanes. δ13C3 displayed a negative trend shift from EasyRo = 3.5 %, resulting in a partially δ13C-reversed gas (δ13C1 < δ13C3 < δ13C2) formed at EasyRo ≈ 4.1 %. Moreover, intramolecular δ13C3 (both terminal and central carbons, termed δ13Ca and δ13Cb, respectively) reversed alongside the overall δ13C3 trend. Additionally, the evolution of site preference in δ13C3 (termed ‰SP = δ13Ca – δ13Cb) transitioned from progressively negative to positive. The results of this study demonstrate that the potential conversion between saturated hydrocarbons, aromatic hydrocarbons, and alkane gases is at least partially responsible for δ13C anomalies, but also that gaseous hydrocarbons formed from other fractions at high maturity cannot be ruled out, such as kerogen and pyrobitumen.

Analytical monitoring of harmful chemicals in the air of the working area of main pipeline transport facilities for oil and petroleum products

RATIONALE: At main pipeline transport facilities, the entry of harmful chemicals into the air of the working area can negatively affect the body of workers. The absence in the existing regulatory documents of clearly formulated criteria for the selection of specific harmful chemical compounds to control their content, especially if they are a multicomponent mixture, introduces certain difficulties in identifying pollutants in the air of the work area. The presence of criteria will allow the employer to correctly draw up a production program, the frequency of laboratory tests to obtain more objective and reliable information about the potential harmful effects of chemicals on workers and timely take measures to prevent their negative effects. AIM: Justification of the list of harmful substances for analytical monitoring of their content in the air of the working area of main pipeline transport facilities for oil and petroleum products. MATERIAL AND METHODS: Qualitative and quantitative analysis of the air in the working area was carried out at 12 oil pumping stations and 5 oil product pumping stations located in Russia. RESULTS: Using chromatography-mass spectrometry, the composition of the gas-air environment formed as a result of oil evaporation was determined, which made it possible to determine a list of harmful chemicals for further planned analytical monitoring of their content in the air of the working area.CONCLUSION: Sampling should be carried out in places with the highest probability of gas emissions into the air. When transporting oil, it is necessary to establish strict analytical control at workplaces over the content of aliphatic saturated hydrocarbons C2-C10, dihydrosulfide mixed with hydrocarbons, benzene in the air, when pumping petroleum products - benzene, gasoline or kerosene, i.e. depending on the type of petroleum product transported.

New molecular and macroscopic understandings of novel green chemicals based on Xanthan Gum and bio-surfactants for enhanced oil recovery

This research investigates the interactions between a novel environmentally friendly chemical fluid consisting of Xanthan gum and bio-based surfactants, and crude oil. The surfactants, derived from various leaves using the spray drying technique, were characterized using Fourier-transform infrared (FTIR) spectroscopy, zeta potential analysis, Dynamic light scattering, and evaluation of critical micelle concentration. Static emulsion tests were conducted to explore the emulsification between crude oil and the polymer-surfactant solution. Analysis of the bulk oil FTIR spectra revealed that saturated hydrocarbons and light aromatic hydrocarbons exhibited a higher tendency to adsorb onto the emulsion phase. Furthermore, the increased presence of polar hydrocarbons in emulsion phases generated by polar surfactants confirmed the activation of electrostatic forces in fluid–fluid interactions. Nuclear magnetic resonance spectroscopy showed that the xanthan solution without surfactants had a greater potential to adsorb asphaltenes with highly fused aromatic rings, while the presence of bio-based surfactants reduced the solution's ability to adsorb asphaltenes with larger cores. Microfluidic tests demonstrated that incorporating surfactants derived from Morus nigra and Aloevera leaves into the xanthan solution enhanced oil recovery. While injection of the xanthan solution resulted in a 49.8% recovery rate, the addition of Morus nigra and Aloevera leaf-derived surfactants to the xanthan solution increased oil recovery to 58.1% and 55.8%, respectively.

Effect of Pd content in multi-component alloys [CoFeNi]Pdx on their behavior in hydrocarbon-containing atmosphere

Multicomponent metal systems attract growing interest today, especially as catalysts for various processes. In the present work, a series of [CoFeNi]Pdx alloys (equal atomic content of base metals) doped with palladium in the amount of 0–10 at.% were synthesized via thermolysis of multicomponent precursors. The resulting [CoFeNi]Pdx alloys were found to be single-phase solid solutions with a fcc structure represented by agglomerates of grains fused. The performance of the alloys was explored in a mixture of saturated hydrocarbons (C2–C4) within the temperature range of 600–675 °C. As a result of interaction with the reaction mixture, spontaneous disintegration of the alloys containing above 2 at.% Pd occurs with the formation of dispersed particles responsible for the catalytic growth of carbon nanofibers (CNF). The dependence of the productivity of the [CoFeNi]Pdx alloys towards CNFs on the x parameter was studied. The highest CNF yield (YC = 25–46 g/gcat, 30 min) was achieved at an optimal Pd concentration of 8 at.% within the entire temperature range. According to TEM and EDX data, regardless of the reaction temperature and Pd concentration in the alloy, the catalyst particles have the same composition as defined at the synthesis of the alloys. The resulting CoFeNiPd@CNF composite can be considered as a catalyst for other heterogeneous catalysis processes.

Puffing/micro-explosion of two-liquid droplets: Effect of fuel shell composition

Theoretical research into the heat and mass transfer, hydrodynamic and physicochemical processes in combustion chambers of gas turbine engines usually implies that multi-component jet fuels are modeled using single-component liquids (saturated or cyclic hydrocarbons) and their substitutes. Due to an insoluble dispersed phase (e.g., water) in their composition, droplets consist of a noncombustible core and a liquid fuel shell. During heating, water droplets coalesce in fuel droplets to produce explosion-triggering volumes of liquid superheated to the boiling point. When heated, these heterogeneous droplets breakup in the micro-explosion and puffing modes. This study reports the numerical simulation results providing the temporal characteristics of heating and evaporation of heterogeneous droplets until puffing/micro-explosive breakup, when varying the composition of the fuel shell in the homologous series of saturated and cyclic (as illustrated by monocycloparaffins) hydrocarbons from C7 to C16. The conducted research has revealed that the variations in the breakup delay times in the homologous series of saturated and cyclic hydrocarbons are nonlinear. The breakup delay rates were found to increase substantially in the boundary points of the investigated series. Mechanisms to control droplet fragmentation delay time were identified for different initial and boundary conditions. A dimensionless complex reflecting the correlation between the critical conditions of composite liquid droplet breakup and the physicochemical properties of the fuel shell components was proposed.

Hydrothermal recycling of polyolefins as potential alternative method for fuel production

The hydrothermal degradation of different polyolefins (virgin and recycled HDPE, recycled LLDPE, metallocene LLDPE, LDPE waste, virgin and recycled PP, PP waste) and their blends in different forms (granulate, foil) was investigated with supercritical water at 450 °C. The degradation of HDPE was investigated in a time range from 15 min to 240 min. The maximum yield of the oil phase was obtained at a degradation time of 60 min and was over 90 %, therefore all further experiments were carried out at a reaction time of 60 min. It was found that the composition of the oil obtained, and its calorific value depend on the type of material degraded. The oils obtained from PE materials contained between 65.3 % and 69.5 % saturated hydrocarbons, 11.4 %–17 % olefins and 8.9 %–20 % aromatics, while the oils from PP materials contained 40.8 %–45.9 % aromatics, 28.4 %–33.4 % saturated hydrocarbons and 10.6 % to 19.2% olefins. The main compounds in the oils from PP materials were the C9 compounds and from PE materials the C16 compounds. An exception were the oils from rLLDPE-1-g and LDPE-b, in which C8 compounds were most abundant and which contained the highest proportion of C17 – C31 hydrocarbons (approx. 17 %) compared to oils from other PE and PP materials (1.3 %–7.1 %). The HHV of the oils was between 29.4 and 45.7 MJ/kg and was highest for the oils where the gasoline/heavy oil ratio was less than 1, while the HHV of the gas phase was between 48.4 MJ/kg and 50.7 MJ/kg.

Study on the swelling of macromolecular geological organic matter with hydrocarbons and heteroatomic compounds

In this study, we conducted swelling experiments on eleven macromolecular geological organic materials using five types of organic solvents. Our primary objective was to investigate the absorption capacity of different solid organic materials in organic fluids and analyze the influence of their chemical structures. The samples utilized in this research included solid bitumen, kerogen, and coal samples from various basins. The chemical structure of the samples was assessed using solid-state 13C nuclear magnetic resonance (NMR), while X-ray diffraction (XRD) was employed to monitor any detect the structural changes during the swelling process. Our findings reveal that macromolecular geological organic compounds demonstrate a preferential expulsion of saturated hydrocarbons, followed by polycyclic aromatic hydrocarbons, upon interaction with liquid organic matter. The sulfur-containing compounds in solid organic matter demonstrated higher solubility than hydrocarbon compounds, while the solubility of oxygen-containing compounds varied based on the structure of the aliphatic chain and the proportion of oxygen atoms. This research, introduces LA [= Lac × Aac] as a new parameter to assess the combination of aliphatic chain length [Lac] and [Aac] abundance in solid organic matter. Furthermore, XRD testing revealed that the chemical structure unit of heteroatom compounds in solid organic matter consists of amorphous carbon, primarily composed of aliphatic chains. In this study, we evaluated the retention capacity of various macromolecular geological organic matter for both hydrocarbons and heteroatomic compounds. Additionally, the extent of swelling was investigated, providing theoretical support to diverse fields including organic petrology, petroleum geology, coal geology, and organic geochemistry.

Enhanced Molecular Descriptors Using Degree-Distance Invariants And Their Efficacy In QSPR Quadratic Modelling Of Chemical Compounds

In this study, we introduce an enhanced version of topological descriptors based on degree-distance invariants of connected graphs designed to effectively capture the structural characteristics of graphs with convex cuts, utilizing both vertex degrees and distances. We use this concept to analyze the Schultz and Gutman indices from reverse and neighbourhood degree perspectives. Motivated by the necessity for more effective descriptors in graph theory, our approach involves the development of algebraic expressions facilitating efficient computation, illustrated in some generalized benzenoid hydrocarbons. Moreover, the efficacy of the newly derived descriptors is evaluated through Linear and Quadratic Quantitative Structure-Property Relationship (QSPR) modelling on a dataset of carboxylic acids, and a set of structural isomers of saturated hydrocarbons revealing their effectiveness compared to existing descriptors.

Exclusively Ligand-Redox-Promoted C–H Tertiary Alkylation of Heteroarenes

Exclusively Ligand-Redox-Promoted C–H Tertiary Alkylation of Heteroarenes

Photoinduced Alkenylation of Alkenyl Sulfones with EDA Complexes between NHPI Esters and HE

AbstractA novel alkenylation reaction between N‐hydroxyphthalimide (NHPI) esters and alkenyl sulfones is reported. It undergoes the formation of electron donor‐acceptor (EDA) complex and a series of alkenes are obtained in good to excellent yields. It has the advantages of simple operation, mild reaction conditions, and metal‐free.

Investigation of the Stability Mechanism of Stimulus-Responsive Wormlike Micelle-CO2 Foams in the Oil Phase.

Foam flooding is an important tool for reservoir development. This study aims to further investigate the interaction between stimulus-responsive wormlike micelle (WLM)-CO2 foams and crude oil. We performed micromorphology experiments as our major studies and used molecular dynamics simulations as an auxiliary tool for interfacial analysis. We utilized foam generation, liquid separation, and defoaming as the entry points of experimental research and energy as the quantitative assessment index to investigate the dynamic process of the action of different oil contents and oil phase types in a DOAPA@NaSal-H+ foam system. We also examined the role of NaSal in the generation and development of the foam system. Results indicated that the law of crude oil's effect on foam could be summarized as "low contents are beneficial and high contents are harmful." In addition, although the DOAPA@NaSal-H+ foam system has high compatibility for saturated and aromatic hydrocarbons, it is highly suitable for application in reservoir environments with relatively high asphaltene and resin contents. Through combined experimental and simulation approaches, we clarified the law governing the stability of the DOAPA@NaSal-H+ foam system in different oil-containing environments, identified the key role of NaSal, and provided a reference for the targeted application of the DOAPA@NaSal-H+ foam system in different oil reservoirs.

Influence mechanism of original components on mechanical properties and transformation behaviors of natural bitumen

Natural bitumen is an important component with high-purity organic matter in fossil energy and energy engineering scenarios. However, the production and application of natural bitumen could be severely hindered by the lacking of understanding the effects and influencing mechanisms of original components on physical properties of natural bitumen. Therefore, the main purpose of this work is to illustrate the influence mechanisms of original components (saturated hydrocarbon, aromatic hydrocarbon, resin and asphaltene) on mechanical properties of natural bitumen by the combination of nanoindentation technology and molecular structure analysis. The effects of each original component on the mechanical properties were carried out for Wuerhe natural bitumen which collected from Junggar Basin of China, and the influencing mechanisms were further revealed based on nanoindentation and X-ray diffraction (XRD) results. The occurrence units of each component in the chemical structural stacking of bitumen were established for the first time. It was found that hydrocarbons and resins can disintegrate the chemical structural stacking, thereby reducing the mechanical strength of natural bitumen. According to our micro-scale analysis results, the plastic and elastic deformation of natural bitumen were controlled by the structural units of amorphous carbon and aromatic carbon microcrystalline, as determined by saturated and aromatic hydrocarbons, respectively. And the schematic diagram of occurrence of each component in solid bitumen for the first time. Hence, the mechanical strength of natural bitumen can be effectively reduced by retaining or increasing the content of alkanes during exploitation, transportation and processing of natural bitumen. This research provided a new understanding for the stacking structure and physical property change mechanism of natural bitumen.

A Study on Mineral Oil Hydrocarbons (MOH) Contamination in Pig Diets and Its Transfer to Back Fat and Loin Tissues.

This study assessed saturated mineral oil hydrocarbons (MOSH) and aromatic mineral oil hydrocarbons (MOAH) levels in grower-finisher feeds for pigs supplemented with 5% crude palm oil (CP), crude olive pomace oil (COP), olive pomace acid oil (OPA), or a blend of CP and OPA (50:50, w/w); the contribution of the lipid source to that contamination; and the ability of pigs to accumulate MOH in back fat and loin tissues after 60 days of trial. MOSH and MOAH were analyzed with liquid chromatography (LC)-gas chromatography (GC)-flame ionization detection (FID) after sample preparation. Among the lipid sources, CP had the lowest MOH levels, but CP feeds showed the highest contamination. This, along with the different MOSH profiles, indicated the presence of more significant contamination sources in the feeds than the lipid source. The higher MOH contamination in CP feeds was reflected in the highest MOSH levels in pig back fat, whereas MOAH were not detected in animal tissues. Also, MOSH bioaccumulation in pig tissues was influenced by the carbon chain length. In conclusion, feed manufacturing processes can determine the MOSH contamination present in animal adipose tissues that can be included in human diets.

Rapid and scalable photocatalytic C(sp2)–C(sp3) Suzuki−Miyaura cross-coupling of aryl bromides with alkyl boranes

In recent years, there has been a growing demand for drug design approaches that incorporate a higher number of sp3-hybridized carbons, necessitating the development of innovative cross-coupling strategies to reliably introduce aliphatic fragments. Here, we present a powerful approach for the light-mediated B-alkyl Suzuki−Miyaura cross-coupling between alkyl boranes and aryl bromides. Alkyl boranes were easily generated via hydroboration from readily available alkenes, exhibiting excellent regioselectivity and enabling the selective transfer of a diverse range of primary alkyl fragments onto the arene ring under photocatalytic conditions. This methodology eliminates the need for expensive catalytic systems and sensitive organometallic compounds, operating efficiently at room temperature within just 30 min. We further demonstrate the translation of the present protocol to continuous-flow conditions, enhancing scalability, safety, and overall efficiency of the method. This versatile approach offers significant potential for accelerating drug discovery efforts by enabling the introduction of complex aliphatic fragments in a straightforward and reliable manner.

Sustainable biorefining: Hydrothermal liquefaction of diatom biomass for bio-crude and nano-biosilica recovery

Diatom, a unique species of microalgae is a highly promising resource for the production of valuable bio-crude and silica nanomaterial. However, the complex nature of diatom cell structure presents significant downstream processing challenges and leads to inefficient bio-product recovery. To overcome this challenge, this study aimed to develop a one-step approach for the valorization of Denticula sp. dominated diatom consortium using hydrothermal liquefaction (HTL) process with the recovery of three major products. The first output, referred to as biocrude, constituted 22% of the total yield, consisting of 9.5% unbound bio-crude and 12.5% cell wall-bound organic fraction. The bio-crude consisted primarily of oxidized and desirable organic compounds like alcohols (24.4%), long-chain saturated hydrocarbons (23.6%), and esters (17.6%), with only a few undesirable nitrogen-containing compounds (18.9%). The second resultant product comprised nanoporous bio-silica structures, yielding 56%. These silica structures exhibited enhanced quality in comparison to the conventional thermal extraction technique employed for their retrieval and were found to be three-dimensional, highly porous, intact silica structures with low trace elements and a high surface area (53.7 m2 g−1). The third acquired product, the aqueous fraction, was observed to possess elevated levels of nitrate-nitrogen (440 mg L−1) and total dissolved phosphate (975 mg L−1). Overall, the study highlights the potential of HTL as an efficient diatom downstream processing method that allows for the complete valorization of intermediates, resulting in a sustainable biomass conversion and product recovery technology.

Purple Light-Promoted Coupling of Bromopyridines with Grignard Reagents via SET.

Alkyl- and arylpyridines and 2,2'-bipyridines are conventionally prepared by Minisci reactions of pyridines and transition metal-catalyzed coupling reactions of halopyridines. Herein, purple light-promoted radical coupling reactions of 2- or 4-bromopyridines with Grignard reagents in Et2O or a mixture of Et2O and tetrahydrofuran in regular glassware without the need for a transition metal catalyst were disclosed for the first time. Methyl, primary and secondary alkyl, cycloalkyl, aryl, heteroaryl, pyridyl, and alkynyl Grignard reagents were compatible with the protocol. As a result, alkyl- and arylpyridines and 2,2'-bipyridines were easily prepared. Single electron transfer from the Grignard reagent to bromopyridine was stimulated by purple light. An electron extruded from the dimerization of the Grignard reagent worked as the catalyst. Light on/off experiments indicated that constant irradiation was required for product formation. Studies of radical clock substrates verified the involvement of a pyridyl radical from bromopyridine and the noninvolvement of an alkyl or aryl radical from the Grignard reagent. The available proof supports a photoinduced SRN mechanism for the new coupling reactions.

Ni‐Catalyzed Linearizable Cyclization/Coupling with Detachable Silicon‐Oxygen Linker: Access to 1,2‐Oxasilolanes, 3‐Hydroxysilanes and 4‐Arylalkanols

AbstractWe disclose a Ni‐catalyzed cyclization/alkylmetal interception reaction in which products are readily linearized to permit regiodefined alkene dicarbofunctionalization. This method offers a convenient route to access 1,2‐oxasilolane heterocycles, 3‐hydroxysilanes and 4‐arylalkanols with the formation of C(sp3)−C(sp3) bonds at primary and secondary alkyl carbon centers. In this reaction, a silicon‐oxygen (Si−O) bond functions as a detachable linker that can be delinked with several hydride, alkyl, aryl and vinyl nucleophiles to create profusely functionalized 3‐hydroxysilanes. A silicon motif in the cyclic C(sp3)−Si−O construct in 1,2‐oxasilolane heterocycles can also be selectively deleted by Pd‐catalyzed hydrodesilylation affording Si‐ablated linear alcohol products reminiscent of vicinal ethylene dicarbofunctionalization with C(sp3) and C(sp2) carbon sources.

Ni-Catalyzed Linearizable Cyclization/Coupling with Detachable Silicon-Oxygen Linker: Access to 1,2-Oxasilolanes, 3-Hydroxysilanes and 4-Arylalkanols.

We disclose a Ni-catalyzed cyclization/alkylmetal interception reaction in which products are readily linearized to permit regiodefined alkene dicarbofunctionalization. This method offers a convenient route to access 1,2-oxasilolane heterocycles, 3-hydroxysilanes and 4-arylalkanols with the formation of C(sp3)-C(sp3) bonds at primary and secondary alkyl carbon centers. In this reaction, a silicon-oxygen (Si-O) bond functions as a detachable linker that can be delinked with several hydride, alkyl, aryl and vinyl nucleophiles to create profusely functionalized 3-hydroxysilanes. A silicon motif in the cyclic C(sp3)-Si-O construct in 1,2-oxasilolane heterocycles can also be selectively deleted by Pd-catalyzed hydrodesilylation affording Si-ablated linear alcohol products reminiscent of vicinal ethylene dicarbofunctionalization with C(sp3) and C(sp2) carbon sources.