Month: October 2022

Synthetic Route of C6H5IOIn 2021 ,《Access to S-Stereogenic Free Sulfoximines via Bifunctional Phosphonium Salt-Catalyzed Desymmetrization of Bisphenols》 was published in ACS Catalysis. The article was written by Fang, Siqiang; Liu, Zanjiao; Zhang, Hongkui; Pan, Jianke; Chen, Yuan; Ren, Xiaoyu; Wang, Tianli. The article contains the following contents:

Sulfur-stereogenic sulfoximines particularly with a free N-H unit exhibit intriguing chem. and biol. activities, and thus have received continuous attention from chemists. However, there are currently no examples of guiding catalytic asym. strategies available to directly access these mols. Herein, an efficient and practical protocol for the direct enantioenrichment of free N-H sulfoximines via a bifunctional phosphonium salt-catalyzed desymmetrization triggered by the Atherton-Todd reaction together with a further extended nucleophilic acyl substitution-type reaction has been disclosed. A series of free N-H sulfoximines bearing an assortment of aromatic groups (70 examples) was tolerated in this desymmetrization with incidentally involving minority kinetic resolution (KR). The desymmetrized products can be easily transformed into chiral sulfoxides and other classes of active sulfur-stereogenic compounds Mechanistic studies provided insights into the reaction pathway particularly suggesting a desymmetrization/KR synergic process, and also offered support on hydrogen-bonding interactions as the key elements to successful stereocontrol. In the experiment, the researchers used 3-Iodophenol(cas: 626-02-8Synthetic Route of C6H5IO)

3-Iodophenol(cas: 626-02-8) belongs to organic iodides. The carbon-iodine bond is weaker than other carbon-halogen bonds due to the poor electronegative nature of the iodine atom. Alkyl iodides react at a faster rate than alkyl fluorides due to the weak C-I bond.Synthetic Route of C6H5IO

Referemce:
Iodide – Wikipedia,
Iodide – an overview | ScienceDirect Topics – ScienceDirect.com

《Revisiting the Urech Synthesis of Hydantoins: Direct Access to Enantiopure 1,5-Substituted Hydantoins Using Cyanobenziodoxolone》 was written by Declas, Nina; Le Vaillant, Franck; Waser, Jerome. Category: iodides-buliding-blocksThis research focused onurech synthesis enantiopure substituted hydantoin preparation; hydantoin preparation hypervalent iodine cyanation reagent amino acid reaction. The article conveys some information:

A method for the synthesis of enantiopure 1,5-substituted hydantoins was developed using a hypervalent iodine cyanation reagent (cyanobenziodoxolone, CBX) as a source of electrophilic carbon. Starting from inexpensive com. available enantiopure protected amino acids, the method allowed the synthesis of various hydantoins without epimerization. Formation of hydantoins from dipeptides was also possible, but partial epimerization was observed in this case. This synthetic strategy is user friendly as CBX is a bench-stable easy-to-handle crystalline reagent and avoids conventional multistep protocols, thus allowing the facile synthesis of a library of chiral hydantoins. In addition to this study using 2-Iodobenzoic acid, there are many other studies that have used 2-Iodobenzoic acid(cas: 88-67-5Category: iodides-buliding-blocks) was used in this study.

2-Iodobenzoic acid(cas: 88-67-5) belongs to organic iodides. The carbon-iodine bond is weaker than other carbon-halogen bonds due to the poor electronegative nature of the iodine atom. In general, organic iodides are light-sensitive and turn yellow during storage, owing to the formation of iodine.Category: iodides-buliding-blocks

Referemce:
Iodide – Wikipedia,
Iodide – an overview | ScienceDirect Topics – ScienceDirect.com

Quality Control of (R)-3,3′-Diiodo-2,2′-bis(methoxymethoxy)-1,1′-binaphthaleneOn September 17, 2021 ,《Catalytic Asymmetric (3 + 3) Cycloaddition of Oxyallyl Zwitterions with α-Diazomethylphosphonates》 was published in Organic Letters. The article was written by Liu, Yan; Peng, Xian; She, Rui; Zhou, Xin; Peng, Yungui. The article contains the following contents:

The unique structure of oxyallyls represents a significant challenge for their catalytic asym. applications. Herein, an unprecedented chiral imidodiphosphoric acid-catalytic enantioselective (3 + 3) cycloaddition between oxyallyl zwitterions generated in situ from α-haloketones and α-diazomethylphosphonates was developed. Pharmaceutically interesting chiral pyridazine-4(1H)-ones were obtained in up to 98% yields with excellent stereoselectivities (up to 99% ee, > 99:1 dr). In the experiment, the researchers used (R)-3,3′-Diiodo-2,2′-bis(methoxymethoxy)-1,1′-binaphthalene(cas: 189518-78-3Quality Control of (R)-3,3′-Diiodo-2,2′-bis(methoxymethoxy)-1,1′-binaphthalene)

(R)-3,3′-Diiodo-2,2′-bis(methoxymethoxy)-1,1′-binaphthalene(cas: 189518-78-3) belongs to organic iodides. The carbon-iodine bond is weaker than other carbon-halogen bonds due to the poor electronegative nature of the iodine atom. Organic iodides can be alkyl, alkenyl, or alkynyl, and all of them are very reactive toward with many kinds of nucleophiles.Quality Control of (R)-3,3′-Diiodo-2,2′-bis(methoxymethoxy)-1,1′-binaphthalene

Referemce:
Iodide – Wikipedia,
Iodide – an overview | ScienceDirect Topics – ScienceDirect.com

Application In Synthesis of 2-Chloro-5-iodo-3-(trifluoromethyl)pyridineOn September 2, 2022 ,《PdII-Catalyzed γ-C(sp3)-H (Hetero)arylation of Ketones Enabled by Transient Directing Groups》 was published in ACS Catalysis. The article was written by Li, Yi-Hao; Ouyang, Yuxin; Chekshin, Nikita; Yu, Jin-Quan. The article contains the following contents:

Pd(II)-catalyzed γ-C(sp3)-H (hetero)arylation of aliphatic ketones is developed using α-amino acids as transient directing groups (TDG). A variety of aliphatic ketones were (hetero)arylated at the γ-position via a 5,6-membered fused cyclopalladation intermediate to afford the remotely arylated products in up to 88% yield. The crucial ligand effect of 2-pyridone is further enhanced by reducing the loading of acid additives. Consequentially, the improved reactivity of this catalytic system has also made possible the cyclic γ-methylene C(sp3)-H arylation of ketones. Mechanistic investigation and comparison to the γ-C-H arylation of aldehydes revealed a structural insight for designing site-selective TDG. The results came from multiple reactions, including the reaction of 2-Chloro-5-iodo-3-(trifluoromethyl)pyridine(cas: 887707-25-7Application In Synthesis of 2-Chloro-5-iodo-3-(trifluoromethyl)pyridine)

2-Chloro-5-iodo-3-(trifluoromethyl)pyridine(cas: 887707-25-7) belongs to pyridine. Pyridine, its benzo and pyridine-based compounds play diverse roles in organic chemistry. As ligands, solvents, and catalysts they facilitate reactions; thus descriptions of these new ligands and their applications abound each year.Application In Synthesis of 2-Chloro-5-iodo-3-(trifluoromethyl)pyridine

Referemce:
Iodide – Wikipedia,
Iodide – an overview | ScienceDirect Topics – ScienceDirect.com

In 2015,Miao, Jinmin; Yang, Ke; Kurek, Martin; Ge, Haibo published 《Palladium-Catalyzed Site-Selective Fluorination of Unactivated C(sp3)-H Bonds》.Organic Letters published the findings.Product Details of 624-73-7 The information in the text is summarized as follows:

The transition-metal-catalyzed direct C-H bond fluorination is an attractive synthetic tool toward the preparation of organofluorines. While many methods exist for the direct sp3 C-H functionalization, site-selective fluorination of unactivated sp3 carbons remains a challenge. Direct, highly site-selective and diastereoselective fluorination of aliphatic amides via a palladium-catalyzed bidentate ligand-directed C-H bond functionalization process on unactivated sp3 carbons is reported. With this approach, a wide variety of β-fluorinated amino acid derivatives and aliphatic amides, important motifs in medicinal and agricultural chem., were prepared with palladium acetate as the catalyst and Selectfluor as the fluorine source. The experimental part of the paper was very detailed, including the reaction process of 1,2-Diiodoethane(cas: 624-73-7Product Details of 624-73-7)

1,2-Diiodoethane(cas: 624-73-7) is one of organic iodides. Organic iodides are used in veterinary products (Organic Iodide Powder) as a nutritional source of iodine. In the chemical industry, alkyl iodides serve as excellent alkylating agents and, specifically, methyl iodide is used as a methylating agent in the synthesis of various pharmaceutical drugs. Oceanic alkyl iodides are believed to be the principal source of atmospheric iodine.Product Details of 624-73-7

Referemce:
Iodide – Wikipedia,
Iodide – an overview | ScienceDirect Topics – ScienceDirect.com

In 2019,Tetrahedron Letters included an article by Fu, Fang; Gurung, Laxman; Czaun, Miklos; Mathew, Thomas; Prakash, G. K. Surya. Synthetic Route of C6H4BrI. The article was titled 《ipso-Bromination/iodination of arylboronic acids: Poly(4-vinylpyridine)-Br2/I2 complexes as safe and efficient reagents》. The information in the text is summarized as follows:

Poly(4-vinyl pyridine) supported bromine/iodine complexes were prepared and probed for ipso-bromination/iodination of arylboronic acids ArB(OH)2 (Ar = 4-methylphenyl, 3-nitrophenyl, naphthalen-2-yl, etc.). These solid complexes with catalytic amount of additive are found to be safe and efficient reagent system for the ipso-bromination/iodination. The reaction occurs under mild conditions and tolerates various functional groups resulting in products ArX (X = Br, I) with high selectivity and yields. The results came from multiple reactions, including the reaction of 1-Bromo-4-iodobenzene(cas: 589-87-7Synthetic Route of C6H4BrI)

1-Bromo-4-iodobenzene(cas: 589-87-7) has been employed as reagent for in situ desilylation and coupling of silylated alkynes, as starting reagent in the total syntheses of ent-conduramine A and ent-7-deoxypancratistatin (alkaloids), as substrate in copper-free Sonogashira coupling in aqueous acetone in synthesis of β,β,dibromostyrenesSynthetic Route of C6H4BrI

Referemce:
Iodide – Wikipedia,
Iodide – an overview | ScienceDirect Topics – ScienceDirect.com

In 2019,Green Chemistry included an article by Gong, Xinchi; Wu, Jie; Meng, Yunge; Zhang, Yulan; Ye, Long-Wu; Zhu, Chunyin. Product Details of 624-31-7. The article was titled 《Ligand-free palladium catalyzed Ullmann biaryl synthesis: ‘household’ reagents and mild reaction conditions》. The information in the text is summarized as follows:

A palladium catalyzed Ullmann biaryl ArAr1, Ar1Ar1, ArAr, (Ar = 4-CNC6H4, pyridin-2-yl, 3-MeC6H4, etc.; Ar1 = 4-CNC6H4, 4-MeOC6H4) synthesis has been developed using hydrazine hydrate as the reducing reagent at room temperature The combination of Pd(OAc)2 and hydrazine hydrate works smoothly for the coupling of both electron-rich and electron-deficient aryl iodides ArI and Ar1I, as well as 2-iodopyridine, leading to a wide range of biaryls in good to excellent yields. The reaction requires only 1 mol% Pd(OAc)2 and the in situ generated palladium nanoparticles are found to be active catalysts. After reading the article, we found that the author used 1-Iodo-4-methylbenzene(cas: 624-31-7Product Details of 624-31-7)

1-Iodo-4-methylbenzene(cas: 624-31-7) undergoes Suzuki-Miyaura coupling reaction with phenylboronic acid catalyzed by (Ni,Mg)3Si2O5(OH)4 solid-solution nanotubes loaded with palladium.Product Details of 624-31-7

Referemce:
Iodide – Wikipedia,
Iodide – an overview | ScienceDirect Topics – ScienceDirect.com

In 2019,Journal of Catalysis included an article by Ji, Wei; Wang, Hao; Li, Cheng-An; Gao, Fei; An, Zhong-Fu; Huang, Ling; Wang, He; Pan, Yue; Zhu, Dun-Ru; Wang, Jian-Qiang; Guo, Cheng; Mayoral, Jose A.; Jing, Su. Quality Control of 1-Chloro-3-iodobenzene. The article was titled 《Cuprous cluster as effective single-molecule metallaphotocatalyst in white light-driven C-H arylation》. The information in the text is summarized as follows:

This study investigated a series of ferrocenyltelluroether based cuprous halide clusters as effective single-mol. metallaphotocatalysts (SMP) in white light-driven C-H arylation at room temperature and air. A systematic mechanistic study reveals that Cu(I) cluster can be irradiated by visible light to promote proton-coupled electron transfer (PCET), during which the electron from Cu(I)* leaves together with the proton from benzothiazole C-H, leading to the formation of benzothiazolate-coordinated Cu(II) intermediate and aryl radical. Subsequently, the electron transfer (ET) from the ferrocene unit to the Cu(II) center releases the reactive benzothiazolate to form the target product with aryl radical. The advantages of these copper(I) halide clusters as SMP include high photocatalytic efficiency, structure adjustability, mild reaction conditions and good functional group tolerance. In the experimental materials used by the author, we found 1-Chloro-3-iodobenzene(cas: 625-99-0Quality Control of 1-Chloro-3-iodobenzene)

1-Chloro-3-iodobenzene(cas: 625-99-0) belongs to organic iodides. The carbon-iodine bond is weaker than other carbon-halogen bonds due to the poor electronegative nature of the iodine atom. Quality Control of 1-Chloro-3-iodobenzene Organic iodides can be alkyl, alkenyl, or alkynyl, and all of them are very reactive toward with many kinds of nucleophiles.

Referemce:
Iodide – Wikipedia,
Iodide – an overview | ScienceDirect Topics – ScienceDirect.com

In 2019,Chemical Science included an article by Liu, Gongyi; Zhang, Heng; Huang, Yi; Han, Zhengyu; Liu, Gang; Liu, Yuanhua; Dong, Xiu-Qin; Zhang, Xumu. Product Details of 625-99-0. The article was titled 《Efficient synthesis of chiral 2,3-dihydro-benzo[b]thiophene 1,1-dioxides via Rh-catalyzed hydrogenation》. The information in the text is summarized as follows:

Rh-catalyzed asym. hydrogenation of prochiral substituted benzo[b]thiophene 1,1-dioxides was successfully developed, affording various chiral 2,3-dihydrobenzo[b]thiophene 1,1-dioxides I (R = H, 6-MeO; R1 = C6H5, 4-MeOC6H4, 4-FC6H4, etc.; R2 = C6H5, 4-MeOC6H4, 3-H3CC6H4, etc.) with high yields and excellent enantioselectivities (up to 99% yield and >99% ee). In particular, for challenging substrates, such as aryl substituted substrates with sterically hindered groups and alkyl substituted substrates, the reaction proceeded smoothly in catalytic system with excellent results. The gram-scale asym. hydrogenation proceeded well with 99% yield and 99% ee in the presence of 0.02 mol% (S/C = 5000) catalyst loading. The possible hydrogen-bonding interaction between the substrate and the ligand may play an important role in achieving high reactivity and excellent enantioselectivity. The experimental process involved the reaction of 1-Chloro-3-iodobenzene(cas: 625-99-0Product Details of 625-99-0)

1-Chloro-3-iodobenzene(cas: 625-99-0) belongs to organic iodides. Generally organic iodides can be divided into two classes of alkyl iodides and aryl iodides. Typical reactions of alkyl iodides include nucleophilic substitution, elimination, reduction, and the formation of organometallics.Product Details of 625-99-0Halogenation of aromatic hydrocarbons is a very important reaction via an electrophilic aromatic substitution.

Referemce:
Iodide – Wikipedia,
Iodide – an overview | ScienceDirect Topics – ScienceDirect.com

In 2019,Nature Chemistry included an article by Xia, Guoqin; Weng, Jiang; Liu, Luoyan; Verma, Pritha; Li, Ziqi; Yu, Jin-Quan. Reference of 1-Iodo-4-methylbenzene. The article was titled 《Reversing conventional site-selectivity in C(sp3)-H bond activation》. The information in the text is summarized as follows:

One of the core barriers to developing C-H activation reactions is the ability to distinguish between multiple C-H bonds that are nearly identical in terms of electronic properties and bond strengths. Through recognition of distance and mol. geometry, remote C(sp2)-H bonds have been selectively activated in the presence of proximate ones. Yet achieving such unconventional site selectivity with C(sp3)-H bonds remains a paramount challenge. Here we report a combination of a simple pyruvic acid-derived directing group and a 2-pyridone ligand that enables the preferential activation of the distal γ-C(sp3)-H bond over the proximate β-C(sp3)-H bonds for a wide range of alc.-derived substrates [e.g., I + Me 4-iodobenzoate → II (52%, + 23% diarylated, after esterification)]. A competition experiment between the five- and six-membered cyclopalladation step, as well as kinetic experiments, demonstrate the feasibility of using geometric strain to reverse the conventional site selectivity in C(sp3)-H activation. The experimental process involved the reaction of 1-Iodo-4-methylbenzene(cas: 624-31-7Reference of 1-Iodo-4-methylbenzene)

1-Iodo-4-methylbenzene(cas: 624-31-7) undergoes Suzuki-Miyaura coupling reaction with phenylboronic acid catalyzed by (Ni,Mg)3Si2O5(OH)4 solid-solution nanotubes loaded with palladium.Reference of 1-Iodo-4-methylbenzene

Referemce:
Iodide – Wikipedia,
Iodide – an overview | ScienceDirect Topics – ScienceDirect.com