Organic & Biomolecular Chemistry最新文献_第6页

Visible-light driven macrocyclization of peptides: from a vinyl to an α-selenoketone motif. 可见光驱动的多肽大环化：从乙烯基到α-硒酮基序。

IF 2.8 3区化学

Organic & Biomolecular Chemistry Pub Date : 2026-10-13 DOI: 10.1039/d6ob01411a

Mateusz Waliczek, Zuzanna Słomiana, Klaudia Faba, Martyna Strączek, Piotr Stefanowicz

引用次数: 0

Mild acid-catalyzed pinacol rearrangement of phorbol derivatives: a mechanistic and synthetic study. 温和酸催化苯酚衍生物重排：机理和合成研究。

IF 2.8 3区化学

Organic & Biomolecular Chemistry Pub Date : 2026-10-12 DOI: 10.1039/d6ob01082b

Felipe Escobar-Montaño, Jesús Sánchez-Márquez, José M Botubol-Ares, Rosa Durán-Patrón, David Zorrilla, Antonio J Macías-Sánchez, Rosario Hernández-Galán

引用次数: 0

Recent advances in manganese-catalyzed sp³ C-H functionalization. 锰催化sp3碳氢官能化的研究进展。

IF 2.8 3区化学

Organic & Biomolecular Chemistry Pub Date : 2026-10-12 DOI: 10.1039/d6ob01239f

Mohan M Mokariya, Shreeya Dave, Arpan Patel, Shivam Vispute, Maulik Pethani, Togati Naveen

{"title":"Recent advances in manganese-catalyzed sp3 C-H functionalization.","authors":"Mohan M Mokariya, Shreeya Dave, Arpan Patel, Shivam Vispute, Maulik Pethani, Togati Naveen","doi":"10.1039/d6ob01239f","DOIUrl":"https://doi.org/10.1039/d6ob01239f","url":null,"abstract":"Manganese, the 12th most abundant element in Earth's crust, offers unprecedented opportunities to produce valuable products from simple hydrocarbon scaffolds via C-H bond transformations. Owing to its rich redox chemistry, low toxicity, and natural abundance, manganese has emerged as a versatile tool for derivatizing sp3 C-H bonds, particularly unactivated ones. Its outstanding tunability and ability to generate high-valent, redox-active intermediates have enabled direct modification and activation of a remote sp3 C-H bond. Decades of studies show that manganese has been used to convert unactivated sp3 C-H bonds into vital C-Z bonds. These protocols demonstrate that manganese, combined with selective oxidants and additives, provides powerful synthetic utility for the functionalization of distant, unactivated sp3 C-H bonds into desired C-Z bonds. This review offers a thorough summary of current developments and limitations in manganese-catalyzed functionalization of unactivated sp3 C-H bonds, reported in the past seven years (2020-2026).","PeriodicalId":96,"journal":{"name":"Organic & Biomolecular Chemistry","volume":" ","pages":""},"PeriodicalIF":2.8,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149163935","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Improving the transallylation activity of halide methyltransferase from Arabidopsis thaliana through rational design. 通过合理设计提高拟南芥卤化物甲基转移酶转烯丙基化活性。

IF 2.8 3区化学

Organic & Biomolecular Chemistry Pub Date : 2026-10-12 DOI: 10.1039/d6ob01133k

Yunbin Wu, Qinyao Jia, Hong Yang, Weihua Wang, Wenyan Wang, Heng Song

{"title":"Improving the transallylation activity of halide methyltransferase from Arabidopsis thaliana through rational design.","authors":"Yunbin Wu, Qinyao Jia, Hong Yang, Weihua Wang, Wenyan Wang, Heng Song","doi":"10.1039/d6ob01133k","DOIUrl":"https://doi.org/10.1039/d6ob01133k","url":null,"abstract":"The allyl group is a ubiquitous structural motif found in numerous natural products and bioactive molecules. It can also serve as a highly reactive and versatile building block for the preparation of pharmaceuticals and functional materials in organic chemistry. Currently, the introduction of allyl groups mainly relies on chemical methods that require transition metals, especially precious ones. Although biocatalytic allylation using allylated S-adenosyl-L-methionine (SAM) as the allyl donor provides a promising, sustainable route to allylated compounds, the current access to allylated SAM is still not sufficiently efficient for further preparative-scale applications. In this study, we successfully engineered an Arabidopsis thaliana halide methyltransferase mutant named AtHMT A144G for the efficient synthesis of allylated SAM. Experimental results showed that the A144G variant (∼2.6 × 10-5 s-1 μM-1) exhibited an ∼44-fold higher catalytic efficiency (kcat/KM) relative to the previously reported V140T mutant (∼5.9 × 10-7 s-1 μM-1, newly measured in our study). In addition, the mutation did not alter the stereoselectivity of the enzyme, which still exclusively afforded the reactive (S)-diastereoisomer. To fully exploit the superior catalytic performance of A144G, we systematically optimized the reaction conditions, including the buffer system (KPi buffer), pH (7.5), and temperature (30 °C). With the optimal reaction conditions in hand, the feasibility of using AtHMT A144G as a catalyst to efficiently supply allylated SAM was validated in a cascade reaction with C/N/O-methyltransferases (e.g., NovO, COMT, and NMT) for allyl transfer. Furthermore, the desired allylated products were successfully obtained, confirming the practicality of A144G as an allyl donor platform for diverse downstream allyl transfer reactions.","PeriodicalId":96,"journal":{"name":"Organic & Biomolecular Chemistry","volume":" ","pages":""},"PeriodicalIF":2.8,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149163445","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Total synthesis of (±)-cephanolide B and formal syntheses of (±)-cephanolide C and (±)-cephinoid H. （±）-头孢内酯B的全合成和（±）-头孢内酯C和（±）-头孢内酯H的正式合成。

IF 2.8 3区化学

Organic & Biomolecular Chemistry Pub Date : 2026-10-12 DOI: 10.1039/d6ob01421f

Anirban Maity, Krishna P Kaliappan

引用次数: 0

Divergent synthesis of polysubstituted 2H-imidazoles and 3-imidazolines from α-aminoketones, ketones, and ammonium acetate. α-氨基酮、酮和乙酸铵催化合成多取代2h -咪唑和3-咪唑。

IF 2.8 3区化学

Organic & Biomolecular Chemistry Pub Date : 2026-10-12 DOI: 10.1039/d6ob01254j

Hanming Yang, Feng Zhao

引用次数: 0

Insights into the role that Pt- and carbon-electrodes play in controlling the selectivity of electrochemical reactions. 铂电极和碳电极在控制电化学反应选择性中的作用。

IF 2.8 3区化学

Organic & Biomolecular Chemistry Pub Date : 2026-10-12 DOI: 10.1039/d6ob01159d

Kaida Liu, Nhu H Quach, Enqi Feng, Qiwei Jing, Kevin D Moeller, Matthew Neurock

{"title":"Insights into the role that Pt- and carbon-electrodes play in controlling the selectivity of electrochemical reactions.","authors":"Kaida Liu, Nhu H Quach, Enqi Feng, Qiwei Jing, Kevin D Moeller, Matthew Neurock","doi":"10.1039/d6ob01159d","DOIUrl":"https://doi.org/10.1039/d6ob01159d","url":null,"abstract":"While significant efforts have been devoted to understanding the mechanisms that govern electrolysis reactions, relatively little emphasis has been placed on elucidating the electrode/substrate interactions that are often key to reaction success. Toward this goal, the present work specifically examines the selectivity of competition studies using the TEMPO-mediated oxidation of 4-methoxybenzyl alcohol (MBA) and 4-nitrobenzyl alcohol (NBA). The selectivity for the reaction was found to be 1 : 1 when the reactions were confined to the surface of a Pt anode, but 19 : 1 when the reactions were confined to the surface of a reticulated vitreous carbon (RVC) anode. Potential-dependent ab initio molecular dynamics (AIMD) and density functional theory (DFT) simulations were carried out with explicit substrate and solvent molecules to elucidate the mechanistic features that control the observed selectivity differences. Our results indicate that the different selectivity originates from the changes in the substrate adsorption energies on the different electrodes along with the changes in their intrinsic activation barriers for selective oxidation. The Pt electrode strongly binds both benzyl alcohols and induces significant structural changes to the adsorbed aromatic. On the contrary, the positively charged carbon-electrode binds weakly to the two benzyl alcohols via van der Waals and π-π interactions, a situation that preserves the structure of the aromatic rings and allows for the electronic differences between the rings to dictate the selectivity of the reactions. This computational model was experimentally confirmed with studies that illustrated how fundamental insights into substrate/electrode interactions can be translated into new chemical selectivity.","PeriodicalId":96,"journal":{"name":"Organic & Biomolecular Chemistry","volume":" ","pages":""},"PeriodicalIF":2.8,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149163362","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Theoretical study of the effects of reversible post-translational modifications on the bond dissociation energies of amino acid C-H bonds. 可逆翻译后修饰对氨基酸C-H键解离能影响的理论研究。

IF 2.8 3区化学

Organic & Biomolecular Chemistry Pub Date : 2026-10-12 DOI: 10.1039/d6ob01102k

Akira Shigenaga

{"title":"Theoretical study of the effects of reversible post-translational modifications on the bond dissociation energies of amino acid C-H bonds.","authors":"Akira Shigenaga","doi":"10.1039/d6ob01102k","DOIUrl":"https://doi.org/10.1039/d6ob01102k","url":null,"abstract":"Elucidating the radical reactivity of amino acid residues in peptides and proteins is crucial for understanding oxidative stress and biosynthesizing ribosomally synthesized and post-translationally modified peptides. Although the bond dissociation energy (BDE) serves as a key predictive indicator of radical susceptibility, computational studies on how reversible post-translational modifications (PTMs) modulate the BDEs of neighboring C-H bonds remain limited. In this study, I comprehensively investigated the impacts of various reversible PTMs-including phosphorylation, methylation, acylation, and supersulfidation-on the BDEs of amino acid derivative C-H bonds using density functional theory methods. The results revealed that side-chain acetylation of Lys significantly decreased the BDE of its ε C-H bond, which is rationalized by enhanced radical stabilization through spin delocalization into the acetamide group. Interestingly, while the BDE at the Lys α-position increased in the gas phase upon acetylation, it decreased in aqueous solution. Structural analyses indicated that this solvent-dependent behavior is primarily dictated by changes in the planarity of the peptide main chain, which alters the captodative effect, rather than the intrinsic electronic properties of the PTM itself. These findings provide fundamental computational insights into how reversible PTMs influence the radical reactivity and chemical stability of proteins in physiological environments.","PeriodicalId":96,"journal":{"name":"Organic & Biomolecular Chemistry","volume":" ","pages":""},"PeriodicalIF":2.8,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149163302","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

A tetrachloroanthracene-walled glycoluril trimer: solvent-dependent conformational switching and host-guest binding. 四氯蒽壁糖三聚体：依赖溶剂的构象转换和主-客体结合。

IF 2.8 3区化学

Organic & Biomolecular Chemistry Pub Date : 2026-10-12 DOI: 10.1039/d6ob01088a

Niyati Arora, Alok Shaurya, Jessica Arcudia, Gabriel Merino, Lyle Isaacs

引用次数: 0

Click assembly using trivalent platforms bearing three distinct functional groups. 点击组装使用三价平台承载三个不同的官能团。

IF 2.8 3区化学

Organic & Biomolecular Chemistry Pub Date : 2026-10-09 DOI: 10.1039/d6ob01334a

Takahiro Yasuda, Suguru Yoshida

引用次数: 0