Month: December 2022

Modular Difunctionalization of Unactivated Alkenes through Bio-Inspired Radical Ligand Transfer Catalysis was written by Bian, Kang-Jie;Nemoto, David Jr.;Kao, Shih-Chieh;He, Yan;Li, Yan;Wang, Xi-Sheng;West, Julian G.. And the article was included in Journal of the American Chemical Society in 2022.Application of 2216-51-5 This article mentions the following:

Herein, the first modular, dual catalytic difunctionalization of unactivated alkenes viz., but-3-en-1-ylbenzene, 3-methylbut-2-en-1-yl benzoate, pent-4-en-1-yl 2-[4-[(2-oxocyclopentyl)methyl]phenyl]propanoate, etc. via manganese-catalyzed radical ligand transfer (RLT) was reported. This RLT elementary step involves a coordinated nucleophile rebounding to a carbon-centered radical to form a new C-X bond in analogy to the radical rebound step in metalloenzymes. The protocol leverages the synergetic cooperation of both a photocatalyst and earth-abundant manganese complex to deliver two radical species in succession to minimally functionalized alkenes, enabling modular diversification of the radical intermediate by a high-valent manganese species capable of delivering various external nucleophiles. A broad scope (97 examples, including drugs/natural product motifs), mild conditions, and excellent chemoselectivity were shown for a variety of substrates and fluoroalkyl fragments. Mechanistic and kinetic studies provide insights into the radical nature of the dual catalytic transformation and support radical ligand transfer (RLT) as a new strategy to deliver diverse functionality selectively to carbon-centered radicals. In the experiment, the researchers used many compounds, for example, (1R,2S,5R)-2-Isopropyl-5-methylcyclohexanol (cas: 2216-51-5Application of 2216-51-5).

(1R,2S,5R)-2-Isopropyl-5-methylcyclohexanol (cas: 2216-51-5) belongs to alcohols. Alcohols are among the most common organic compounds. They are used as sweeteners and in making perfumes, are valuable intermediates in the synthesis of other compounds, and are among the most abundantly produced organic chemicals in industry. The most common reactions of alcohols can be classified as oxidation, dehydration, substitution, esterification, and reactions of alkoxides.Application of 2216-51-5

Referemce:
Alcohol – Wikipedia,
Alcohols – Chemistry LibreTexts

Synthesis, Structure, and Reactivity of Rhodium and Iridium Complexes of the Chelating Bis-Sulfoxide tBuSOC₂H₄SOtBu. Selective O-H Activation of 2-Hydroxy-isopropyl-pyridine was written by Schaub, Thomas;Diskin-Posner, Yael;Radius, Udo;Milstein, David. And the article was included in Inorganic Chemistry in 2008.Reference of 1122-71-0 This article mentions the following:

The chloro-bridged Rh and Ir complexes [M₂(BTSE)₂Cl₂] (M = Rh 1, Ir 2) bearing the chelating bis-sulfoxide tBuSOC₂H₄SOtBu (BTSE) were prepared by the reaction of [M₂(COE)₄Cl₂] (M = Rh, Ir; COE = cyclooctene) with an excess of a racemic mixture of the ligand. The cationic compounds [M(BTSE)₂][PF₆] (M = Rh 3, Ir 4), bearing one S- and one O-bonded sulfoxide, were also obtained in good yields. The chloro-bridges in 2 can be cleaved with 2-methyl-6-pyridinemethanol and 2-aminomethyl pyridine, resulting in the Ir(I) complexes [Ir(BTSE)(Py)(Cl)] (Py = 2-methyl-6-pyridinemethanol 5, 2-aminomethyl-pyridine 6). In case of the bulky 2-hydroxy-isopropyl-pyridine, selective OH oxidative addition took place, forming the Ir(III)-hydride [Ir(BTSE)(2-isopropoxy-pyridine)(H)(Cl)] (7), with no competition from the six properly oriented C-H bonds. Cationic Rh(I) and Ir(I) compounds [M(BTSE)(2-aminomethylpyridine)][X] (M = Rh 8, Ir 10), [Rh(BTSE)(2-hydroxy-isopropyl-pyridine)][X] (9) (stabilized by intramol. H bonding), [Ir(BTSE)(pyridine)₂][PF₆] (12), [Ir(BTSE)(α-picoline)₂][PF₆] (13), and [Rh(BTSE)(1,10-phenanthroline)][PF₆] (14) were prepared either by chloride abstraction from the dimeric precursors or replacement of the labile O bonded sulfoxide in 3 or 4. Complex 14 exhibits a dimeric structure in the solid state by π-π stacking of the phenanthroline ligands. In the experiment, the researchers used many compounds, for example, 6-Methyl-2-pyridinemethanol (cas: 1122-71-0Reference of 1122-71-0).

6-Methyl-2-pyridinemethanol (cas: 1122-71-0) belongs to alcohols. The oxygen atom of the strongly polarized O―H bond of an alcohol pulls electron density away from the hydrogen atom. This polarized hydrogen, which bears a partial positive charge, can form a hydrogen bond with a pair of nonbonding electrons on another oxygen atom. Secondary alcohols are easily oxidized without breaking carbon-carbon bonds only as far as the ketone stage. No further oxidation is seen except under very stringent conditions.Reference of 1122-71-0

Referemce:
Alcohol – Wikipedia,
Alcohols – Chemistry LibreTexts

Improvement of the antioxidant activity of thyme essential oil against biosynthesized titanium dioxide nanoparticles-induced oxidative stress, DNA damage, and disturbances in gene expression in vivo was written by Sallam, Mohamed F.;Ahmed, Helmy M. S.;Diab, Kawther A.;El-Nekeety, Aziza A.;Abdel-Aziem, Sekena H.;Sharaf, Hafiza A.;Abdel-Wahhab, Mosaad A.. And the article was included in Journal of Trace Elements in Medicine and Biology in 2022.Application In Synthesis of 5-Isopropyl-2-methylphenol This article mentions the following:

Titanium dioxide nanoparticles (TiO₂-NPs) are widely utilized in medicine and industry; however, their safety in biol. organisms is still unclear. In this study, we determined the bioactive constitutes of thyme essential oil (TEO) and utilized the nanoemulsion technique to improve its protective efficiency against oxidative stress, genotoxicity, and DNA damage of biosynthesized titanium dioxide nanoparticles (TiO₂-NPs). TEO nanoemulsion (TEON) was prepared using whey protein isolate (WPI). Sixty male Sprague-Dawley rats were divided into six groups and treated orally for 21 days including the control group, TEO, or TEON- treated groups (5 mg/kg b.w), TiO₂-NPs-treated group (50 mg/kg b.w) and the groups received TiO₂-NPs plus TEO or TEON. Blood and tissues samples were collected for different assays. The GC-MS anal. identified 17 bioactive compounds in TEO and thymol and carvacrol were the major compounds TEON was irregular with average particles size of 230 ± 3.7 nm and ζ-potential of -24.17 mV. However, TiO₂-NPs showed a polygonal shape with an average size of 50 ± 2.4 nm and ζ-potential of -30.44 mV. Animals that received TiO₂-NPs showed severe disturbances in liver and kidney indexes, lipid profile, oxidant/antioxidant indexes, inflammatory cytokines, gene expressions, increased DNA damage, and pathol. changes in hepatic tissue. Both TEO and TEON showed potential protection against these hazards and TEON was more effective than TEO. The nanoemulsion of TEO enhances the oil bioactivity, improves its antioxidant characteristics, and protects against oxidative damage and genotoxicity of TiO₂-NPs. In the experiment, the researchers used many compounds, for example, 5-Isopropyl-2-methylphenol (cas: 499-75-2Application In Synthesis of 5-Isopropyl-2-methylphenol).

5-Isopropyl-2-methylphenol (cas: 499-75-2) belongs to alcohols. The oxygen atom of the strongly polarized O―H bond of an alcohol pulls electron density away from the hydrogen atom. This polarized hydrogen, which bears a partial positive charge, can form a hydrogen bond with a pair of nonbonding electrons on another oxygen atom. Converting an alcohol to an alkene requires removal of the hydroxyl group and a hydrogen atom on the neighbouring carbon atom. Dehydrations are most commonly carried out by warming the alcohol in the presence of a strong dehydrating acid, such as concentrated sulfuric acid.Application In Synthesis of 5-Isopropyl-2-methylphenol

Referemce:
Alcohol – Wikipedia,
Alcohols – Chemistry LibreTexts

Design and synthesis of new 4-alkylthio monocyclic β-lactams was written by Lee, Sang Hyup. And the article was included in Bulletin of the Korean Chemical Society in 2013.Related Products of 29364-29-2 This article mentions the following:

New types of monocyclic β-lactams constitute an important class of compounds due to their unique structures and natures. Here, the design and synthesis of new 4-alkylthio monocyclic β-lactams 2a and 3a are reported. Significantly, compounds 2a and 3a, while keeping a monocyclic system, were designed to contain all of the substructures provided by the cleavage of C(2)-C(3) bond in penicillins. Efficient synthetic pathways for compounds 2a and 3a were established based on two different strategies. Compound 2a was synthesized from raw materials, using 4-acetoxyazetidin-2-one as a key intermediate, through a ten-step synthetic sequence in 3% overall yield. Compound 3a was synthesized from potassium salt of penicillin G, using the degraded product 20 as a key intermediate, through a six-step synthetic sequence in 11% overall yield. 4-Alkylthioazetidin- 2-one derivatives, introduced could serve as valuable intermediates for the development of new monocyclic β-lactams. In the experiment, the researchers used many compounds, for example, Sodium 2-methyl-2-propanethiolate (cas: 29364-29-2Related Products of 29364-29-2).

Sodium 2-methyl-2-propanethiolate (cas: 29364-29-2) belongs to alcohols. Because alcohols are easily synthesized and easily transformed into other compounds, they serve as important intermediates in organic synthesis. Under carefully controlled conditions, simple alcohols can undergo intermolecular dehydration to give ethers. This reaction is effective only with methanol, ethanol, and other simple primary alcohols.Related Products of 29364-29-2

Referemce:
Alcohol – Wikipedia,
Alcohols – Chemistry LibreTexts

Mechanism of proton transfer to coordinated thiolates: encapsulation of acid stabilizes precursor intermediate was written by Alwaaly, Ahmed;Clegg, William;Harrington, Ross W.;Petrou, Athinoula L.;Henderson, Richard A.. And the article was included in Dalton Transactions in 2015.Application In Synthesis of Sodium 2-methyl-2-propanethiolate This article mentions the following:

Earlier kinetic studies on the protonation of the coordinated thiolate in the square-planar [Ni(SC₆H₄R’-4)(triphos)]⁺ (R’ = NO₂, Cl, H, Me or MeO) by lutH⁺ (lut = 2,6-dimethylpyridine) indicate a two-step mechanism involving initial formation of a (kinetically detectable) precursor intermediate, {[Ni(SC₆H₄R’-4)(triphos)]···Hlut}²⁺ (K^R₁), followed by an intramol. proton transfer step (k^R₂). The analogous [Ni(SR)(triphos)]BPh₄ {R = Et, Bu^t or Cy; triphos = PhP(CH₂CH₂PPh₂)₂} were prepared and characterized by spectroscopy and x-ray crystallog. Similar to the aryl thiolate complexes, [Ni(SR)(triphos)]⁺ are protonated by lutH⁺ in an equilibrium reaction but the observed rate law is simpler. Anal. of the kinetic data for both [Ni(SR)(triphos)]⁺ and [Ni(SC₆H₄R’-4)(triphos)]⁺ shows that both react by the same mechanism, but that K^R₁ is largest when the thiolate is poorly basic, or the 4-R’ substituent in the aryl thiolates is electron-withdrawing. It is both NH···S hydrogen bonding and encapsulation of the bound lutH⁺ (by the Ph groups on triphos) which stabilize the precursor intermediate. In the experiment, the researchers used many compounds, for example, Sodium 2-methyl-2-propanethiolate (cas: 29364-29-2Application In Synthesis of Sodium 2-methyl-2-propanethiolate).

Sodium 2-methyl-2-propanethiolate (cas: 29364-29-2) belongs to alcohols. Similar to water, an alcohol can be pictured as having an sp3 hybridized tetrahedral oxygen atom with nonbonding pairs of electrons occupying two of the four sp3 hybrid orbitals. Under carefully controlled conditions, simple alcohols can undergo intermolecular dehydration to give ethers. This reaction is effective only with methanol, ethanol, and other simple primary alcohols.Application In Synthesis of Sodium 2-methyl-2-propanethiolate

Referemce:
Alcohol – Wikipedia,
Alcohols – Chemistry LibreTexts

Reagent-switch controlled metal-free intermolecular geminal diamination and aminooxygenation of vinylarenes was written by Venkatesan Balaji, Pandur;Chandrasekaran, Srinivasan. And the article was included in Tetrahedron in 2016.Product Details of 5856-63-3 This article mentions the following:

The authors report here the first general method for the geminal diamination and an intermol. metal-free, geminal aminooxygenation of vinylarenes using hypervalent iodine reagent (i.e., iodane). A new m-CPBA mediated geminal aminooxygenation is also reported. A novel reagent-switch for the control of migrating group by controlling the two independent geminal addition paths is developed. Deuterium labeling studies and the control studies have provided unambiguous evidences for the Ph migration and hydride migration in the oxidative geminal difunctionalization process mediated by PhI(OCOCF₃)₂ and m-CPBA, resp. through a semi-pinacol rearrangement. Under optimized conditions the synthesis of the target compounds was achieved using (phenyl)bis(2,2,2-trifluoroacetato-κO)iodine and 4-methylbenzenesulfonic acid hydrate as reagent combination. Starting materials included (ethenyl)benzene derivatives (i.e., stryrene) and chiral amino alc. derivatives, such as N-[(1S)-1-(hydroxymethyl)-2-phenylethyl]-4-methylbenzenesulfonamide, N-[(1R)-1-(hydroxymethyl)propyl]-4-methylbenzenesulfonamide, N-[(1S,2R)-1-(hydroxymethyl)-2-methylbutyl]-4-methylbenzenesulfonamide, amino acids such as N-[(4-methylphenyl)sulfonyl]-L-serine Me ester, N-[(4-methylphenyl)sulfonyl]-L-threonine Me ester. The title compounds thus formed included (2S,4S)-3-[(4-methylphenyl)sulfonyl]-2,4-bis(phenylmethyl)oxazolidine and related substances. (2S,3AS,8aR)-3,3a,8,8a-tetrahydro-3-[(4-methylphenyl)sulfonyl]-2-(phenylmethyl)-2H-indeno[1,2-d]oxazole was also reported. An amino acid reactant delivered (2R,4S)-3-[(4-methylphenyl)sulfonyl]-2-(phenylmethyl)-4-oxazolidinecarboxlyic acid Me estert. Diamine reactants included N,N‘-(1-methyl-1,2-ethanediyl)bis[4-methylbenzenesulfonamide] derivatives The diamine-derived products thus formed included chiral imidazolidine derivatives In the experiment, the researchers used many compounds, for example, (R)-2-Aminobutan-1-ol (cas: 5856-63-3Product Details of 5856-63-3).

(R)-2-Aminobutan-1-ol (cas: 5856-63-3) belongs to alcohols. Similar to water, an alcohol can be pictured as having an sp3 hybridized tetrahedral oxygen atom with nonbonding pairs of electrons occupying two of the four sp3 hybrid orbitals. The most common reactions of alcohols can be classified as oxidation, dehydration, substitution, esterification, and reactions of alkoxides.Product Details of 5856-63-3

Referemce:
Alcohol – Wikipedia,
Alcohols – Chemistry LibreTexts

C1-Symmetric PNP Ligands for Manganese-Catalyzed Enantioselective Hydrogenation of Ketones: Reaction Scope and Enantioinduction Model was written by Zeng, Liyao;Yang, Huaxin;Zhao, Menglong;Wen, Jialin;Tucker, James H. R.;Zhang, Xumu. And the article was included in ACS Catalysis in 2020.Formula: C8H9ClO This article mentions the following:

A family of ferrocene-based chiral PNP ligands I (R = t-Bu, cyclohexyl, Ph, R’ = Ph; R = Ph, R’ = H, i-Pr, PhCH₂) has been reported. These tridentate ligands were successfully applied in Mn-catalyzed asym. hydrogenation of ketones with high enantioselectivities (92-99% ee for aryl alkyl ketones) as well as high efficiencies (TON up to 2000). In addition, dialkyl ketones could also be hydrogenated smoothly. Manganese intermediates that might be involved in the catalytic cycle were analyzed. DFT calculation was carried out to help understand the chiral induction model. The Mn/PNP catalyst could discriminate two groups with different steric properties by deformation of the phosphine moiety in the flexible 5-membered ring. In the experiment, the researchers used many compounds, for example, (R)-1-(3-Chlorophenyl)ethanol (cas: 120121-01-9Formula: C8H9ClO).

(R)-1-(3-Chlorophenyl)ethanol (cas: 120121-01-9) belongs to alcohols. Under appropriate conditions, inorganic acids also react with alcohols to form esters. To form these esters, a wide variety of specialized reagents and conditions can be used. A multistep synthesis may use Grignard-like reactions to form an alcohol with the desired carbon structure, followed by reactions to convert the hydroxyl group of the alcohol to the desired functionality.Formula: C8H9ClO

Referemce:
Alcohol – Wikipedia,
Alcohols – Chemistry LibreTexts

Integration of transcriptomic and metabonomic reveals molecular differences of sweetness and aroma between postharvest and vine ripened tomato fruit was written by Min, Dedong;Li, Zilong;Fu, Xiaodong;Wang, Jihan;Li, Fujun;Li, Xiaoan;Zhang, Xinhua. And the article was included in Food Control in 2022.Formula: C10H14O This article mentions the following:

The quality of vine ripened (PR) fruit is better than that of postharvest ripened (VR) fruit, which is reflected in taste and aroma. The results indicated that there was a remarkable increase in soluble sugars (sucrose, fructose, and glucose) and volatile organic compounds (VOCs) contents during the process of maturity. At the full red stage, VR fruit possessed higher soluble sugars and VOCs contents, especially (E)-2-Octenal, 6-methyl-5-Hepten-2-one, 6,10-dimethyl-5,9-Undecadien-2-one trans-β-Ionone, Me salicylate, compared to PR fruit, which partly explained why VR fruit has better flavor quality. The transcriptome anal. indicated that 4989 and 4847 differentially expressed genes (DEGs) were up- and down-regulated in PR vs.VR, resp. These DEGs participated in multiple metabolic pathways related to sugar and VOCs metabolism Moreover, MYB transcription factors were critical in sugar metabolism And, seven hub genes were found which played key roles in the regulation of fruit flavor. These results laid a foundation for the flavor research of postharvest fruit and enhanced our understanding of the differences in flavor, especially sweetness and aroma between PR and VR fruit. In the experiment, the researchers used many compounds, for example, 5-Isopropyl-2-methylphenol (cas: 499-75-2Formula: C10H14O).

5-Isopropyl-2-methylphenol (cas: 499-75-2) belongs to alcohols. A strong base can deprotonate an alcohol to yield an alkoxide ion (R―O−). For example, sodamide (NaNH2), a very strong base, abstracts the hydrogen atom of an alcohol. Tertiary alcohols cannot be oxidized at all without breaking carbon-carbon bonds, whereas primary alcohols can be oxidized to aldehydes or further oxidized to carboxylic acids.Formula: C10H14O

Referemce:
Alcohol – Wikipedia,
Alcohols – Chemistry LibreTexts

Metal ions and biological action. XXXIV. The complex-forming ability of some pyridylcarbinols was written by Luz, W. D.;Fallab, S.;Erlenmeyer, H.. And the article was included in Helvetica Chimica Acta in 1955.Quality Control of 6-Methyl-2-pyridinemethanol This article mentions the following:

Reaction of 2-ethylpyridine and H₂O₂, and acetylation of the product give an Ac derivative b₁₃ 106-8° which hydrolyzes to give 36% 2-pyridylmethylcarbinol (I), b₁₂ 95-7°. MeMgI and 2-C₆H₄NCHO give 62% I. LiAlH₄ and Et pipecolinate give 2-piperidylcarbinol, m. 60° (picrate m. 128-9.5°). HOCH₂CH₂NH₂ and II do not form complexes with bivalent Cu or Ni ions. 2-Pyridylcarbinol is almost as strong a complexing agent as is oxine. Introduction of a Me group as in I decreases complex formation. In 2-(6-methylpyridyl)carbinol complex formation fails, probably owing to steric factors. In the experiment, the researchers used many compounds, for example, 6-Methyl-2-pyridinemethanol (cas: 1122-71-0Quality Control of 6-Methyl-2-pyridinemethanol).

6-Methyl-2-pyridinemethanol (cas: 1122-71-0) belongs to alcohols. Under appropriate conditions, inorganic acids also react with alcohols to form esters. To form these esters, a wide variety of specialized reagents and conditions can be used. Alcohols may be oxidized to give ketones, aldehydes, and carboxylic acids. These functional groups are useful for further reactions. Oxidation of organic compounds generally increases the number of bonds from carbon to oxygen (or another electronegative element, such as a halogen), and it may decrease the number of bonds to hydrogen.Quality Control of 6-Methyl-2-pyridinemethanol

Referemce:
Alcohol – Wikipedia,
Alcohols – Chemistry LibreTexts

Synthesis of 2-aminomethylpyridine-appended [60]fullerenes. On the difference in the metal-binding properties between 5,6-open and 6,6-closed isomers was written by Ikeda, Atsushi;Fukuhara, Chie;Shinkai, Seiji. And the article was included in Chemistry Letters in 1998.Reference of 1122-71-0 This article mentions the following:

Two 2-aminomethylpyridine-appended [60]fullerenes with the 5,6-open and the 6,6-closed structure were synthesized to examine the influence of the structural difference on the metal-binding ability. Both compounds could form the 1:1 complex with Ag⁺ but the K_ass for the 5,6 isomer was larger by more than two orders of magnitude than that for the 6,6 isomer. In the experiment, the researchers used many compounds, for example, 6-Methyl-2-pyridinemethanol (cas: 1122-71-0Reference of 1122-71-0).

6-Methyl-2-pyridinemethanol (cas: 1122-71-0) belongs to alcohols. Alcohols are among the most common organic compounds. They are used as sweeteners and in making perfumes, are valuable intermediates in the synthesis of other compounds, and are among the most abundantly produced organic chemicals in industry. Converting an alcohol to an alkene requires removal of the hydroxyl group and a hydrogen atom on the neighbouring carbon atom. Dehydrations are most commonly carried out by warming the alcohol in the presence of a strong dehydrating acid, such as concentrated sulfuric acid.Reference of 1122-71-0

Referemce:
Alcohol – Wikipedia,
Alcohols – Chemistry LibreTexts