Precision Chemistry最新文献

{"title":"Salt Metathesis: An Ultimate Click Reaction⊥","authors":"Christopher M. Butch,&nbsp;Patrick C. Hillesheim* and Arsalan Mirjafari*,&nbsp;","doi":"10.1021/prechem.4c0008810.1021/prechem.4c00088","DOIUrl":"https://doi.org/10.1021/prechem.4c00088https://doi.org/10.1021/prechem.4c00088","url":null,"abstract":"<p >In this Comment, we suggest salt metathesis (or ion exchange) as an ultimate click reaction, extending click chemistry principles beyond covalent bonds to ionic interactions. These universal and robust reactions, which nature utilizes in marine organisms' biomineralization processes, proceed spontaneously under mild conditions with minimal waste, embodying the core principles of click philosophy. This perspective expands the traditional scope of click chemistry and opens new opportunities in synthetic accessibility across organic, inorganic, and materials science spaces.</p>","PeriodicalId":29793,"journal":{"name":"Precision Chemistry","volume":"3 2","pages":"105–107 105–107"},"PeriodicalIF":0.0,"publicationDate":"2024-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/prechem.4c00088","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143473821","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A Practical Approach to Quantitatively Assessing Equilibrium-Constant Accuracy from a Single Binding Isotherm.","authors":"Tong Ye Wang, Jessica Latimer, Jean-Luc Rukundo, Isaac Kogan, Svetlana M Krylova, Sebastian Schreiber, Philip Kohlmann, Joachim Jose, Sergey N Krylov","doi":"10.1021/prechem.4c00085","DOIUrl":"10.1021/prechem.4c00085","url":null,"abstract":"<p><p>Equilibrium constants are essential for understanding and predicting the behavior of chemical systems across various scientific disciplines. Traditionally, these constants are computed via nonlinear regression of reaction isotherms, which show the dependence of the unreacted fraction of one reactant on the total concentration of another reactant. However, while these equilibrium constants can be precise (with small random errors), they may also be grossly inaccurate (with large systematic errors), leading to potential misinterpretations. Although some statistical methods exist for assessing the accuracy of nonlinear regression, their limited practicality for molecular scientists has resulted in their neglect by this research community. The objective of this work is to develop a practical method for quantitatively assessing the accuracy of equilibrium constants that could be easily understood and immediately adopted by researchers routinely determining these constants. Our approach integrates error-propagation and regression-stability analyses to establish the accuracy confidence interval (ACI)-a range within which the true value of the computed parameter lies with a defined probability. In a proof-of-principle study, we applied this approach to develop a workflow for determining the ACI of the equilibrium dissociation constant (<i>K</i> _d) of affinity complexes from a single binding isotherm. We clearly explained how the input parameters for this workflow can be determined, and finally, we have implemented this workflow in a user-friendly web application (https://aci.sci.yorku.ca) to facilitate its immediate adoption by molecular scientists, regardless of their mathematical and computer proficiency. We further conducted three case studies exemplifying the use of the ACI in the context of simultaneous assessment of precision and accuracy of determined <i>K</i> _d values. By understanding the ACI of equilibrium constants and other parameters computed through nonlinear regression, researchers can avoid misconceptions that arise from relying solely on precision.</p>","PeriodicalId":29793,"journal":{"name":"Precision Chemistry","volume":"3 2","pages":"89-104"},"PeriodicalIF":0.0,"publicationDate":"2024-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11863166/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143524255","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A Practical Approach to Quantitatively Assessing Equilibrium-Constant Accuracy from a Single Binding Isotherm","authors":"Tong Ye Wang,&nbsp;Jessica Latimer,&nbsp;Jean-Luc Rukundo,&nbsp;Isaac Kogan,&nbsp;Svetlana M. Krylova,&nbsp;Sebastian Schreiber,&nbsp;Philip Kohlmann,&nbsp;Joachim Jose and Sergey N. Krylov*,&nbsp;","doi":"10.1021/prechem.4c0008510.1021/prechem.4c00085","DOIUrl":"https://doi.org/10.1021/prechem.4c00085https://doi.org/10.1021/prechem.4c00085","url":null,"abstract":"<p >Equilibrium constants are essential for understanding and predicting the behavior of chemical systems across various scientific disciplines. Traditionally, these constants are computed via nonlinear regression of reaction isotherms, which show the dependence of the unreacted fraction of one reactant on the total concentration of another reactant. However, while these equilibrium constants can be precise (with small random errors), they may also be grossly inaccurate (with large systematic errors), leading to potential misinterpretations. Although some statistical methods exist for assessing the accuracy of nonlinear regression, their limited practicality for molecular scientists has resulted in their neglect by this research community. The objective of this work is to develop a practical method for quantitatively assessing the accuracy of equilibrium constants that could be easily understood and immediately adopted by researchers routinely determining these constants. Our approach integrates error-propagation and regression-stability analyses to establish the accuracy confidence interval (ACI)─a range within which the true value of the computed parameter lies with a defined probability. In a proof-of-principle study, we applied this approach to develop a workflow for determining the ACI of the equilibrium dissociation constant (<i>K</i>_d) of affinity complexes from a single binding isotherm. We clearly explained how the input parameters for this workflow can be determined, and finally, we have implemented this workflow in a user-friendly web application (https://aci.sci.yorku.ca) to facilitate its immediate adoption by molecular scientists, regardless of their mathematical and computer proficiency. We further conducted three case studies exemplifying the use of the ACI in the context of simultaneous assessment of precision and accuracy of determined <i>K</i>_d values. By understanding the ACI of equilibrium constants and other parameters computed through nonlinear regression, researchers can avoid misconceptions that arise from relying solely on precision.</p>","PeriodicalId":29793,"journal":{"name":"Precision Chemistry","volume":"3 2","pages":"89–104 89–104"},"PeriodicalIF":0.0,"publicationDate":"2024-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/prechem.4c00085","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143473861","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Catalytic Reductive Homocoupling of Benzyl Chlorides Enabled by Zirconocene and Photoredox Catalysis","authors":"Ryota Tajima,&nbsp;Keisuke Tanaka,&nbsp;Kazuhiro Aida,&nbsp;Eisuke Ota* and Junichiro Yamaguchi*,&nbsp;","doi":"10.1021/prechem.4c0007710.1021/prechem.4c00077","DOIUrl":"https://doi.org/10.1021/prechem.4c00077https://doi.org/10.1021/prechem.4c00077","url":null,"abstract":"<p >The bibenzyl skeleton is prevalent in numerous natural products and other biologically active compounds. Radical homocoupling provides a straightforward approach for synthesizing bibenzyls in a single step with the reductive homocoupling of benzyl halides undergoing extensive development. Unlike benzyl bromides and other tailored precursors used in visible-light-mediated homocoupling, benzyl chlorides offer greater abundance and chemical stability. Nevertheless, achieving chemoselective cleavage of the C–Cl bond poses significant challenges, with only a limited number of studies reported to date. Herein, we demonstrate a catalytic reductive homocoupling of benzyl chlorides facilitated by zirconocene and photoredox catalysis. This cooperative catalytic system promotes C–Cl bond cleavage in benzyl chlorides under mild conditions and supports the homocoupling of a wide range of benzyl chlorides, including those derived from pharmaceutical agents. Our preliminary mechanistic investigations highlight the pivotal role of hydrosilane in the catalytic cycle.</p>","PeriodicalId":29793,"journal":{"name":"Precision Chemistry","volume":"3 1","pages":"43–50 43–50"},"PeriodicalIF":0.0,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/prechem.4c00077","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143091843","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Catalytic Reductive Homocoupling of Benzyl Chlorides Enabled by Zirconocene and Photoredox Catalysis.","authors":"Ryota Tajima, Keisuke Tanaka, Kazuhiro Aida, Eisuke Ota, Junichiro Yamaguchi","doi":"10.1021/prechem.4c00077","DOIUrl":"10.1021/prechem.4c00077","url":null,"abstract":"<p><p>The bibenzyl skeleton is prevalent in numerous natural products and other biologically active compounds. Radical homocoupling provides a straightforward approach for synthesizing bibenzyls in a single step with the reductive homocoupling of benzyl halides undergoing extensive development. Unlike benzyl bromides and other tailored precursors used in visible-light-mediated homocoupling, benzyl chlorides offer greater abundance and chemical stability. Nevertheless, achieving chemoselective cleavage of the C-Cl bond poses significant challenges, with only a limited number of studies reported to date. Herein, we demonstrate a catalytic reductive homocoupling of benzyl chlorides facilitated by zirconocene and photoredox catalysis. This cooperative catalytic system promotes C-Cl bond cleavage in benzyl chlorides under mild conditions and supports the homocoupling of a wide range of benzyl chlorides, including those derived from pharmaceutical agents. Our preliminary mechanistic investigations highlight the pivotal role of hydrosilane in the catalytic cycle.</p>","PeriodicalId":29793,"journal":{"name":"Precision Chemistry","volume":"3 1","pages":"43-50"},"PeriodicalIF":0.0,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11775857/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143068168","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Artificial-Intelligence Driven Precision Chemistry","authors":"Zhenyu Li*,&nbsp;","doi":"10.1021/prechem.4c0008610.1021/prechem.4c00086","DOIUrl":"https://doi.org/10.1021/prechem.4c00086https://doi.org/10.1021/prechem.4c00086","url":null,"abstract":"","PeriodicalId":29793,"journal":{"name":"Precision Chemistry","volume":"3 1","pages":"1–2 1–2"},"PeriodicalIF":0.0,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/prechem.4c00086","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143091877","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Artificial-Intelligence Driven Precision Chemistry.","authors":"Zhenyu Li","doi":"10.1021/prechem.4c00086","DOIUrl":"10.1021/prechem.4c00086","url":null,"abstract":"","PeriodicalId":29793,"journal":{"name":"Precision Chemistry","volume":"3 1","pages":"1-2"},"PeriodicalIF":0.0,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11775847/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143068143","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Stepwise Chemical Reduction of [4]Cyclo[4]helicenylene: Stereo Transformation and Site-Selective Metal Complexation.","authors":"Zheng Zhou, Yong Yang, Jianwei Liang, Sota Sato, Zhenyi Zhang, Zheng Wei","doi":"10.1021/prechem.4c00064","DOIUrl":"10.1021/prechem.4c00064","url":null,"abstract":"<p><p>A highly strained macrocycle comprising four [4]helicene panels, [4]cyclo[4]helicenylene ([4]CH, <b>1</b>), was synthesized through a one-pot macrocyclization and chemically reduced by alkali metals (Na and K), revealing a four-electron reduction process. The resulting di-, tri-, and tetraanions of compound <b>1</b> were isolated and crystallographically characterized by X-ray diffraction. Owing to the four axially chiral bi[4]helicenyl fragments, a reversible stereo transformation of <b>1</b> between the (<i>S</i>,<i>R</i>,<i>S</i>,<i>R</i>)- and (<i>S</i>,<i>S</i>,<i>R</i>,<i>R</i>)-configurations was disclosed upon the two-electron uptake, which was rationally understood by theoretical calculations. The (<i>S</i>,<i>S</i>,<i>R</i>,<i>R</i>)-configuration of <b>1</b> ^2- was further stabilized in triply reduced and tetra-reduced states, where structural deformation led by charges and metal complexation was observed. This study proposed an approach to alter the configuration of cycloarylenes in addition to thermal treatment.</p>","PeriodicalId":29793,"journal":{"name":"Precision Chemistry","volume":"3 1","pages":"27-34"},"PeriodicalIF":0.0,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11775854/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143068248","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Stepwise Chemical Reduction of [4]Cyclo[4]helicenylene: Stereo Transformation and Site-Selective Metal Complexation","authors":"Zheng Zhou*,&nbsp;Yong Yang*,&nbsp;Jianwei Liang,&nbsp;Sota Sato,&nbsp;Zhenyi Zhang and Zheng Wei,&nbsp;","doi":"10.1021/prechem.4c0006410.1021/prechem.4c00064","DOIUrl":"https://doi.org/10.1021/prechem.4c00064https://doi.org/10.1021/prechem.4c00064","url":null,"abstract":"<p >A highly strained macrocycle comprising four [4]helicene panels, [4]cyclo[4]helicenylene ([4]CH, <b>1</b>), was synthesized through a one-pot macrocyclization and chemically reduced by alkali metals (Na and K), revealing a four-electron reduction process. The resulting di-, tri-, and tetraanions of compound <b>1</b> were isolated and crystallographically characterized by X-ray diffraction. Owing to the four axially chiral bi[4]helicenyl fragments, a reversible stereo transformation of <b>1</b> between the (<i>S</i>,<i>R</i>,<i>S</i>,<i>R</i>)- and (<i>S</i>,<i>S</i>,<i>R</i>,<i>R</i>)-configurations was disclosed upon the two-electron uptake, which was rationally understood by theoretical calculations. The (<i>S</i>,<i>S</i>,<i>R</i>,<i>R</i>)-configuration of <b>1</b>^2– was further stabilized in triply reduced and tetra-reduced states, where structural deformation led by charges and metal complexation was observed. This study proposed an approach to alter the configuration of cycloarylenes in addition to thermal treatment.</p>","PeriodicalId":29793,"journal":{"name":"Precision Chemistry","volume":"3 1","pages":"27–34 27–34"},"PeriodicalIF":0.0,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/prechem.4c00064","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143091669","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Whole-Process Precision Chemistry for Clusters","authors":"Jianping Xie*,&nbsp;","doi":"10.1021/prechem.4c0008310.1021/prechem.4c00083","DOIUrl":"https://doi.org/10.1021/prechem.4c00083https://doi.org/10.1021/prechem.4c00083","url":null,"abstract":"","PeriodicalId":29793,"journal":{"name":"Precision Chemistry","volume":"2 11","pages":"559–562 559–562"},"PeriodicalIF":0.0,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/prechem.4c00083","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142694516","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}