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Carboalumination of Seven-Membered-Ring trans-Alkenes.

ABSTRACT: Seven-membered-ring trans-alkenes undergo rapid hydro- and carboalumination reactions in the absence of a catalyst with complete regio- and diastereoselectivity. Control experiments, including deuterium labeling, adding radical inhibitors, and using a radical clock, suggest that these reactions proceed by a concerted mechanism. The products of the reaction possess a new carbon-aluminum bond that can then undergo subsequent transformations, particularly oxidation, providing functionalized products as single stereoisomers.

SUBMITTER: Greene MA

PROVIDER: S-EPMC7541770 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Diastereoselective synthesis of seven-membered-ring trans-alkenes from dienes and aldehydes by silylene transfer.

Project description:Silver-catalyzed silylene transfer to alkenes forms vinylsilacyclopropanes regioselectively. These allylic silanes undergo additions to aldehydes to form seven-membered-ring trans-alkenes with high diastereoselectivity. The high reactivity of the trans-alkenes is evidenced by their formal [1,3]-sigmatropic rearrangement reactions and the rapid additions of oxygen-hydrogen bonds across the carbon-carbon double bonds.

| S-EPMC3437758 | biostudies-literature

Seven-membered ring nucleobases as inhibitors of human cytidine deaminase and APOBEC3A.

Project description:The APOBEC3 (APOBEC3A-H) enzyme family as a part of the human innate immune system deaminates cytosine to uracil in single-stranded DNA (ssDNA) and thereby prevents the spread of pathogenic genetic information. However, APOBEC3-induced mutagenesis promotes viral and cancer evolution, thus enabling the progression of diseases and development of drug resistance. Therefore, APOBEC3 inhibition offers a possibility to complement existing antiviral and anticancer therapies and prevent the emergence of drug resistance, thus making such therapies effective for longer periods of time. Here, we synthesised nucleosides containing seven-membered nucleobases based on azepinone and compared their inhibitory potential against human cytidine deaminase (hCDA) and APOBEC3A with previously described 2'-deoxyzebularine (dZ) and 5-fluoro-2'-deoxyzebularine (FdZ). The nanomolar inhibitor of wild-type APOBEC3A was obtained by the incorporation of 1,3,4,7-tetrahydro-2H-1,3-diazepin-2-one in the TTC loop of a DNA hairpin instead of the target 2'-deoxycytidine providing a Ki of 290 ± 40 nM, which is only slightly weaker than the Ki of the FdZ-containing inhibitor (117 ± 15 nM). A less potent but notably different inhibition of human cytidine deaminase (CDA) and engineered C-terminal domain of APOBEC3B was observed for 2'-deoxyribosides of the S and R isomers of hexahydro-5-hydroxy-azepin-2-one: the S-isomer was more active than the R-isomer. The S-isomer shows resemblance in the position of the OH-group observed recently for the hydrated dZ and FdZ in the crystal structures with APOBEC3G and APOBEC3A, respectively. This shows that 7-membered ring analogues of pyrimidine nucleosides can serve as a platform for further development of modified ssDNAs as powerful A3 inhibitors.

| S-EPMC10282898 | biostudies-literature

Stereoelectronic Model To Explain Highly Stereoselective Reactions of Seven-Membered-Ring Oxocarbenium-Ion Intermediates.

Project description:Nucleophilic attack on seven-membered-ring oxocarbenium ions is generally highly stereoselective. The preferred mode of nucleophilic attack forms the product in a conformation that minimizes transannular interactions, thus leading to different stereoselectivity as compared to that of reactions involving six-membered-ring oxocarbenium ions.

| S-EPMC4811184 | biostudies-literature

Lewis acid-assisted Ir(iii) reductive elimination enables construction of seven-membered-ring sulfoxides.

Project description:Iridium has played an important role in the evolution of C-H activation chemistry over the last half century owing to its high reactivity towards stoichiometric C-H bond cleavage; however, the use of Ir(iii) complexes in catalytic C-H functionalization/C-C bond formation appears to have fallen off significantly. The main problem lies in the reductive elimination step, as iridium has a tendency to form stable and catalytically inactive Ir(iii) species. Herein, with a rationally designed Lewis acid assisted oxidatively induced strategy, the sluggish Ir(iii) reductive elimination is successfully facilitated, enabling the facile C-C bond formation. The X-ray crystal structure of a silver salt adduct of iridacycle and DFT calculations demonstrate that the sulfoxide group acts as a key bridge connecting the Ir(iii) metal centre with the silver Lewis acid, which facilitates the reductive elimination of the Ir(iii) metallacycle. Further identification of oxidants was carried out by performing stoichiometric reactions, which enables the development of catalytic construction of various highly functionalized seven-membered-ring sulfoxides, that are of great interest in medicinal chemistry and materials science.

| S-EPMC8162422 | biostudies-literature

Rhodium-catalyzed ring expansion of cyclopropanes to seven-membered rings by 1,5 C-C bond migration.

Project description: Not available

| S-EPMC3329940 | biostudies-literature

Seven-Membered Cyclic Potassium Diamidoalumanyls.

Project description:The seven-membered cyclic potassium alumanyl species, [{SiNMes }AlK]2 [{SiNMes }={CH2 SiMe2 N(Mes)}2 ; Mes=2,4,6-Me3 C6 H2 ], which adopts a dimeric structure supported by flanking K-aryl interactions, has been isolated either by direct reduction of the iodide precursor, [{SiNMes }AlI], or in a stepwise manner via the intermediate dialumane, [{SiNMes }Al]2 . Although the intermediate dialumane has not been observed by reduction of a Dipp-substituted analogue (Dipp=2,6-i-Pr2 C6 H3 ), partial oxidation of the potassium alumanyl species, [{SiNDipp }AlK]2 , where {SiNDipp }={CH2 SiMe2 N(Dipp)}2 , provided the extremely encumbered dialumane [{SiNDipp }Al]2 . [{SiNDipp }AlK]2 reacts with toluene by reductive activation of a methyl C(sp3 )-H bond to provide the benzyl hydridoaluminate, [{SiNDipp }AlH(CH2 Ph)]K, and as a nucleophile with BPh3 and RN=C=NR (R=i-Pr, Cy) to yield the respective Al-B- and Al-C-bonded potassium aluminaborate and alumina-amidinate products. The dimeric structure of [{SiNDipp }AlK]2 can be disrupted by partial or complete sequestration of potassium. Equimolar reactions with 18-crown-6 result in the corresponding monomeric potassium alumanyl, [{SiNDipp }Al-K(18-cr-6)], which provides a rare example of a direct Al-K contact. In contrast, complete encapsulation of the potassium cation of [{SiNDipp }AlK]2 , either by an excess of 18-cr-6 or 2,2,2-cryptand, allows the respective isolation of bright orange charge-separated species comprising the 'free' [{SiNDipp }Al]- alumanyl anion. Density functional theory (DFT) calculations performed on this moiety indicate HOMO-LUMO energy gaps in the of order 200-250 kJ mol-1 .

| S-EPMC8596455 | biostudies-literature

Fully reagent-controlled asymmetric synthesis of (-)-spongidepsin via the Zr-catalyzed asymmetric carboalumination of alkenes (ZACA reaction).

Project description:The ZACA reaction has been shown to proceed satisfactorily with internally OH-substituted 1-alkenes, provided that the OH group is unprotected and non-allylic. This reaction was used for reagent-controlled asymmetric construction of 3. Allylic alcohol was converted to 2 in seven steps via iterative ZACA processes and simple chromatography. (-)-Spongidepsin (1) was synthesized by using 2 and 3 through application of the esterification-amidation-ring-closing metathesis protocol previously reported.

| S-EPMC3891660 | biostudies-literature

Access to benzo-fused nine-membered heterocyclic alkenes with a trifluoromethyl carbinol moiety via a double decarboxylative formal ring-expansion process under palladium catalysis.

Project description:Direct access to pharmaceutically attractive benzo-fused nine-membered heterocyclic alkenes 3 with a trifluoromethyl carbinol moiety was achieved via a palladium-catalyzed double-decarboxylative formal ring-expansion process from six-membered trifluoromethyl benzo[d][1,3]oxazinones 1 to nine-membered trifluoromethyl benzo[c][1,5]oxazonines 3 in the presence of vinylethylene carbonates 2. Generation of a Pd-π-allyl zwitterionic intermediate was proposed in the catalytic cycle. The trifluoromethyl group in the benzoxazinanones 1 plays an important role throughout the transformation. Diastereoselective chemical transformations of products 3 were also demonstrated.

| S-EPMC5915791 | biostudies-literature

A three-membered ring approach to carbonyl olefination.

Project description:The carbon-carbon double bond, with its diverse and multifaceted reactivity, occupies a prominent position in organic synthesis. Although a variety of simple alkenes are readily available, the mild and chemoselective introduction of a unit of unsaturation into a functionalized organic molecule remains an ongoing area of research, and the olefination of carbonyl compounds is a cornerstone of such approaches. Here we show the direct olefination of hydrazones via the intermediacy of three-membered ring species generated by addition of sulfoxonium ylides, departing from the general dogma of alkenes synthesis from carbonyls. Moreover, the mild reaction conditions and operational simplicity of the transformation render the methodology appealing from a practical point of view.

| S-EPMC5653658 | biostudies-literature

Six-membered-ring inorganic materials: definition and prospects.

Project description:The six-membered ring (SMR) is a common structure unit for numerous material systems. These materials include, but are not limited to, the typical two-dimensional materials such as graphene, h-BN, and transition metal dichalcogenides, as well as three-dimensional materials such as beryllium, magnesium, MgB2 and Bi2Se3. Although many of these materials have already become 'stars' in materials science and condensed-matter physics, little attention has been paid to the roles of the SMR unit across a wide range of compositions and structures. In this article, we systematically analyze these materials with respect to their very basic SMR structural unit, which has been found to play a deterministic role in the occurrence of many intriguing properties and phenomena, such as Dirac electronic and phononic spectra, superconductivity and topology. As a result, we have defined this group of materials as SMR inorganic materials, opening up a new perspective on materials research and development. With their unique properties, SMR materials deserve wide attention and in-depth investigation from materials design, new physical discoveries to target-wizard applications. It is expected that SMR materials will find niche applications in next-generation information technology, renewable energy, space, etc.

| S-EPMC8294346 | biostudies-literature

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