IF 19.1 1区化学

Chem Pub Date : 2024-11-14 DOI: 10.1016/j.chempr.2024.08.005

Hao Wu , Yiyao Wang , Shiyuan Sui , Gongming Chen , Lei Wang , Jiaxin Yang , Junbiao Chang , Dachang Bai

{"title":"Enantioselective desymmetrization and parallel kinetic resolution of cyclopropanes via C–C activation: Synthesis of chiral β-lactams","authors":"Hao Wu , Yiyao Wang , Shiyuan Sui , Gongming Chen , Lei Wang , Jiaxin Yang , Junbiao Chang , Dachang Bai","doi":"10.1016/j.chempr.2024.08.005","DOIUrl":"10.1016/j.chempr.2024.08.005","url":null,"abstract":"<div><div>β-Lactams are privileged and appealing motifs in medicinal chemistry. Herein, we report enantioselective desymmetrization and parallel kinetic resolution of aminocyclopropanes for the synthesis of chiral β-lactams through Rh(I)-catalyzed asymmetric C–C bond activation. The chiral Rh(I) catalyzed C–C bond cleavage of aminocyclopropanes first and then underwent β-hydride elimination to generate π-allylic hydridorhodium(III) intermediates, which could be trapped by tethered alkyne units, and gave various strained chiral β-lactams with excellent <em>regio</em>- and enantioselectivity (90%–99% ee). Moreover, parallel kinetic resolution was realized when using unsymmetrical aminocyclopropanes with pre-existing C2-stereocenters through C–C bond activation, delivering two types of β-lactams in one pot with excellent enantiomeric excesses. Notably, these systems achieve complete atom and step economy. The obtained enantioenriched β-lactams exhibit the capability to undergo a variety of stereospecific transformations. Theoretical calculations reveal the origin of enantioselectivity and support the alkyne unit insertion to allylic Rh(III) –C bond mechanisms.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"10 11","pages":"Pages 3503-3516"},"PeriodicalIF":19.1,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142138191","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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

Quantifying zinc and manganese reduction potentials in organic solvents 量化锌和锰在有机溶剂中的还原电位

IF 19.1 1区化学

Chem Pub Date : 2024-11-14 DOI: 10.1016/j.chempr.2024.10.015

Sagnik Chakrabarti , Liviu M. Mirica

引用次数: 0

Inherently chiral resorcinarene cavitands through ionic catalyst-controlled cross-coupling 通过离子催化剂控制的交叉偶联获得固有手性的间苯二酚空穴剂

IF 19.1 1区化学

Chem Pub Date : 2024-11-14 DOI: 10.1016/j.chempr.2024.06.012

Mingfeng Li , Clement Kim Soon Ho , Ivan Keng Wee On , Vincent Gandon , Ye Zhu

{"title":"Inherently chiral resorcinarene cavitands through ionic catalyst-controlled cross-coupling","authors":"Mingfeng Li , Clement Kim Soon Ho , Ivan Keng Wee On , Vincent Gandon , Ye Zhu","doi":"10.1016/j.chempr.2024.06.012","DOIUrl":"10.1016/j.chempr.2024.06.012","url":null,"abstract":"<div><div>Cavitands have emerged as privileged architectures in supramolecular chemistry. Nonetheless, achieving structural diversity and tunability through heterofunctionalization along the rims of macrocycles has remained a formidable challenge. As a rudimental example, stepwise conversion of <em>C</em><sub>4v</sub>-symmetric scaffolds to inherently chiral ABCD patterns is synthetically impractical owing to the low theoretical yields (0.8%) and the need for chromatographic enantioseparation.</div><div>Herein, we report a catalytic desymmetrization strategy to access inherently chiral cavitands. Through engineering ionic chiral palladium catalysts, diverse functionalities, including aryl, alkenyl, alkynyl, and amino groups, can be installed on the large rims with high site- and stereoselectivity. An adaptable stepwise protocol has been established to furnish designer ABCD-type cavitands in accordance with the choreography of coupling partners. Experimental and computational studies reveal synergistic electrostatic steering and electrostatic catalysis by the ionic catalyst–substrate interactions.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"10 11","pages":"Pages 3323-3341"},"PeriodicalIF":19.1,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141546260","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

On the road to isolable geminal carbodications 通往可分离的宝石碳化物之路

IF 19.1 1区化学

Chem Pub Date : 2024-11-14 DOI: 10.1016/j.chempr.2024.09.008

Yiwei Gong , Jan Langwald , Florian F. Mulks

引用次数: 0

New light on proton transfer: Spectral and kinetic signature of a transient Eigen complex 质子转移的新发现：瞬态特征复合体的光谱和动力学特征

IF 19.1 1区化学

Chem Pub Date : 2024-11-14 DOI: 10.1016/j.chempr.2024.10.017

Niklas Sülzner

引用次数: 0

Self-activated energy release cascade from anthracene-based solid-state molecular solar thermal energy storage systems 蒽基固态分子太阳能热储存系统的自激活能量释放级联

IF 19.1 1区化学

Chem Pub Date : 2024-11-14 DOI: 10.1016/j.chempr.2024.06.033

Subhayan Chakraborty , Han P.Q. Nguyen , Junichi Usuba , Ji Yong Choi , Zhenhuan Sun , Cijil Raju , Gustavo Sigelmann , Qianfeng Qiu , Sungwon Cho , Stephanie M. Tenney , Katherine E. Shulenberger , Klaus Schmidt-Rohr , Jihye Park , Grace G.D. Han

{"title":"Self-activated energy release cascade from anthracene-based solid-state molecular solar thermal energy storage systems","authors":"Subhayan Chakraborty , Han P.Q. Nguyen , Junichi Usuba , Ji Yong Choi , Zhenhuan Sun , Cijil Raju , Gustavo Sigelmann , Qianfeng Qiu , Sungwon Cho , Stephanie M. Tenney , Katherine E. Shulenberger , Klaus Schmidt-Rohr , Jihye Park , Grace G.D. Han","doi":"10.1016/j.chempr.2024.06.033","DOIUrl":"10.1016/j.chempr.2024.06.033","url":null,"abstract":"<div><div>We introduce donor-acceptor substituted anthracenes as effective molecular solar thermal energy storage compounds that operate exclusively in the solid state. The donor-acceptor anthracenes undergo a visible light-induced [4+4] cycloaddition reaction, producing metastable cycloadducts—dianthracenes with quaternary carbons—and storing photon energy. The triggered cycloreversion of dianthracenes to anthracenes discharges the stored energy as heat in the order of 100 kJ/mol (200 J/g). The series of compounds displays remarkable self-heating, or cascading heat release, upon the initial triggering. Such self-activated energy release is enabled by the large energy storage in dianthracenes, low activation energy for their thermal reversion, and effective heat transfer to unreacted molecules in the solid state. This process mirroring the self-ignition of fossil fuels opens up opportunities to use dianthracenes as effective and renewable solid-state fuels that can release energy rapidly and completely upon initial activation.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"10 11","pages":"Pages 3309-3322"},"PeriodicalIF":19.1,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141746613","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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 skeletally diverse library of bioactive natural-product-like compounds enabled by late-stage P450-catalyzed oxyfunctionalization 通过后期 P450 催化氧官能化作用，建立一个骨架多样化的生物活性天然产物类化合物库

IF 19.1 1区化学

Chem Pub Date : 2024-11-14 DOI: 10.1016/j.chempr.2024.08.003

Andrew R. Bortz , John M. Bennett , Rudi Fasan

{"title":"A skeletally diverse library of bioactive natural-product-like compounds enabled by late-stage P450-catalyzed oxyfunctionalization","authors":"Andrew R. Bortz , John M. Bennett , Rudi Fasan","doi":"10.1016/j.chempr.2024.08.003","DOIUrl":"10.1016/j.chempr.2024.08.003","url":null,"abstract":"<div><div>Natural products have historically represented a major source of therapeutics and small-molecule probes for interrogating biological systems. Here, we describe the design and implementation of P450-mediated chemoenzymatic diversity-oriented synthesis (CeDOS), a strategy in which selective, regiodivergent P450-catalyzed oxyfunctionalizations are leveraged as key steps for enabling the skeletal rearrangement and diversification of a parent compound. Using this strategy and plant-derived parthenolide as the parent molecule, a structurally diverse library of over 50 unprecedented natural-product-like scaffolds was generated via divergent chemoenzymatic routes. Importantly, several members of this CeDOS library were found to exhibit notable cytotoxicity against human cancer cells as well as diversified anticancer activity profiles. This work demonstrates the power of CeDOS as a strategy for directing the construction and discovery of novel bioactive molecules, and it offers a blueprint for the broader application of this approach toward the creation and exploration of natural-product-like chemical libraries.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"10 11","pages":"Pages 3488-3502"},"PeriodicalIF":19.1,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142138190","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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 high-throughput workflow to analyze sequence-conformation relationships and explore hydrophobic patterning in disordered peptoids 分析序列构象关系和探索无序蛋白胨疏水模式的高通量工作流程

IF 19.1 1区化学

Chem Pub Date : 2024-11-14 DOI: 10.1016/j.chempr.2024.07.025

Erin C. Day , Supraja S. Chittari , Keila C. Cunha , Roy J. Zhao , James N. Dodds , Delaney C. Davis , Erin S. Baker , Rebecca B. Berlow , Joan-Emma Shea , Rishikesh U. Kulkarni , Abigail S. Knight

{"title":"A high-throughput workflow to analyze sequence-conformation relationships and explore hydrophobic patterning in disordered peptoids","authors":"Erin C. Day , Supraja S. Chittari , Keila C. Cunha , Roy J. Zhao , James N. Dodds , Delaney C. Davis , Erin S. Baker , Rebecca B. Berlow , Joan-Emma Shea , Rishikesh U. Kulkarni , Abigail S. Knight","doi":"10.1016/j.chempr.2024.07.025","DOIUrl":"10.1016/j.chempr.2024.07.025","url":null,"abstract":"<div><div>Understanding how a macromolecule’s primary sequence governs its conformational landscape is crucial for elucidating its function, yet these design principles are still emerging for macromolecules with intrinsic disorder. Herein, we introduce a high-throughput workflow that implements a practical colorimetric conformational assay, introduces a semi-automated sequencing protocol using matrix-assisted laser desorption/ionization and tandem mass spectrometry (MALDI-MS/MS), and develops a generalizable sequence-structure algorithm. Using a model system of 20mer peptidomimetics containing polar glycine and hydrophobic <em>N</em>-butylglycine residues, we identified nine classifications of conformational disorder and isolated 122 unique sequences across varied compositions and conformations. Conformational distributions of three compositionally identical library sequences were corroborated through atomistic simulations and ion mobility spectrometry coupled with liquid chromatography. A data-driven strategy was developed using existing sequence variables and data-derived “motifs” to inform a machine-learning algorithm toward conformation prediction. This multifaceted approach enhances our understanding of sequence-conformation relationships and offers a powerful tool for accelerating the discovery of materials with conformational control.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"10 11","pages":"Pages 3444-3458"},"PeriodicalIF":19.1,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142142935","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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

Nanocellulose: New horizons in organic chemistry and beyond 纳米纤维素：有机化学及其他领域的新视野

IF 19.1 1区化学

Chem Pub Date : 2024-11-14 DOI: 10.1016/j.chempr.2024.09.007

Sayad Doobary , Varvara Apostolopoulou-Kalkavoura , Aji P. Mathew , Berit Olofsson

引用次数: 0

Deuteration of arenes in pharmaceuticals via photoinduced solvated electrons 通过光诱导溶电子使药物中的炔烃发生氘化反应

IF 19.1 1区化学

Chem Pub Date : 2024-11-14 DOI: 10.1016/j.chempr.2024.06.029

Yi Tao , Cuihua Jin , Chuanwang Liu , Jiawei Bu , Ling Yue , Xipan Li , Kangjiang Liang , Chengfeng Xia

引用次数: 0

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