Unsymmetric Ir2 and RhIr Dinuclear Complexes Supported by a Linear Tetraphosphine meso-dpmppp, Showing High Reactivity for O2, H2, and HCl.

Unsymmetric dinuclear Ir(I) complexes, [Ir2Cl2(L)(meso-dpmppp)] (L = XylNC (1aIr2), tBuNC (1bIr2), CO (1cIr2)), were synthesized using meso-Ph2PCH2P(Ph)(CH2)3P(Ph)CH2PPh2 (meso-dpmppp), which supports cis-P,P (M1) and trans-P,P (M2) metal sites, and exhibited high reactivity for O2, H2, and HCl. The IrRh heterodinuclear complexes, [M1M2Cl2(L)(meso-dpmppp)] (1xM1M2) (M1M2 = IrRh, RhIr; L = XylNC, CO (x = a, c)), were also synthesized and used together with the Rh2 complexes (1a,cRh2) to elucidate the role of each metal site. For the reactions of O2, 1aIr2 and 1aRhIr showed higher reactivity than those of 1aIrRh and 1aRh2, giving η2-peroxide complexes [{M1Cl2}{M2(η2-O2)(XylNC)}(meso-dpmppp)] (2aIr2, 2aRhIr), from which O2 would not dissociate. All the CO complexes 1cM1M2 (M1, M2 = Ir or Rh) showed no reactivity for O2. In the reactions with H2, 1aIr2 reacted with H2 to give the dihydride complex, [{IrCl2}{Ir(H)2L}(meso-dpmppp)] (11aIr2) and the tetrahydride complex, [{Ir(H)Cl2}(µ-H){Ir(H)2L}(meso-dpmppp)] (12aIr2), while 1aRhIr gave the dihydride complex, and 1aIrRh and 1aRh2 gave no hydride complexes. Reactions of 1a,cM1M2 with HCl afforded the dihydride complexes, [{IrCl3}(µ-H){Ir(H)Cl(XylNC)}(meso-dpmppp)] (14aIr2), [{Ir(H)Cl2}(µ-H){M2Cl2(L)}(meso-dpmppp)] (M2 = Ir, L = CO (15cIr2); M2 = Rh, L = XylNC (15aIrRh), CO (15cIrRh)), and [{Rh(H)Cl2}(µ-Cl){Ir(H)Cl(XylNC)}(meso-dpmppp)] (18aRhIr), the structures varying depending on M1 and M2 as well as L.

Unsymmetrization of 1,8-Dibromonaphthalenes by Acid-Induced Halogen Dance Reaction.

A simple and powerful tool for preparing uncommon bromoarenes via the unsymmetrization of a naphthalene ring was developed. The steric repulsion between the peri-bromo groups of 1,8-dibromonaphthalene distorts the naphthalene ring, allowing for nonelectronical activation. Ring distortion facilitates the 1,2-rearrangement of the bromo group, affording 1,7-dibromonaphthalene upon treatment with trifluoromethanesulfonic acid (halogen dance reaction). For 1,4,5,8-tetrabromonaphthalene, stepwise 1,2-rearrangements proceeded successively to furnish 1,3,5,7-tetrabromonaphthalene. Density functional theory calculations suggest that this reaction is initiated by ipso-protonation, with a subsequent 1,2-rearrangement occurring via the bromonium transition state. Utilizing 1,7-dibromonaphthalene, which is characterized by two C-Br bonds arranged at a 60° angle, a unique metal-organic framework comprising a 52-membered ring network was synthesized.

Highly electron-deficient 1-propyl-3,5-dinitropyridinium: evaluation of electron-accepting ability and application as an oxidative quencher for metal complexes.

Impacts of the nitro groups on the electron-accepting and oxidizing abilities of N-propylpyridinium were evaluated quantitatively. A 3,5-dinitro derivative has efficiently quenched emission from photosensitizing Ru(ii) and Ir(iii) complexes owing to the thermodynamically-favored electron transfer to the pyridinium whose LUMO is greatly lowered by the presence of electron-withdrawing nitro groups.

Cationic Iridium-Catalyzed Decarboxylation of Aromatic Carboxylic Acids.

Practical synthetic applications of catalytic decarboxylation in producing useful molecules are limited. We report herein the cationic Ir-catalyzed decarboxylations of various electron-rich and -poor aromatic carboxylic acids to produce hydrocarbons in good yield (up to >99%). Additionally, this reaction is applicable in decarboxylative hydroarylation of bicyclic alkenes and decarboxylative fluorination, indicating the potential utility of this catalytic decarboxylation in synthetic chemistry.

A Study of the Correlation between the Bulkiness of peri-Substituents and the Distortion of a Naphthalene Ring.

A systematic study on the distortion of a naphthalene ring was performed using steric repulsion between peri-substituents at the 1- and 8-positions. The introduction of bromo groups into the methyl groups of the 1,8-dimethylnaphthalene enhanced the steric repulsion to distort the naphthalene ring. X-ray crystallography revealed that 1,8-bis(bromomethyl)naphthalene had a vertical distortion with a 11.0° dihedral angle (α) between peri-substituents which disturbed the coplanarity of the naphthalene ring. On the other hand, the dihedral angle of 1,8-bis(dibromomethyl)naphthalene was smaller (α = 8.3°) despite the bulkier substituents. In this case, horizontal distortion of the naphthalene ring increased. These distortions should non-electronically activate the naphthalene framework. In order to evaluate their reactivity, nitration and hydrogenation were carried out; however, the 1,8-bis(dibromomethyl)naphthalene was intact under the employed conditions. A DFT calculation suggested that the inertness of the 1,8-bis(dibromomethyl)naphthalene is presumably due to the negative hyperconjugation of the (dibromo)methyl group.

Halo-Jacobsen Rearrangement Induced by Steric Repulsion between peri-Iodo Groups.

The naphthalene ring is distorted due to steric repulsion between iodo groups at the peri-positions. Due to the distortion, 1,8-diiodonaphthalene underwent a halo-Jacobsen rearrangement when treated with trifluoromethanesulfonic acid, producing 1,5-diiodonaphthalene and 1,4-diiodonaphthalene. In this reaction, acid-induced dehalogenative homocoupling also proceeded to form 4,4'-diiodo-1,1'-binaphthyl. The reaction selectivity could be controlled by varying the reaction temperature. DFT calculations and some control experiments revealed that these compounds were formed by different pathways.

First synthesis of acylated nitrocyclopropanes.

Although nitrocyclopropanedicarboxylic acid esters are widely used in organic syntheses, nitrocyclopropanes with an acyl group have not yet been synthesized. When adducts of ß-nitrostyrene and 1,3-dicarbonyl compounds are treated with (diacetoxyiodo)benzene and tetrabutylammonium iodide, iodination occurs at the α-position of the nitro group, and the subsequent O-attack of the enol moiety leads to 2,3-dihydrofuran. Cyclopropane was successfully synthesized through C-attack as the acyl group became bulkier. The obtained nitrocyclopropane was transformed into furan upon treatment with tin(II) chloride via a ring-opening/ring-closure process.

Synthesis of Bis(functionalized) Aminals via Successive Nucleophilic Amidation and Amination.

The central carbonyl group of diethyl mesoxalate (DEMO) exhibits high electrophilicity that allows it to be attacked by versatile nucleophiles. Even a less nucleophilic acid amide serves as a nucleophile to produce N,O-acetal upon treatment with DEMO in the presence of acetic anhydride. When the obtained N,O-acetal was treated with a base, the elimination of acetic acid generated N-acylimine in situ. N-Acylimine is also highly electrophilic, allowing it to accept the second nucleophilic addition by an amine, resulting in α,α-bis(functionalized) aminals. This protocol facilitates the modification of the two different amino groups by altering nucleophiles, resulting in the production of tetra-functionalized methane derivatives on demand. The ring closure between the amide moiety and the amino group was achieved using the structural features to form a six-membered ring.

Unusual Reactivities of ortho-Hydroxy-ß-nitrostyrene.

Nitrostyrene derivatives are widely used in organic syntheses as a substrate for Michael addition, photoisomerization and cycloaddition. In contrast, ortho-hydroxy derivatives exhibit unusual behaviors in these reactions. Conjugate addition proceeded upon treatment of the ortho-hydroxy-ß-nitrostyrene with an amine; however, subsequent C-C bond cleavage readily occurred to afford the corresponding imine. Moreover, conversion of the trans-isomer to a cis-isomer did not occur efficiently, even when UV light was irradiated. We studied these unusual behaviors of ß-nitrostyrene, focusing on the role of the ortho-hydroxy group.

A new approach to 10-arylated 5H-dibenzo[b,f]azepines using syn-selective hydrohalogenation of ethynylaniline.

A new synthetic method for 10-arylated dibenzo[b,f]azepines was developed. The pseudo-intramolecular hydrohalogenation of 2-(2'-bromophenyl)ethynylaniline, which proceeded in a syn-selective manner without forming any detectable over-addition product, was a crucial step. All attempts of subsequent arylation via Suzuki-Miyaura cross coupling and construction of a seven membered ring via Ullmann-type intramolecular coupling were unsuccessful because of dehydrohalogenation or other side reactions. This problem was overcome by the N-acetylation of the amino group, which facilitated the abovementioned coupling reactions to afford the desired 10-arylated dibenzoazepines.

Recent Advances in Synthesis of Multiply Arylated/Alkylated Pyridines.

Multiply aryl/alkyl-substituted pyridines are some of the untapped synthetic targets because of the challenge in regioselectively introducing less polar aryl/alkyl groups at the desired positions in the pyridine framework. Interestingly, the importance of this family of compounds has increased annually, particularly in biological and materials engineering applications. The syntheses of such pyridines have been extensively reported, but there is a lack of comprehensive review articles. Hence, this review discusses recent advances by grouping reaction patterns that generally deliver tri-, tetra-, and penta-aryl/alkyl pyridines.

A Mechanistic Study for Aziridination of Nitroalkenes Mediated by N-Chlorosuccinimide.

Direct aziridination of a nitrostyrene is achieved upon treatment with an alkylamine and N-chlorosuccinimide. The reaction is initiated by the Michael addition of amine to nitroalkene. Subsequent N-chlorination and nucleophilic substitution at the nitrogen atom afford 1-alkyl-2-nitroaziridine diastereoselectively. This reaction mechanism was clarified by NMR studies.

Development of a synthetic equivalent of α,α-dicationic acetic acid leading to unnatural amino acid derivatives via tetrafunctionalized methanes.

Diethyl mesoxalate (DEMO) exhibits high electrophilicity and accepts the nucleophilic addition of a less nucleophilic acid amide to afford N,O-hemiacetal. However, our research showed that elimination of the amide moiety proceeded more easily than dehydration upon treatment with a base. This problem was overcome by reacting DEMO with an acid amide in the presence of acetic anhydride to efficiently obtain N,O-acetal. Acetic acid was eliminated leading to the formation of N-acylimine in situ upon treatment with the base. N-Acylimine is also electrophilic, accepting the second nucleophilic addition by pyrrole or indole to form α,α-disubstituted malonates. Subsequent hydrolysis followed by decarboxylation resulted in (α-indolyl-α-acylamino)acetic acid formation; homologs of tryptophan. Through this process, DEMO serves as a synthetic equivalent of α,α-dicationic acetic acid to facilitate nucleophilic introduction of the two substituents.

Synthesis of Unsymmetrical Ketones Using Chelation-Controlled Sequential Substitution of N-Triazinylamide/Weinreb Amide by Organometallic Reagents.

N-(2,4-Dimethoxy-1,3,5-triazinyl)amide was found to exhibit similar behavior to N-methoxy-N-methylamide (Weinreb amide) but higher reactivity for nucleophilic substitution by organometallic reagents. Triazinylamide suppresses overaddition, leading to the formation of a tertiary alcohol by the chelating ability of the triazinyl and carbonyl groups. Ureas possessing both triazinylamino and methoxy(methyl)amino groups underwent sequential nucleophilic substitution with different organometallic reagents, which furnished unsymmetrical ketones without any detectable tertiary alcohols.

Nitroacetonitrile and Its Synthetic Equivalents.

Nitroacetonitrile (NAN) serves as a cyano(nitro)methylating agent facilitating the construction of polyfunctionalized compounds; however, its explosive property is a significant drawback in terms of practical handling. Alkali metal salts of NAN are thermally stable, but their insolubility in organic solvents restricts their use as a synthetic reagents. On the contrary, dipyrrolidinium cyano-aci-nitroacetate is soluble in common organic solvents and thermally stable, allowing for its use as an alternative synthetic equivalent of nitroacetonitrile for the construction of polyfunctionalized frameworks via cyano(nitro)methylation.

2,2-Bis[3,5-bis-(di-methyl-amino)-phen-yl]-1,1,1,3,3,3-hexa-methyl-tris-ilane.

The title compound, C26H48N4Si3, was synthesized by the reaction of 2,2-di-chloro-tris-ilane with 3,5-bis-(di-methyl-amino)-phenyl-lithium. In the mol-ecule, the dihedral angle between the benzene rings is 57.57 (7)° and the Si-Si-Si bond angle is 110.08 (2)°. In the crystal, mol-ecules are linked via an SiC-H⋯π(ar-yl) inter-action, forming a chain along the c-axis direction.

Development of a safely handleable synthetic equivalent of cyanonitrile oxide by 1,3-dipolar cycloaddition of nitroacetonitrile.

Dianionic cyano-aci-nitroacetate affords 3-cyanoisoxazol(in)es upon heating with a range of dipolarophiles in the presence of hydrochloric acid. In this reaction, nitroacetonitrile is formed as an intermediate active species, which serves as a synthetic equivalent of cyanonitrile oxide that can participate in a 1,3-dipolar cycloaddition reaction.

Phosphine Induced Dimerization of Propargyl Alcohols Leading to Allyl Propargyl Ethers.

A facile method for synthesizing allyl propargyl ethers (APEs) was developed based on the dimerization of propargyl alcohols. The reaction proceeded via an oxaphosphetane intermediate, which was generated without the use of a strong base, thus making this process a pseudo-Wittig reaction under mild reaction conditions. A wide variety of functional groups, including formyl and pyridyl groups were tolerated, thus yielding the corresponding functionalized APEs, which are otherwise not readily prepared via conventional methods. Moreover, a cross-reaction was found to occur when the reaction was conducted in the presence of alcohols that were more acidic than propargyl alcohol, which suggests that the proton transfer from the intermediately formed betaine to the second alcohol is crucial for undergoing the dimerization.

Synthesis of Functionalized 3-Cyanoisoxazoles Using a Dianionic Reagent.

A series of 5-acylated 3-cyanoisoxazoles were efficiently synthesized by the Michael addition of dianionic cyano-aci-nitroacetate to α-chloro-α,ß-unsaturated ketones followed by intramolecular nucleophilic substitution of the nitronate ion intermediate. In this process, the dianionic reagent serves as the safe synthetic equivalent of the explosive nitroacetonitrile. The 3-cyano group is sufficiently reactive toward ethanolysis and 1,3-dipolar cycloaddition with an azide to afford ethyl ester and tetrazole, respectively. A pyridine ring between the 5-acyl and the 4-aryl group was also constructed. This led to the formation of the isoxazolo[5,4-c]quinoline derivative.