Copper-Catalyzed Intramolecular Olefinic C(sp2)-H Amidation for the Synthesis of γ-Alkylidene-γ-lactams.

Herein, we report the copper-catalyzed dehydrogenative C(sp2)-N bond formation of 4-pentenamides via nitrogen-centered radicals. This reaction provides a straightforward and efficient preparation method for γ-alkylidene-γ-lactams. Notably, we could controllably synthesize α,ß-unsaturated- or α,ß-saturated-γ-alkylidene-γ-lactams depending on the reaction conditions.

Defluorinative Transformation of (2,2,2-Trifluoroethyl)arenes Catalyzed by the Phosphazene Base t-Bu-P2.

In this study, we demonstrated that 1-tert-butyl-2,2,4,4,4-pentakis(dimethylamino)-2λ5,4λ5-catenadi(phosphazene) (t-Bu-P2) catalyzes the defluorinative functionalization reactions of (2,2,2-trifluoroethyl)arenes with alkanenitriles to produce monofluoroalkene products. The reaction proceeds through HF elimination from a (2,2,2-trifluoroethyl)arene to form a gem-difluorostyrene intermediate, which is followed by nucleophilic addition of an alkanenitrile and elimination of a fluoride anion. The catalysis is compatible with a variety of functional groups.

Palladium(0)-Catalyzed Anti-Selective Addition-Cyclizations of Alkynyl Electrophiles.

Invited for the cover of this issue is the group of Hirokazu Tsukamoto at Tohoku University (current affiliation: Yokohama University of Pharmacy). The image depicts anti-selective arylative cyclization reactions of alkynyl aldehydes with arylboronic acids under palladium catalysis in methanol to afford endo- and exo-cyclic products. Read the full text of the article at 10.1002/chem.202203068.

Transition-Metal-Free Intermolecular Hydrocarbonation of Styrenes Mediated by NaH/1,10-Phenanthroline.

A transition-metal-free intermolecular coupling reaction of halocompounds with styrenes in the presence of NaH and 1,10-phenanthroline was developed. This reaction afforded hydrocarbonated products with complete anti-Markovnikov selectivity. The method allows the use of a wide range of halocompounds, including aryl and alkyl halides, and good functional group tolerance. Detailed mechanistic studies indicated that an anilide anion generated in situ by the NaH-mediated reduction of 1,10-phenanthroline works as an electron donor and a hydrogen source.

Palladium(0)-Catalyzed Anti-Selective Addition-Cyclizations of Alkynyl Electrophiles.

Palladium(0)/monophosphine complexes catalyze anti-selective alkylative, arylative, and alkynylative cyclizations of alkynyl electrophiles with organometallic reagents. The remarkable anti-selectivity results from novel oxidative addition, that is, the nucleophilic attack of electron-rich palladium(0) on the electrophile across the alkyne followed by transmetalation and reductive elimination ("anti-Wacker"-type cyclization). With regard to 5-alkynals, triphenylphosphine (PPh3 )-ligated palladium(0) catalyzes the cyclization of terminal alkynes and conjugated alkenyl- or alkynyl-substituted ones to afford 2-cyclohexen-1-ol and 2-alkylidene-cyclopentanol derivatives, respectively. For 6-alkyl- or 6-aryl-5-alkynals, the cyclization does not proceed with the palladium/PPh3 catalyst; however, it does proceed with palladium/tricyclohexylphosphine (PCy3 ), to yield the former products predominantly. Remarkably, the latter catalyst completely switches the regioselectivity in the cyclization of the conjugated diyne-aldehydes. Notably, palladium/PPh3 -catalyzed cyclizations also proceed with other organometallics or even without them.

LiHMDS-Mediated Deprotonative Coupling of Toluenes with Ketones.

We demonstrate that lithium hexamethyldisilazide (LiHMDS) acts as an effective base for deprotonative coupling reactions of toluenes with ketones to afford stilbenes. Various functionalities (halogen, OCF3 , amide, Me, aryl, alkenyl, alkynyl, SMe, and SPh) are allowed on the toluenes. Notably, this system proved successful with low-reactive toluenes bearing a large pKa value compared to that of the conjugate acid of LiHMDS (hexamethyldisilazane, 25.8, THF), as demonstrated by 4-phenyltoluene (38.57, THF) and toluene itself (∼43, DMSO).

Palladium-Catalyzed Borylative Cyclizations of α-(2-Bromoaryl) Ketones to Form 1,2-Benzoxaborinines.

Herein, we report that palladium catalyzes the borylative cyclization of α-(2-bromoaryl) ketones to afford 1,2-benzoxaborinines. The developed system is compatible with a variety of functionalities (Me, t-Bu, OMe, NMe2, F, Cl, CN, CF3, CO2Me, and heteroaryl groups) and is applicable to the synthesis of B-O-containing tri- and tetracyclic fused-ring compounds.

Combined Brønsted Base-Promoted CO2 Fixation into Benzylic C-H Bonds of Alkylarenes.

Interest in developing methods for direct CO2 fixation into readily available unfunctionalized C-H bonds in organic substances has recently surged. In contrast to the well-studied carboxylations of alkynyl C(sp)-H and aromatic C(sp2)-H bonds, carboxylation of benzylic C(sp3)-H bonds to produce 2-arylacetic acids is limited to photoirradiation reactions and continues to be a challenging issue because of the low chemical reactivity. We herein describe that a combined Brønsted base (i.e., LiO-t-Bu/CsF and LiOCEt3/CsF) achieves benzylic carboxylation of electron-deficient, -neutral, and -rich alkylarenes and enables various functionalities, including fragile ones such as bromide, alkene, alkyne, and carbonyl moieties. Dicarboxylation at the benzylic position is also established. Cs-alkoxide generated in situ acts as a reactive base, as demonstrated in experiments with independently prepared CsO-t-Bu and by 133Cs nuclear magnetic resonance studies.

Copper-catalyzed aerobic benzylic C(sp3)-H lactonization of 2-alkylbenzamides via N-centered radicals.

Herein, we describe the copper-catalyzed aerobic C(sp3)-H functionalization of 2-alkylbenzamides for the synthesis of benzolactones. This reaction proceeds via 1,5-hydrogen atom transfer of N-centered radicals directly generated by N-H bond cleavage and does not require the synthesis of pre-functionalized N-centered radical precursors or the use of strong stoichiometric oxidants.

Direct C-H Carboxylation Forming Polyfunctionalized Aromatic Carboxylic Acids by Combined Brønsted Bases.

CO2 fixation into electron-deficient aromatic C-H bonds proceeds with the combined Brønsted bases LiO-t-Bu and LiO-t-Am/CsF/18-crown-6 (t-Am = CEtMe2) under a CO2 atmosphere to afford a variety of polyfunctionalized aromatic carboxylic acids.

Nitrous acid (HONO) emission factors for diesel vehicles determined using a chassis dynamometer.

Vehicle exhaust gases are important sources of nitrous acid (HONO). In this study, HONO in diesel vehicle exhaust was measured by incoherent broadband cavity-enhanced absorption spectroscopy using a chassis dynamometer system. The mean HONO concentrations in exhaust gases emitted by passenger cars and light-duty trucks were high when the after treatment devices were not fully working during the warming up period. The HONO/NOx ratio is a good index of HONO formation. The HONO/NOx ratios were 9.7 × 10-3-18.1 × 10-3, and were higher than what we found in a previous study. The estimated HONO emission factors were 7.71-64.70 mg (kg fuel)-1, and were lower than were found in previous studies. The results indicated that the frequency particulate matter is removed from a diesel particle filter affects the HONO concentration in the emitted gases and the HONO emission factor.

Construction of 1,2,3-Benzodiazaborole by Electrophilic Borylation of Azobenzene and Nucleophilic Dialkylative Cyclization.

1,2,3-Benzodiazaboroles can be conveniently prepared from azobenzenes by a two-step protocol involving electrophilic ortho-borylation with BBr3 and dialkylative cyclization with the Grignard reagent. The methodology provides a diverse range of products equipped with functionalities from azobenzenes containing substituents (Me, t-Bu, F, Cl, Br, I, and OCF3) and a series of Grignard reagents (alkyl- and arylmagnesium reagents). Moreover, this study displays the moderate aromaticity of the B-N-N-containing five-membered ring and mechanistic investigations of the cyclization reaction.

Regio- and Stereoselective Hydroiodination of Internal Alkynes with Ex Situ-Generated HI.

Herein, we report an efficient and practical hydroiodination of internal alkynes using HI generated ex situ from the readily available triethylsilane and I2. This system offers high regio- and stereoselectivity to afford (E)-vinyl iodides in good yields under mild conditions. Furthermore, the hydroiodination reaction shows high functional group tolerance toward alkyl, methoxy, halogen, trifluoromethyl, cyano, ester, halomethyl, acid-sensitive silyl ether, and acetal moieties.

Copper-catalyzed aerobic double functionalization of benzylic C(sp3)-H bonds for the synthesis of 3-hydroxyisoindolinones.

A copper-catalyzed aerobic 3-hydroxyisoindolinone synthesis was developed via the benzylic double C(sp3)-H functionalization of 2-alkylbenzamides. In this reaction, molecular oxygen was used as both an oxidant for C(sp3)-H functionalization and an oxygen source. Our method can be extended to diverse benzylic C(sp3)-H bonds and shows excellent functional group tolerance.

Effect of cytosine-Ag+-cytosine base pairing on the redox potential of the Ag+/Ag couple and the chemical reduction of Ag+ to Ag by tetrathiafulvalene.

The redox properties of metallo-base pairs remain to be elucidated. Herein, we report the detailed 1H/13C/109Ag NMR spectroscopic and cyclic voltammetric characterisation of the [Ag(cytidine)2]+ complex as isolated cytosine-Ag+-cytosine (C-Ag+-C) base pairs. We also performed comparative studies between cytidine/Ag+ and other nucleoside/Ag+ systems by using cyclic voltammetry measurements. In addition, to evaluate the effect of [Ag(cytidine)2]+ formation on the chemical reduction of Ag+ to Ag, we utilised the redox reaction between Ag+ and tetrathiafulvalene (TTF). We found that Ag+-mediated base pairing lowers the redox potential of the Ag+/Ag couple. In addition, C-Ag+-C base pairing makes it more difficult to reduce captured Ag+ ions than in other nucleoside/Ag+ systems. Remarkably, the cytidine/Ag+ system can be utilised to control the redox potential of the Ag+/Ag couple in DMSO. This feature of the cytidine/Ag+ system may be exploited for Ag nanoparticle synthesis by using the redox reaction between Ag+ and TTF.

Source contributions to multiple toxic potentials of atmospheric organic aerosols.

Fine particulate matter (PM2.5) in the atmosphere is of high priority for air quality management efforts to address adverse health effects in human. We believe that emission control policies, which are traditionally guided by source contributions to PM mass, should also consider source contributions to PM health effects or toxicity. In this study, we estimated source contributions to the toxic potentials of organic aerosols (OA) as measured by a series of chemical and in-vitro biological assays and chemical mass balance model. We selected secondary organic aerosols (SOA), vehicles, biomass open burning, and cooking as possible important OA sources. Fine particulate matter samples from these sources and parallel atmospheric samples from diverse locations and seasons in East Asia were collected for the study. The source and atmospheric samples were analyzed for chemical compositions and toxic potentials, i.e. oxidative potential, inflammatory potential, aryl hydrocarbon receptor (AhR) agonist activity, and DNA-damage, were measured. The toxic potentials per organic carbon (OC) differed greatly among source and ambient particulate samples. The source contributions to oxidative and inflammatory potentials were dominated by naphthalene-derived SOA (NapSOA), followed by open burning and vehicle exhaust. The AhR activity was dominated by open burning, followed by vehicle exhaust and NapSOA. The DNA damage was dominated by vehicle exhaust, followed by open burning. Cooking and biogenic SOA had smaller contributions to all the toxic potentials. Regarding atmospheric OA, urban and roadside samples showed stronger toxic potentials per OC. The toxic potentials of remote samples in summer were consistently very weak, suggesting that atmospheric aging over a long time decreased the toxicity. The toxic potentials of the samples from the forest and the experimentally generated biogenic SOA were low, suggesting that toxicity of biogenic primary and secondary particles is relatively low.

Chemical reduction of Ag+ to Ag employing organic electron donors: evaluation of the effect of Ag+-mediated cytosine-cytosine base pairing on the aggregation of Ag nanoparticles.

Ag+-mediated base pairing is valuable for synthesising DNA-based silver nanoparticles (AgNPs) and nanoclusters (AgNCs). Recently, we reported the formation of a [Ag(cytidine)2]+ complex in dimethyl sulfoxide (DMSO), which facilitated the evaluation of the effect of cytosine-Ag+-cytosine (C-Ag+-C) base pairing on the degree of AgNP aggregation in solution. As an aprotic solvent, DMSO was expected to dissolve the [Ag(cytidine)2]+ complex, and powerful reducing agents, such as organic electron donors. In this study, the chemical reduction of a cytidine/Ag+ system using a powerful reducing agent tetrakis(dimethylamino)ethylene (TDAE) was investigated. 1H/13C/15N NMR spectroscopic evidence was obtained to identify the iminium dication (TDAE2+), which is an oxidised form of TDAE. The results were compared with those obtained using another organic electron donor, tetrathiafulvalene (TTF), which exhibits a relatively lower reduction activity than TDAE. AgNPs prepared via redox reaction between [Ag(cytidine)2]+ and organic electron donors (TDAE and TTF) were characterised using UV-Vis spectroscopy and nanoparticle tracking analysis. It was found that the formation of C-Ag+-C base pairing inhibited the aggregation of AgNPs in solution. In addition, in the presence of cytidine, the total concentration of the AgNP solution was affected by the reduction activity of the reducing agent.

Catalytic amide base system generated in situ for 1,3-diene formation from allylbenzenes and carbonyls.

The amide base generated in situ from tetramethylammonium fluoride and N(TMS)3 catalyzes the synthesis of 1,3-diene from an allylbenzene and carbonyl compound. The system is applicable to the transformations of a variety of allylbenzenes with functional groups (halogen, methyl, phenyl, methoxy, dimethylamino, ester, and amide moieties). Acyclic and cyclic diaryl ketones, pivalophenone, pivalaldehyde, and isobutyrophenone are used as coupling partners. The role of transß-methyl stilbenes in product formation is also elucidated.

Di-tert-butyl Peroxide (DTBP)-Mediated Oxysilylation of Unsaturated Carboxylic Acids for the Synthesis of Silyl Lactones.

Herein, we describe the first oxysilylation of unsaturated carboxylic acids mediated by di-tert-butyl peroxide (DTBP), which enables the rapid and efficient preparation of silyl lactone compounds. This process tolerates functional groups, such as methyl, methoxy, halogen (fluoride and chloride), and cyano moieties. Furthermore, the strategy allows the application of a wide range of primary, secondary, and tertiary hydrosilanes for functionalization.