Pub Date : 2024-12-19DOI: 10.1021/acs.orglett.4c03458
Mathias Christmann
A Python script for the systematic, high-throughput analysis of accurate mass data was developed and tested on more than 3000 Supporting Information (SI) PDFs from Organic Letters. For each SI file, quadruplets of molecular formula, measured ion, e.g., [M + Na]+, and reported calculated and found masses were extracted and analyzed. Interestingly, only 40% of the files containing readable accurate mass data were both internally consistent and in compliance with The ACS Guide to Scholarly Communication. The analysis revealed unexpected errors and provided actionable advice on how to improve data quality.
{"title":"What I Learned from Analyzing Accurate Mass Data of 3000 Supporting Information Files","authors":"Mathias Christmann","doi":"10.1021/acs.orglett.4c03458","DOIUrl":"https://doi.org/10.1021/acs.orglett.4c03458","url":null,"abstract":"A Python script for the systematic, high-throughput analysis of accurate mass data was developed and tested on more than 3000 Supporting Information (SI) PDFs from <i>Organic Letters</i>. For each SI file, quadruplets of molecular formula, measured ion, e.g., [M + Na]<sup>+</sup>, and reported calculated and found masses were extracted and analyzed. Interestingly, only 40% of the files containing readable accurate mass data were both internally consistent and in compliance with <i>The ACS Guide to Scholarly Communication</i>. The analysis revealed unexpected errors and provided actionable advice on how to improve data quality.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"40 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2024-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142857833","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}
Pub Date : 2024-12-19DOI: 10.1021/acs.orglett.4c03980
Molhm Nassir, Luca Gherardi, Richard L. Redman, Yonghao Jin, Feng Yao, Yang Yang, Nicholas Raheja, Arjun Natarajan, David Butler, Kyle W. Knouse, Phil S. Baran
Three critical advances in simplifying the adoption of P(V)-based stereopure, phosphorothioate-containing oligonucleotide synthesis are reported. A more inexpensive phosphorus–sulfur incorporation reagent (ΨBr) is introduced, a robust linker system was developed, and a systematic study of common nucleobase protecting groups was performed to significantly reduce the barrier to adoption of this technology.
{"title":"An Improved P(V) Thio-Oligonucleotide Synthesis Platform","authors":"Molhm Nassir, Luca Gherardi, Richard L. Redman, Yonghao Jin, Feng Yao, Yang Yang, Nicholas Raheja, Arjun Natarajan, David Butler, Kyle W. Knouse, Phil S. Baran","doi":"10.1021/acs.orglett.4c03980","DOIUrl":"https://doi.org/10.1021/acs.orglett.4c03980","url":null,"abstract":"Three critical advances in simplifying the adoption of P(V)-based stereopure, phosphorothioate-containing oligonucleotide synthesis are reported. A more inexpensive phosphorus–sulfur incorporation reagent (<b>Ψ</b><sup><b>Br</b></sup>) is introduced, a robust linker system was developed, and a systematic study of common nucleobase protecting groups was performed to significantly reduce the barrier to adoption of this technology.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"97 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2024-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142857835","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}
Developing asymmetric transformations using electroredox and N-heterocyclic carbene (NHC)-catalyzed radical pathways is still desirable and challenging. Herein, we report an iodide-promoted β-carbon activation (LUMO-lowering process) of enals via electroredox carbene catalysis coupled with a hydrogen evolution reaction (HER). This strategy offers an environmentally friendly and sustainable route for rapidly assembling synthetically useful chiral naphthopyran-3-one in good to excellent yield and enantioselectivity using traceless electrons as inexpensive and greener oxidants. The mechanistic studies and cyclic voltammetry suggest that the reaction proceeds via direct single electron transfer (SET) of the in situ-generated Breslow intermediate.
{"title":"Electroredox N-Heterocyclic Carbene-Catalyzed Enantioselective (3 + 3) Annulation of Enals with 2-Naphthols","authors":"Vikas Kale, Sayan Shee, Shiv Dutt, Nidhi Sinha, Akkattu T. Biju, Prabal Banerjee","doi":"10.1021/acs.orglett.4c03879","DOIUrl":"https://doi.org/10.1021/acs.orglett.4c03879","url":null,"abstract":"Developing asymmetric transformations using electroredox and N-heterocyclic carbene (NHC)-catalyzed radical pathways is still desirable and challenging. Herein, we report an iodide-promoted β-carbon activation (LUMO-lowering process) of enals via electroredox carbene catalysis coupled with a hydrogen evolution reaction (HER). This strategy offers an environmentally friendly and sustainable route for rapidly assembling synthetically useful chiral naphthopyran-3-one in good to excellent yield and enantioselectivity using traceless electrons as inexpensive and greener oxidants. The mechanistic studies and cyclic voltammetry suggest that the reaction proceeds via direct single electron transfer (SET) of the in situ-generated Breslow intermediate.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"23 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2024-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142849697","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}
Pub Date : 2024-12-19DOI: 10.1021/acs.orglett.4c03409
Han-Xiao Li, Zeyuan Shen, Jiguo Ma, Zhi-Xiang Yu
Under mild conditions and without the need of inert gas protection, a Rh-catalyzed rearrangement of trans-divinylcyclopropanes to form 1,5-disubstituted 1,4-cycloheptadienes has been developed and is disclosed here. This reaction can expedite the synthesis of challenging seven-membered carbocycles.
{"title":"Rh-Catalyzed trans-Divinylcyclopropane Rearrangement: An Approach to 1,5-Disubstituted 1,4-Cycloheptadienes","authors":"Han-Xiao Li, Zeyuan Shen, Jiguo Ma, Zhi-Xiang Yu","doi":"10.1021/acs.orglett.4c03409","DOIUrl":"https://doi.org/10.1021/acs.orglett.4c03409","url":null,"abstract":"Under mild conditions and without the need of inert gas protection, a Rh-catalyzed rearrangement of <i>trans</i>-divinylcyclopropanes to form 1,5-disubstituted 1,4-cycloheptadienes has been developed and is disclosed here. This reaction can expedite the synthesis of challenging seven-membered carbocycles.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"30 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2024-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142849696","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}
Pub Date : 2024-12-19DOI: 10.1021/acs.orglett.4c04141
Kaili Miao, Jin Zhang, Jiaxin Chen, Lin-Bao Zhang, Ming Li, Lirong Wen, Weisi Guo
The site-selective functionalization of cyclic amides provides an attractive protocol for the synthesis of valuable molecules. We report herein an electrochemical desaturation and β-thiocyanation of cyclic amides under external oxidant-free conditions. This method exhibits broad functional group tolerance, excellent selectivity, mild reaction conditions and can be applied for late-stage functionalization of bioactive molecules. Mechanistic studies indicate that an enamide intermediate might be involved.
{"title":"Electrochemical Desaturation and β-Thiocyanation of Cyclic Amides","authors":"Kaili Miao, Jin Zhang, Jiaxin Chen, Lin-Bao Zhang, Ming Li, Lirong Wen, Weisi Guo","doi":"10.1021/acs.orglett.4c04141","DOIUrl":"https://doi.org/10.1021/acs.orglett.4c04141","url":null,"abstract":"The site-selective functionalization of cyclic amides provides an attractive protocol for the synthesis of valuable molecules. We report herein an electrochemical desaturation and β-thiocyanation of cyclic amides under external oxidant-free conditions. This method exhibits broad functional group tolerance, excellent selectivity, mild reaction conditions and can be applied for late-stage functionalization of bioactive molecules. Mechanistic studies indicate that an enamide intermediate might be involved.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"1 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2024-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142849797","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}
Pub Date : 2024-12-19DOI: 10.1021/acs.orglett.4c04230
Jie Sun, Lijun Zheng, Heng Zhang, Jintong Xie, Guan Wang, Shengjie Song, Jianjun Li
A method was found to construct sulfur-containing five- and six-membered heterocyclic alkyl sulfonyl compounds by using visible light and free radicals activated and/or generated by EDA complexes/homolytic cleavage as initiators to stimulate the relay reaction of alkynes/alkynones. This method puts forward a new strategy to initiate alkyl sulfonation of alkynes/alkynones with only a catalytic amount of the initiator. This strategy of generating the initiator by EDA complex activation/homolytic cleavage provides a new idea for the following substances that must be excited.
{"title":"Photoinduced Radical Relay Reaction of 2-Methylthiolated Phenylacetylenes/Alkynones Initiated by Electron Donor–Acceptor Complexes","authors":"Jie Sun, Lijun Zheng, Heng Zhang, Jintong Xie, Guan Wang, Shengjie Song, Jianjun Li","doi":"10.1021/acs.orglett.4c04230","DOIUrl":"https://doi.org/10.1021/acs.orglett.4c04230","url":null,"abstract":"A method was found to construct sulfur-containing five- and six-membered heterocyclic alkyl sulfonyl compounds by using visible light and free radicals activated and/or generated by EDA complexes/homolytic cleavage as initiators to stimulate the relay reaction of alkynes/alkynones. This method puts forward a new strategy to initiate alkyl sulfonation of alkynes/alkynones with only a catalytic amount of the initiator. This strategy of generating the initiator by EDA complex activation/homolytic cleavage provides a new idea for the following substances that must be excited.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"201 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2024-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142858054","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}
Pub Date : 2024-12-19DOI: 10.1021/acs.orglett.4c03930
Jiaxin Chu, Haoran Wang, Sunewang R. Wang
In sharp contrast to the intuitive modulation by the electronic effect, the [4 + 1] annulation reaction between α-substituted conjugated enones and ylides has been reliably controlled by the match of the α-substituent and the ylide in steric hindrance, providing a straightforward and efficient method for valuable 4-cyano, 4-alkynyl, 4-vinyl, and 4-aryl 2,3-dihydrofurans.
{"title":"Steric Hindrance Tuned [4 + 1] Annulation of α-Substituted Conjugated Enones with Ylides for Dihydrofuran Synthesis","authors":"Jiaxin Chu, Haoran Wang, Sunewang R. Wang","doi":"10.1021/acs.orglett.4c03930","DOIUrl":"https://doi.org/10.1021/acs.orglett.4c03930","url":null,"abstract":"In sharp contrast to the intuitive modulation by the electronic effect, the [4 + 1] annulation reaction between α-substituted conjugated enones and ylides has been reliably controlled by the match of the α-substituent and the ylide in steric hindrance, providing a straightforward and efficient method for valuable 4-cyano, 4-alkynyl, 4-vinyl, and 4-aryl 2,3-dihydrofurans.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"55 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2024-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142858129","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}
The avermectins make up a biologically relevant class of complex natural products that continue to inspire the development of new strategies in chemical synthesis. Herein, we disclose a concise synthesis of the southern core of avermectin aglycon. The key hydrobenzofuran was forged by either reductive cyclization or cycloisomerization, both using a cationic palladium precatalyst. This hydropalladation strategy generated the hydrofuran ring under mild conditions, enabling the rapid construction of the tetra-substituted carbon stereocenter.
{"title":"Palladium-Catalyzed Reductive and Redox-Neutral Cyclization Approach to the Southern Core of Avermectins","authors":"Goh Sennari, Shogo Sato, Aoi Kimishima, Tomoyasu Hirose, Toshiaki Sunazuka","doi":"10.1021/acs.orglett.4c04282","DOIUrl":"https://doi.org/10.1021/acs.orglett.4c04282","url":null,"abstract":"The avermectins make up a biologically relevant class of complex natural products that continue to inspire the development of new strategies in chemical synthesis. Herein, we disclose a concise synthesis of the southern core of avermectin aglycon. The key hydrobenzofuran was forged by either reductive cyclization or cycloisomerization, both using a cationic palladium precatalyst. This hydropalladation strategy generated the hydrofuran ring under mild conditions, enabling the rapid construction of the tetra-substituted carbon stereocenter.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"47 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2024-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142841806","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}
Pub Date : 2024-12-18DOI: 10.1021/acs.orglett.4c04260
Hannah C. Wendlandt, Jacob A. Utley, Byung Joo Lee, Tam D. Ho, Kami L. Hull
We disclose a broad platform for copper-catalyzed atom transfer radical addition (ATRA) of electron-deficient olefins. Catalytic Cu(dtbbpy)2(OTf)2 enables radical addition of electron-deficient alkyl halides to acrylates, acrylamides, and vinyl sulfones in fair to excellent yields. The resultant ATRA products can be used in a variety of telescoped reactions, including substitution with basic amine nucleophiles to afford α-amino esters. The synthetic utility of the products is further demonstrated through derivatization to give substituted cyclopropanes and a γ,δ-unsaturated ester.
{"title":"A General Platform for Copper-Catalyzed Atom Transfer Radical Addition with Electron-Deficient Olefins","authors":"Hannah C. Wendlandt, Jacob A. Utley, Byung Joo Lee, Tam D. Ho, Kami L. Hull","doi":"10.1021/acs.orglett.4c04260","DOIUrl":"https://doi.org/10.1021/acs.orglett.4c04260","url":null,"abstract":"We disclose a broad platform for copper-catalyzed atom transfer radical addition (ATRA) of electron-deficient olefins. Catalytic Cu(dtbbpy)<sub>2</sub>(OTf)<sub>2</sub> enables radical addition of electron-deficient alkyl halides to acrylates, acrylamides, and vinyl sulfones in fair to excellent yields. The resultant ATRA products can be used in a variety of telescoped reactions, including substitution with basic amine nucleophiles to afford α-amino esters. The synthetic utility of the products is further demonstrated through derivatization to give substituted cyclopropanes and a γ,δ-unsaturated ester.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"29 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2024-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142849698","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}
Pub Date : 2024-12-18DOI: 10.1021/acs.orglett.4c04484
Lin Tian, Pu Chen, Xiaochen Ji, Guo-Jun Deng, Huawen Huang
We herein report a photochemical Truce–Smiles rearrangement reaction of N-sulfinyl acrylamides with bromodifluoroacetamides resulting in the synthesis of a series of aryl difluoroglutaramides in moderate to good yields. The asymmetric synthesis using chiral sulfinamides produced quaternary carbon-centered glutaramide products with a modest enantioselectivity. This protocol effectively complements previous Truce–Smiles rearrangement methods involving N-sulfonyl acrylamides.
{"title":"Photoredox Radical Truce–Smiles Rearrangement of N-Sulfinyl Acrylamides with Bromodifluoroacetamides","authors":"Lin Tian, Pu Chen, Xiaochen Ji, Guo-Jun Deng, Huawen Huang","doi":"10.1021/acs.orglett.4c04484","DOIUrl":"https://doi.org/10.1021/acs.orglett.4c04484","url":null,"abstract":"We herein report a photochemical Truce–Smiles rearrangement reaction of <i>N</i>-sulfinyl acrylamides with bromodifluoroacetamides resulting in the synthesis of a series of aryl difluoroglutaramides in moderate to good yields. The asymmetric synthesis using chiral sulfinamides produced quaternary carbon<i>-</i>centered glutaramide products with a modest enantioselectivity. This protocol effectively complements previous Truce–Smiles rearrangement methods involving <i>N</i>-sulfonyl acrylamides.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"23 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2024-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142841822","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}
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