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An asymmetric methanolysis of glutaric anhydride and 6 ensuing steps gave veratrol-annulated dimethylcyclo-heptenone diastereomers with 99% ee; ring closures occurred by Friedel-Crafts acylations of carboxylic acids obtained by stereospecific hydrogenolyses of a pair of diastereomeric δ-lactones. The mentioned cycloheptenones and Ph-NH-NH2 underwent Fischer indole syntheses providing the tetracyclic indoles cis- and trans-14a, respectively. Double lithiations with BuLi and quenchings with ClPPh2 furnished the diphosphanes cis- and trans-15 with perfect (P)- and (M)-atropselectivity, respectively.

A novel 3-phenyl-4-thiaglutaric anhydride was employed as a highly reactive partner for the Castagnoli-Cushman reaction. This, in combination with the use of DMF as a reaction medium, resulted in a drastic lowering of the reaction temperature to ambient (compared to the 110–150 °C range typical for similar processes involving glutaric anhydride) and an extended reaction scope (with respect to substitution pattern in the imine component). Diastereomeric products were separated, in the form of respective methyl esters, and their comparative NMR characterization led to preliminary generalizations regarding the syn- and anti-series.

In this study, the preparation and characterization of biobased thermosets comprising epoxidized linseed oil (ELO), adipic acid and/or glutaric anhydride, initiated by N , N -4-dimethylaminopyridine (DMAP) is reported. By changing the ratio of adipic acid to glutaric anhydride, the obtained resins changed from soft and flexible to hard and brittle materials. The Young’s modulus varied from 25 MPa to 1477 MPa, tensile strength varied from 10.3 MPa to 25.7 MPa, and the elongation at break varied from 2.7% to 67.5%. The maximum toughness was found with the sample containing 20% glutaric anhydride and 80% adipic acid. With the increase of glutaric anhydride content, the total heat released during the curing reaction and the glass transition temperature ( T g ) increased. This is the first paper that reports the combination of glutaric anhydride and adipic acid as curing agents for epoxidized plant oils to produce thermosets ranging from flexible to hard.

The solid–liquid equilibrium (SLE) of glutaric anhydride in three pure solvents, tetrachloromethane, acetic acid and ethanoic anhydride, and three binary solvents of acetic acid + tetrachloromethan...

Significant expansion of heterocyclic product space accessible by the Castagnoli-Cushman reaction (CCR) has been achieved via the use of glutaric anhydride analogues containing endocyclic substitutions with oxygen, nitrogen, and sulfur. Incorporation of these heteroatoms in the anhydride's backbone results in enhanced reactivity and generally lower temperatures that are required for the reactions to go to completion. These findings are particularly significant in light of the CCR recently recognized as an efficient tool for lead-oriented synthesis.

Sulfone-substituted γ- and δ-lactams have been prepared in a single step with high diastereoselectivity. Sulfonylglutaric anhydrides produce intermediates that readily decarboxylate to provide δ-lactams with high diastereoselectivity. Substituents at the 3- or 4-position of the glutaric anhydride induce high levels of stereocontrol. Sulfonylsuccinic anhydrides produce intermediate carboxylic acids that can be trapped as methyl esters or allowed to decarboxylate under mild conditions. This method has been applied to a short synthesis of the pyrrolizidine alkaloid (±)-isoretronecanol. © 2014 American Chemical Society.

Chemical conjugates composed of paclitaxel (PTXL) and hyperbranched polyglycidols (HBP) were synthesized using glutaric anhydride as a “bridge” with esterification in dimethylformamide. A series of HBP–PTXL conjugates (HPCs) were synthesized using different molecular weights of HBP and varying ratios of HBP to PTXL, and they were characterized. An intact form of PTXL was regenerated from HPCs under acidic or basic pH conditions. Furthermore, water-soluble HPCs exhibit a more pronounced cytotoxic effect against cancer cells, suggesting that these HPCs can be utilized as tumor-specific therapeutic agents in the form of an injectable drug.

The asymmetric desymmetrization of 3-(4-fluorophenyl)glutaric anhydride 9 with lithiated chiral oxazolidin-2-one 8 has been studied. The desymmetrized product was formed with >90% de and converted into known intermediates for both (+)- and (−)-paroxetines.

The major products of thermal (acetone, CaCl2 excess, reflux) and photochemical (acetone or CCl4, room temperature) oxidation of 2-acetylcyclopentanone with atmospheric oxygen are 2-acetyl-2-hydroxycyclopentanone, 2-acetyl-2-hydroxymethylcyclopentanone, 1,1′-diacetyl-1,1′-bicyclopentyl-2,2′-dione, 2-acetoxycyclopentanone, 5,6-dioxoheptanoic acid, glutaric acid, and glutaric anhydride. The formation of 2-acetyl-2-hydroxycyclopentanone is the first example of the direct α-hydroxylation of β-dicarbonyl compound under the conditions described.

Solenopsins A, B and C have been synthesized in enantiomerically pure forms from the corresponding anti-1,5-diols which have been obtained from glutaric anhydride by an asymmetric synthesis induced by chiral sulfoxides.

The diastereoselective synthesis of ( S)-4-(2,2,4-trimethyl-1,3-dioxolan-4-yl)butan-1-ol ( 9), an intermediate in the asymmetric synthesis of the pine beetle pheromone (-)-frontalin [(1 S,5 R)-1,5-dimethyl-6,8-dioxabicyclo[3.2.1]octane] ( 1), has been accomplished starting from the β-keto sulfoxide 2, derived from glutaric anhydride. The key step of the synthetic sequence is the diastereoselective hydrocyanation of 2 by diethylaluminum cyanide.

Chiloglottone, a wasp pheromone and attractant of sexually deceptive Chiloglottis orchids, and several structural analogs were synthesized. The synthetic approach is facile, high yielding and versatile, enabling rapid divergence to generate dialkylated analogs of chiloglottone. The key transformation was an organocadmium-mediated desymmetrization of glutaric anhydride derivatives. This library of synthetic 2,5-dialkylated 1,3-cyclohexanediones may assist in future identification of natural products in further species.

New spiroxazine 7 carrying a long alkyl chain was prepared by condensation of spiroxazine 5 with glutaric anhydride. The first example of solid-state photochromism and thermochromism in spiroxazine 7 is reported.

Sulfone-substituted γ- and δ-lactams have been prepared in a single step with high diastereoselectivity. Sulfonylglutaric anhydrides produce intermediates that readily decarboxylate to provide δ-lactams with high diastereoselectivity. Substituents at the 3- or 4-position of the glutaric anhydride induce high levels of stereocontrol. Sulfonylsuccinic anhydrides produce intermediate carboxylic acids that can be trapped as methyl esters or allowed to decarboxylate under mild conditions. This method has been applied to a short synthesis of the pyrrolizidine alkaloid (±)-isoretronecanol.

The copolymerization of oxetane with glutaric anhydride was found to proceed with bulky titanium bisphenolate (1) as the initiator. The 1H NMR spectrum of the produced copolymer shows that the copolymer contains both alternating units and oxytrimethylene units in the polymer main chain. 1 was also effective for the copolymerization of oxetane with other cyclic acid anhydrides, affording the corresponding copolymers. With the titanium bisalkolate complex (4), a copolymer rich in alternating sequences was obtained.

A stereoselective total synthesis of (+)-preussin (1) has been achieved from the σ-symmetric 3-dimethyl(phenyl)silyl substituted glutaric anhydride 4 featuring its desymmetrization using Evans’ oxazolidinone 10. The first homochiral intermediate, the glutarate half-ester 9 was obtained from both the diastereoisomeric acids 11a and 12a in a convergent fashion. The dimethyl(phenyl)silyl group is not only acting as a masked hydroxy group but also restricts elimination reactions and facilitates Curtius reaction. It also stereodirects ester enolate alkylation of 18 and hydrogenation of intermediate Δ1-pyrroline 5.

Bicyclic lactams 8 have been prepared in enantiomerically pure form from the corresponding amino esters 5 and glutaric anhydride. The key step is the reduction of imides 7 in methanol. Selective reduction of 8 furnished N-substituted lactams 9.

The title novel carboxylic acid derivative, C9H17NO3, containing the tert-butyl­carbamoyl group, has been synthesized by the reaction of glutaric anhydride and tert-butyl­amine. In the crystal structure, this compound forms intermolecular hydrogen bonds between the amide and carboxyl groups. However, it does not form a hydrogen-bonded dimer involving two carboxylic acid groups.

Modified ovomucoid (OVM) columns were prepared by reaction with glyceraldehyde, formaldehyde and glutaric anhydride. The retention and enantioselective properties of racemic compounds on these modified OVM columns were compared with those on an unmodified OVM column. The retentions of racemic compounds on the modified OVM columns were lower than or approximately equal to those on the unmodified OVM column (except for basic compounds on the OVM column reacted with glutaric anhydride). The modified OVM columns gave lower or approximately equal enantioselectivities than the unmodified OVM column for acidic and unchanged compounds, whereas the modified OVM columns gave higher enantioselectivity for basic compounds. These differences may be mainly attributed to changes in protein conformation, especially changes in chiral recognition site(s) as a result of modification. The results reveal that modification of OVM proteins may be effective for the chiral separation of basic compounds on an OVM column.

A stereoselective total synthesis of (+)-preussin (1) has been achieved from the σ-symmetric 3-dimethyl(phenyl)silyl substituted glutaric anhydride 4 featuring its desymmetrization using Evans’ oxazolidinone 10. The first homochiral intermediate, the glutarate half-ester 9 was obtained from both the diastereoisomeric acids 11a and 12a in a convergent fashion. The dimethyl(phenyl)silyl group is not only acting as a masked hydroxy group but also restricts elimination reactions and facilitates Curtius reaction. It also stereodirects ester enolate alkylation of 18 and hydrogenation of intermediate Δ1-pyrroline 5.

Axial preference (>ca. 70% at 25 °C) of alkoxy and silyloxy groups of the chair-type six-membered cyclic compounds has been clarified by the 1H-NMR bandwidth mesurement method. Based on the X-ray analysis of 4-substituted cyclohexanones, it has been disclosed that the cyclohexanone ring adopts chair form and the 4-substituent occupies the axial site in all cases.

A rhodium phosphinooxazoline system allows for an efficient enantioselective desymmetrization of dimethyl glutaric anhydride. Both commercially available and in situ generated sp3-organozinc nucleophiles couple efficiently in high enantiomeric excess. This chemistry has also been extended to other 3,5-disubstituted anhydrides, and further elaboration has enabled the synthesis of potentially useful syn-deoxypolypropionate fragments.

The reaction between glutaric anhydride (1) and N-benzylidenebenzylamine (3) was studied in detail by 1H NMR spectroscopy under different reaction conditions. The major product was (±)-trans-1-benzyl-6-oxo-2-phenylpiperidine-3-carboxylic acid (2), which was converted into new substituted piperidin-2-ones via transformations of the carboxylic group. The final products are expected to possess pharmaceutical activities, and the relevant screenings are in course.

We present a flexible and cost-efficient synthetic strategy for the preparation of a new family of phosphoramidite and solid-support reagents that can introduce a broad range of modifications into DNA probes. The key intermediate material 3 is synthesized using the inexpensive and commercially available 3-(tert-butyldimethylsiloxy)glutaric anhydride 1 and can be used as common starting material for the preparation of new labeling reagents.

Alternating poly(ester amide)s 6a - e were prepared by polycondensation of α-carboxyl-ω-hydroxyamides 3a - e which were obtained by aminolysis of glutaric anhydride (1) and α,ω-aminoalcohols, H2N-(CH2)x-OH (x = 2 - 6) 2a - e. The polycondensation was performed in dimethylformamide solution using a carbodiimide as activating agent, or in bulk with Bu2Sn(OMe)2, Ti(OBu)4 and Sn(octoate)2 as a catalyst. For the polycondensation in bulk, the influence of catalyst and of temperature on the number-average molecular weight was studied. 1H NMR analyses of the poly(ester amide)s clearly show the alternating microstructure. The poly(ester amide)s from glutaric anhydride and the homologous series of α,ω-aminoalcohols are semicrystalline materials; their melting points show the odd/even effect observed for other poly(ester amide)s.

Reaction of O-protected amino-1,6-anhydro-β- d -hexopyranoses with succinic or glutaric anhydride and subsequent intramolecular acylation afforded the succinimido- and glutarimido-substituted glycosans. Irradiation with UV light of 254 nm wavelength led to γ-hydrogen abstraction at the pyranose ring by the excited carbonyl function. The stereoselective recombination of the resulting 1,4-diradicals gave annelated azetidinols, which fragmented by a retrotransannular ring opening reaction to give the glycosan-annelated azepanedione and azocanedione systems, respectively.

The first macrocyclic diesters of (–)-platynecine (3) containing 10- and 11-membered rings have been prepared. (–)-Platynecine was obtained by catalytic hydrogenation of readily available (+)retronecine (1). Esterification of (+)-retronecine with different glutaric anhydride derivatives yielded mainly the 9-monoesters of (+)-retronecine. Lactonisation was carried out under high dilution conditions via the S-2-pyridyl thioesters to give the 11-membered macrocyclic diesters [(4)–(7)] of (–)-platynecine. Similar treatment of (–)-platynecine with succinic anhydride, and with cis- and trans-cyclohexane-1,2-dicarboxylic anhydride, produced the 10-membered pyrrolizidine alkaloid analogues (8), (9), and (10), respectively.