Showing papers on "Double bond published in 2022"

Tuning the Electronic Properties of Main-Group Species by N-Heterocyclic Vinyl (NHV) Scaffolds

Abstract: ConspectusMolecules and materials with easily tunable electronic structures and properties are at the forefront of contemporary research. π-Conjugation is fundamental in organic chemistry and plays a key role in the design of molecular materials. In this Account, we showcase the applicability of N-heterocyclic vinyl (NHV) substituents based on classical N-heterocyclic carbenes (NHCs) for tuning the structure, properties, and stability of main-group species (E) via π-conjugation and/or π-donation.NHVs such as [(NHC)═CR] (R = H or aryl) are monoanionic ligands formally derived by the deprotonation of N-heterocyclic olefins (NHOs), (NHC)═CHR. Further deprotonation of [(NHC)═CR] (R = H) is viable, giving rise to N-heterocyclic vinylidene (NHVD) species such as (NHC)═C. NHVs and NHVDs feature a highly polarizable exocyclic CNHC═C bond because of the presence of adjacent π-donor nitrogen atoms. The nature of the NHC, in particular the π-acceptor property, has a direct consequence on the polarity of the CNHC═C bond and hence on the magnitude of π-conjugation in the derived molecules. Thus, the electronic structure, especially the energy and shape of frontier molecular orbitals, HOMO and LUMO, of derived species can be fine-tuned by a judicious choice of the carbene unit. For instance, the HOMO of classical diphosphenes (RP═PR) (R = alkyl or aryl) is invariably the phosphorus lone-pair orbital, while the P═P π-bond is HOMO - 1 or HOMO - 2. In strong contrast, the HOMO of divinyldiphosphenes (R = NHV) is mainly the P═P π-bond. This is owing to the π-conjugation, resulting in the lowering of the LUMO and raising of the HOMO energy. They have a remarkably small HOMO-LUMO energy gap (4.15-4.50 eV) and readily undergo 1e-oxidations, giving rise to stable radical cations and dications.By employing a similar approach, one can access divinyldiarsenes and the corresponding radical cations and dications as crystalline solids. The use of divinyldiphosphenes and divinyldiarsenes as promising ligands in the stabilization of metalloradicals has been shown. By a logical selection of singlet carbenes, stable 2-phosha-1,3-butadiene and 2-arsa-1,3-butadiene compounds, as well as related radical cations and dications, can be prepared as crystalline solids.The relevance of NHV ligands as potent π-donors has been demonstrated for the stabilization of elusive electrophilic phosphinidene and arsinidene complexes {(NHV)E}Fe(CO)4 (E = P or As). Moreover, stable singlet diradicaloid [(NHC)CP]2 and p-quinodimethane derivatives [(NHC)CP2]2 based on an NHVD framework are accessible as stable solids.In this Account, a special emphasis is given to the contributions from this laboratory. The author hopes that this Account will serve as a useful reference guide for researchers interested in studying and applying NHV and NHVD scaffolds in modern molecular chemistry and materials sciences.

Controllable Single and Double Difluoromethylene Insertions into C-Cu Bonds: Copper-Mediated Tetrafluoroethylation and Hexafluoropropylation of Aryl Iodides with TMSCF2H and TMSCF2Br.

Abstract: The selective difluoromethylene insertion into a C-Cu bond is a challenging task and is currently limited to either a single CF2 insertion into CuCF3 or double CF2 insertions into CuC6F5 (or (Z)-CF3CF = CFCu). Achieving both selective single and double CF2 insertions into the same C-Cu bond is even more difficult. Herein, highly controllable single and double CF2 insertions into CuCF2H species with a TMSCF2Br reagent have been described, affording two previously unknown fluoroalkylcopper species "Cu(CF2)nCF2H" (n = 1 and 2) independently under different reaction conditions. This work represents the first example of both single and double CF2 insertions into the same C-Cu bond in a highly selective manner. The synthetic value of the obtained "Cu(CF2)nCF2H" (n = 1 and 2) species is demonstrated by their reactions with aryl iodides, halogenation agents, and cinnamyl chloride, which enables the direct transfer of HCF2CF2 and HCF2CF2CF2 moieties into organic molecules. The key to controllable fluorocarbon chain elongation from C1 to C2 and from C1 to C3 is presumably attributed to the different reactivities of "Cu(CF2)nCF2H" species (n = 0, 1, 2 and 3) and the loading of the TMSCF2Br reagent.

Selective 1,2 addition of polar X-H bonds to the Ga-P double bond of gallaphosphene L(Cl)GaPGaL.

Abstract: Gallaphosphene L(Cl)GaPGaL 1 (L = HC[C(Me)N(2,6-i-Pr2-C6H3)]2) reacts at ambient temperature with a series of polar X-H bonds, i.e. ammonia, primary amines, water, phenol, thiophenol, and selenophenol, selectively with 1,2 addition at the polar Ga-P double bond. The gallium atom serves as electrophile and the phosphorous atom is protonated in all reactions. The resulting complexes L(Cl)GaP(H)Ga(X)L (X = NH22, NHi-Pr 3, NHPh 4, OH 5, OXyl 6, SPh 7, SePh 8) were characterized by IR and heteronuclear (1H, 13C{1H}, 31P{1H}) NMR spectroscopy, elemental analysis, and single-crystal X-ray diffraction.

Dimerizing cascades of enallenamides reveal the visible-light-promoted activation of cumulated C–C double bonds

Abstract: The visible-light-promoted activation of conjugated C–C double bonds is well developed, while that of cumulated systems is underexplored. We present the feasibility of this challenging approach. The localization of a triplet on an allenamide arm can be favored over that on a conjugated alkene. Allenamides with an arylacryloyl arm dimerize at room temperature in the presence of visible light and an iridium(iii) photocatalyst. Two orthogonal polycyclizations took place and their outcome is entirely dictated by the substitution of the alkene partner. Both cascades afford complex molecular architectures with high selectivity. Products form through the ordered rearrangement of twelve π electrons, providing a [3.2.0] bicyclic unit tethered to a fused tricycle, whose formation included an aryl C–H functionalization step, using disubstituted alkenes. The outcome was reverted with trisubstituted ones, which gave rise to taxane-like bridged tricycles that had two six-membered lactams flanking a cyclooctane ring, which was established through the creation of four alternate C–C bonds.

Highly Substrate‐Selective Macrocyclic Ring Closing Metathesis

Abstract: A selective ring-closing metathesis (RCM) reaction for the formation of large macrocycles by using latent sulfur chelated ruthenium iodide benzylidenes, readily activated by thermal and photochemical (UV-A and visible light) stimuli, is reported. For dienes having one terminal alkene and one internal double bond, the specific affinity of diiodo ruthenium alkylidenes for the unhindered terminus, combined with their reluctance to react with internal olefins, favors RCM over oligomerization, providing high macrocyclic yields even at relatively high concentrations. Alternatively, for substrates containing two internal double bonds, a sacrificial methylene donor can be used to obtain the desired products. With this methodology, lactones, lactams, and macrocyclic ketones ranging from 13- to 22-membered rings could be synthesized in moderate to high yields. In addition, synthetic applications for a one-pot cyclization/reduction sequence to produce Exaltolide, a natural macrolide (commercial musk), Dihydrocivetone, and other saturated macrocycles have been explored. Thus, we disclose herein an important advantage for diiodo ruthenium benzylidene catalysts over their less selective dichloro counterparts and provide a more profound understanding of the mechanisms that provide the enhanced cyclization outcome.

The role of the unsaturation degree on the droplet combustion characteristics of fatty acid methyl ester

Abstract: Biodiesel is composed of various types of methyl ester compounds with different concentrations. The role of unsaturation degree was observed through single-molecule droplet combustion from three fatty acid methyl ester compounds. This research was conducted under normal gravity at ambient temperature and atmospheric pressure. Analysis of droplet combustion characteristics was observed along the heating, evaporation, ignition, and combustion stages. The cis configuration and allyl groups in unsaturated molecules related to different unsaturation degrees affect the droplet combustion process. Allyl and bis-allyl groups play an important role in accelerating hydrogen atom abstraction due to the weaker bond dissociation energy of the C H bond adjacent to the carbon double bond. The lower energy gap in unsaturated molecules is prone to electron excitation. Increasing the unsaturation degree resulted in shorter ignition delay and burning duration but higher droplet temperature, burning rate constant, specific power output, and flame dimensions. Soot particles formed above the flame tip on the unsaturated molecules gave a higher flame dimension. A high concentration of linoleic methyl ester in biodiesel fuel is recommended due to of high power output. However, the soot formation at a higher level of unsaturation degree should be considered.

Bioinspired Synthesis of Spirochensilide A from Lanosterol.

Abstract: A bioinspired synthesis of spirochensilide A from commercially available lanosterol is reported. The synthesis features a directed C-H oxidation, a Wagner-Meerwein-type double methyl migration, a Meinwald rearrangement, and a double-bond isomerization/spiroketal formation cascade. The proposed biosynthetic speculation was modified by this synthetic sequence, which also served as a platform for the synthesis of other lanostanes with migrating methyl groups.

Peroxy Radical Autoxidation and Sequential Oxidation in Organic Nitrate Formation during Limonene Nighttime Oxidation.

Abstract: Limonene is an abundant monoterpene released into the atmosphere via biogenic emissions and biomass burning. However, the atmospheric oxidation and secondary organic aerosol (SOA) formation mechanisms of limonene, especially during nighttime, remain largely understudied. In this work, limonene was oxidized synergistically by ozone (O3) and nitrate radicals (NO3) in a flow tube reactor and a continuous flow stirred tank reactor. Upon oxidation, many highly oxidized organic nitrates and nitrooxy peroxy radicals (RO2) were observed in the gas phase within 1 min. Combining quantum chemical calculations with kinetic simulations, we found that the primary nitrooxy RO2 (C10H16NO5) through NO3 addition at the more substituted endocyclic double bond and at the exocyclic double bond (previously considered as minor pathways) can undergo autoxidation with rate constants of around 0.02 and 20 s-1 at 298 K, respectively. These pathways could explain a major portion of the observed highly oxidized organic nitrates. In the SOA, highly oxidized mono- and dinitrates (e.g., C10H17NO7-8 and C10H16,18N2O8-10) make up a significant contribution, highlighting nitrooxy RO2 autoxidation and sequential NO3 oxidation of limonene. The same organic nitrates are also observed in ambient aerosol during biomass burning and nighttime in the southeastern United States. Therefore, the present work provides new insights into the nighttime oxidation of limonene and SOA formation in the atmosphere.

The role of the unsaturation degree on the droplet combustion characteristics of fatty acid methyl ester

Abstract: Biodiesel is composed of various types of methyl ester compounds with different concentrations. The role of unsaturation degree was observed through single-molecule droplet combustion from three fatty acid methyl ester compounds. This research was conducted under normal gravity at ambient temperature and atmospheric pressure. Analysis of droplet combustion characteristics was observed along the heating, evaporation, ignition, and combustion stages. The cis configuration and allyl groups in unsaturated molecules related to different unsaturation degrees affect the droplet combustion process. Allyl and bis-allyl groups play an important role in accelerating hydrogen atom abstraction due to the weaker bond dissociation energy of the CH bond adjacent to the carbon double bond. The lower energy gap in unsaturated molecules is prone to electron excitation. Increasing the unsaturation degree resulted in shorter ignition delay and burning duration but higher droplet temperature, burning rate constant, specific power output, and flame dimensions. Soot particles formed above the flame tip on the unsaturated molecules gave a higher flame dimension. A high concentration of linoleic methyl ester in biodiesel fuel is recommended due to of high power output. However, the soot formation at a higher level of unsaturation degree should be considered.

Ir/f-Ampha complex catalyzed asymmetric sequential hydrogenation of enones: a general access to chiral alcohols with two contiguous chiral centers

Abstract: A general and highly efficient method for asymmetric sequential hydrogenation of α,β-unsaturated ketones has been developed by using an iridium/f-Ampha complex as the catalyst, furnishing corresponding chiral alcohols with two contiguous stereocenters in high yields with excellent diastereo- and enantioselectivities (up to 99% yield, >20 : 1 dr and >99% ee). Control experiments indicated that the C C and CO bonds of the enones were hydrogenated sequentially, and the final stereoselectivities were determined by the dynamic kinetic resolution of ketones. Moreover, DFT calculations revealed that an outer sphere pathway was involved in both reduction of CC and CO bonds of enones. The synthetic utility of this method was demonstrated by a gram-scale reaction with very low catalyst loading (S/C = 20 000) and a concise synthetic route to key chiral intermediates of the antiasthmatic drug CP-199,330.

A Free Phosphaborene Stable at Room Temperature.

Abstract: Free phosphaborenes (R-P═B-R) are PB analogues of alkynes, and their isolation is a long-sought-after goal. Herein, we demonstrate that the combination of a π-donating and a π-accepting substituent with bulky flanking arene rings enables the isolation of a crystalline free phosphaborene 5 at room temperature. This electron push-pull cooperation, combined with the kinetic protection, hinders its inherent tendency to oligomerize. This species features a PB double bond consisting of a conventional σ bond and a delocalized π bond. The lone pair of electrons at P slightly contributes to the PB bonding. Preliminary reactivity studies show that 5 undergoes facile (cyclo)addition reactions with p-methyl benzaldehyde, p-fluoroacetophenone, and carbon disulfide, the last of which results in facile PB double bond cleavage. Our strategy has a significant impact on the future synthesis of ambiphilic heterodiatomic multiply bonded main group species.

Photoinduced Bisphosphination of Alkynes with Phosphorus Interelement Compounds and Its Application to Double-Bond Isomerization

Abstract: The addition of interelement compounds with heteroatom-heteroatom single bonds to carbon-carbon unsaturated bonds under light irradiation is believed to be an atomically efficient method to procure materials with carbon-heteroatom bonds. In this study, we achieved the photoinduced bisphosphination of alkynes using the phosphorus interelement compound, tetraphenyldiphosphine monosulfide (1), to stereoselectively obtain the corresponding (E)-vic-1,2-bisphosphinoalkenes, which are important transition-metal ligands. The bisphosphination reaction was performed by mixing 1 and various alkynes and then exposing the mixture to light irradiation. Optimization of the conditions for the bisphosphination reaction resulted in a wide substrate range and excellent trans-selectivity. Moreover, the completely regioselective introduction of pentavalent and trivalent phosphorus groups to the terminal and internal positions of the alkynes, respectively, was achieved. We also found that the novel double-bond isomerization reaction of the synthesized bisphosphinated products occurred with a catalytic amount of a base under mild conditions. Our method for the photoinduced bisphosphination of carbon-carbon unsaturated compounds may have strong implications for both organic synthesis and organometallic and catalyst chemistry.

Aspersterols A-D, Ergostane-Type Sterols with an Unusual Unsaturated Side Chain from the Deep-Sea-Derived Fungus Aspergillus unguis.

Abstract: Four previously undescribed ergostane-type sterols, aspersterols A-D (1-4), were isolated from a deep-sea-derived fungus, Aspergillus unguis IV17-109. The structures of the new compounds were determined by extensive analyses of their spectroscopic data, pyridine-induced deshielding effect, Mosher's method, and electronic circular dichroism calculations. The key feature of these sterols is the presence of a rare unsaturated side chain with conjugated double bonds at Δ17 and Δ22. The absolute configuration of C-24 in the side chain was determined by hydrogenation and comparing 13C NMR chemical shifts of the hydrogenated products with literature values. In addition, aspersterol A (1) is the second representative of anthrasteroids with a hydroxy group at the C-2 position. Compound 1 showed cytotoxicity against six cancer cell lines, with GI50 values of 3.4 ± 0.3 to 4.5 ± 0.7 μM, while 2-4 showed anti-inflammatory activity, with IC50 values ranging from 11.6 ± 1.6 to 19.5 ± 1.2 μM.

Effect of the double bond content of sizing agents on the mechanical properties of carbon fibre reinforced vinyl ester composites

Abstract: Unsaturated polyester sizing agents with various double bond contents have a significant influence on the interface between carbon fibers (CF) and vinyl ester resins (VER). This paper aims to study the effect of the double bond content of sizing agents on the surface properties of CF and thermo mechanical properties of the sized CF/VER composites. We synthesized five types of self-emulsifying cationic sizing agents with various double bond contents and characterized the samples by FTIR, dynamic light scattering (DLS), cryo-scanning electron microscopy (Cryo-SEM) and thermal gravimetric analysis (TGA). The double bond content of the sizing agents on the cross-linking extent of the CF surface were investigated on factors such as the wettability of VER, the interlaminar shear strength (ILSS) and flexural strength and modulus of CF/VER composites. It was identified that the distribution of the sizing agent emulsions had a mono-dispersion of around 50 nm and were thermally stable below 300 °C. Additionally, it was identified that the double bond content of the sizing agents enhanced the grafting reactions and cross-linking extent between the sizing agent and CF surface. The CF had the best wettability for vinyl ester resin when the double bond content was 10% in the sizing agent. In addition, the ILSS, the flexural strength and the modulus reached maxima.