Eighteen rutaecarpine derivatives were synthesized through [Cp*IrCl2]2-catalyzed cyclization of indole-quinazoline precursors with ethylene glycol in 43%–83% isolated yields. Structural characterization was performed using 1H & 13C NMR spectroscopy, high-resolution electrospray ionization mass spectrometry (HRESI-MS), and X-ray diffraction (XRD) analysis, with data corroborated by literature comparisons. Mechanistic investigations revealed a hydrogen-borrowing cascade facilitating sequential C-alkylation and N-alkylation, wherein regioselectivity was governed by an iridium-chelated intermediate. Density functional theory (DFT) calculations provided further validation of the proposed mechanism. This methodology establishes an environmentally benign approach for synthesizing bioactive alkaloids while elucidating fundamental mechanistic aspects of transition-metal-mediated heterocycle fusion.
{"title":"Concise Two-Step Hydrogen-Borrowing Cascade for Modular Synthesis of Rutaecarpine Derivatives","authors":"Ke Feng, Qiming Cheng, Xu Tang, Liangfeng Wang, Chao Zhou, Caiyao Wang, Xinyu Zhang, Mulan Gong, Shanshan Ran, Jingxian Yu, Guixia Wang, Xiangfei Kong","doi":"10.1002/ejoc.202501143","DOIUrl":"https://doi.org/10.1002/ejoc.202501143","url":null,"abstract":"Eighteen rutaecarpine derivatives were synthesized through [Cp*IrCl<sub>2</sub>]<sub>2</sub>-catalyzed cyclization of indole-quinazoline precursors with ethylene glycol in 43%–83% isolated yields. Structural characterization was performed using <sup>1</sup>H & <sup>13</sup>C NMR spectroscopy, high-resolution electrospray ionization mass spectrometry (HRESI-MS), and X-ray diffraction (XRD) analysis, with data corroborated by literature comparisons. Mechanistic investigations revealed a hydrogen-borrowing cascade facilitating sequential C-alkylation and N-alkylation, wherein regioselectivity was governed by an iridium-chelated intermediate. Density functional theory (DFT) calculations provided further validation of the proposed mechanism. This methodology establishes an environmentally benign approach for synthesizing bioactive alkaloids while elucidating fundamental mechanistic aspects of transition-metal-mediated heterocycle fusion.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"22 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2026-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147507268","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}
Sreejith K. Aravindakshan, Jijy Eliyan, Sreeja Thulasi, Jubi John
Polyacenes and their heteroatom-containing analogs have become essential components in organic electronic materials due to their extended π-conjugation, efficient charge transport, and tunable optoelectronic properties. Heteroacenes incorporating nitrogen and sulfur exhibit improved electronic modulation, enhanced stability, and superior solid-state organization, thereby expanding their utility in advanced optoelectronic devices. Benzothienoindole is a unique class of nitrogen- and sulfur-containing fused heteroacenes, formed by combining indole and benzothiophene units, and is available as four regioisomers with distinct structural and electronic properties. The review provides an extensive summary of the synthetic methodologies for constructing benzothienoindole frameworks, including one-pot, multicomponent, multistep, and transition metal catalyzed approaches. Mechanistic insights into these transformations are examined, and the material applications of selected benzothienoindole derivatives are mentioned.
{"title":"Synthetic Approaches to Benzothienoindole Frameworks: A Review","authors":"Sreejith K. Aravindakshan, Jijy Eliyan, Sreeja Thulasi, Jubi John","doi":"10.1002/ejoc.70422","DOIUrl":"https://doi.org/10.1002/ejoc.70422","url":null,"abstract":"Polyacenes and their heteroatom-containing analogs have become essential components in organic electronic materials due to their extended π-conjugation, efficient charge transport, and tunable optoelectronic properties. Heteroacenes incorporating nitrogen and sulfur exhibit improved electronic modulation, enhanced stability, and superior solid-state organization, thereby expanding their utility in advanced optoelectronic devices. Benzothienoindole is a unique class of nitrogen- and sulfur-containing fused heteroacenes, formed by combining indole and benzothiophene units, and is available as four regioisomers with distinct structural and electronic properties. The review provides an extensive summary of the synthetic methodologies for constructing benzothienoindole frameworks, including one-pot, multicomponent, multistep, and transition metal catalyzed approaches. Mechanistic insights into these transformations are examined, and the material applications of selected benzothienoindole derivatives are mentioned.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"17 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2026-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147506998","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}
Katelyn G. Stevens-Davis, Xiaozheng Dou, Bo Hu, Yangxiong Li, Jiayuan Miao, Yu-Shan Lin, Adam S. Duerfeldt
We report the synthesis and conformational analysis of a methylene-linked acyldepsipeptide (ADEP). The convergent approach hinged on the generation of a protected vinylglycine synthon, a versatile noncanonical amino acid building block. A rationally optimized Grubbs metathesis and a new mode for macrocyclization to provide critical intermediates are also featured. NMR and in silico studies revealed an unusual trans–trans proline orientation for this new unnatural analog, advancing the understanding of ADEP structure–activity relationships and cyclic peptidomimetics in general.
{"title":"Synthesis of a Carbon-Linked Acyldepsipeptide Derivative","authors":"Katelyn G. Stevens-Davis, Xiaozheng Dou, Bo Hu, Yangxiong Li, Jiayuan Miao, Yu-Shan Lin, Adam S. Duerfeldt","doi":"10.1002/ejoc.70366","DOIUrl":"https://doi.org/10.1002/ejoc.70366","url":null,"abstract":"We report the synthesis and conformational analysis of a methylene-linked acyldepsipeptide (ADEP). The convergent approach hinged on the generation of a protected vinylglycine synthon, a versatile noncanonical amino acid building block. A rationally optimized Grubbs metathesis and a new mode for macrocyclization to provide critical intermediates are also featured. NMR and in silico studies revealed an unusual <i>trans–trans</i> proline orientation for this new unnatural analog, advancing the understanding of ADEP structure–activity relationships and cyclic peptidomimetics in general.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"14 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2026-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147496256","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}
Satoshi Horino, Karla Wagner, Anke Hummel, Kyohei Kanomata, Harald Gröger, Shuji Akai
Chemoenzymatic dynamic kinetic resolution (DKR) of racemic alcohols represents a straightforward and sustainable strategy for synthesizing enantiomerically pure alcohols and their derivatives, which serve as important synthetic intermediates in the fine chemical industry, yet its application to tert-alcohols remains challenging due to steric hindrance of the alcohols and inefficient racemization methods. This study presents significant advancement in the chemoenzymatic DKR of tert-alcohols by a compartmentalization strategy using a polydimethylsiloxane (PDMS) thimble, which physically separates involved two reactions, i.e., the lipase-catalyzed enantioselective esterification and racemization, in a single flask. Using commercially available immobilized lipase A from Candida antarctica (CAL-A) and our original, vanadium-based racemization catalyst V-MPS4, we thoroughly optimized the reaction conditions and found that the use of excess Na2CO3 and prewashing of CAL-A were effective in ensuring a high stability of V-MPS4. With additional adjustments of some factors, such as the amount of V-MPS4, applying our protocol led to the synthesis of enantiomerically enriched esters with up to 99% enantiomeric excess (ee) from seven tert-alcohols, in 52%–62% isolated yields in 48 h. These results demonstrate significant improvements in reaction time, catalyst stability, substrate scope, and reaction procedure, highlighting the practical utility of compartmentalized chemoenzymatic DKR for challenging tert-alcohol substrates.
{"title":"Lipase–V-MPS Co-Catalyzed Dynamic Kinetic Resolution of Tertiary Alcohols: Process Intensification Through Catalyst Compartmentalization","authors":"Satoshi Horino, Karla Wagner, Anke Hummel, Kyohei Kanomata, Harald Gröger, Shuji Akai","doi":"10.1002/ejoc.202500980","DOIUrl":"https://doi.org/10.1002/ejoc.202500980","url":null,"abstract":"Chemoenzymatic dynamic kinetic resolution (DKR) of racemic alcohols represents a straightforward and sustainable strategy for synthesizing enantiomerically pure alcohols and their derivatives, which serve as important synthetic intermediates in the fine chemical industry, yet its application to <i>tert</i>-alcohols remains challenging due to steric hindrance of the alcohols and inefficient racemization methods. This study presents significant advancement in the chemoenzymatic DKR of <i>tert</i>-alcohols by a compartmentalization strategy using a polydimethylsiloxane (PDMS) thimble, which physically separates involved two reactions, i.e., the lipase-catalyzed enantioselective esterification and racemization, in a single flask. Using commercially available immobilized lipase A from <i>Candida antarctica</i> (CAL-A) and our original, vanadium-based racemization catalyst V-MPS4, we thoroughly optimized the reaction conditions and found that the use of excess Na<sub>2</sub>CO<sub>3</sub> and prewashing of CAL-A were effective in ensuring a high stability of V-MPS4. With additional adjustments of some factors, such as the amount of V-MPS4, applying our protocol led to the synthesis of enantiomerically enriched esters with up to 99% enantiomeric excess (ee) from seven <i>tert</i>-alcohols, in 52%–62% isolated yields in 48 h. These results demonstrate significant improvements in reaction time, catalyst stability, substrate scope, and reaction procedure, highlighting the practical utility of compartmentalized chemoenzymatic DKR for challenging <i>tert</i>-alcohol substrates.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"52 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2026-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147507269","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}
A novel organophotoredox-catalyzed [3 + 2] cycloaddition strategy for the synthesis of spirocyclopentane oxindoles is reported, employing N-aryl cyclopropylamines and isatin-derived alkenes as readily available coupling partners. This protocol affords diverse spirocyclopentane oxindole derivatives in excellent yields (up to 94%) and good diastereoselectivities (up to 96:4 dr) under mild conditions. The transformation is facilitated by a dual catalytic system consisting of Eosin Y as photoredox catalyst and diphenyl phosphate (PA) as organocatalyst, with N,N-diisopropylethylamine (DIPEA) as a crucial additive.
{"title":"Organophotoredox-Catalyzed [3 + 2] Cycloaddition for the Diastereoselective Synthesis of Spirocyclopentane Oxindoles","authors":"Yingjie Huang, Xufeng Lin","doi":"10.1002/ejoc.202501227","DOIUrl":"https://doi.org/10.1002/ejoc.202501227","url":null,"abstract":"A novel organophotoredox-catalyzed [3 + 2] cycloaddition strategy for the synthesis of spirocyclopentane oxindoles is reported, employing <i>N</i>-aryl cyclopropylamines and isatin-derived alkenes as readily available coupling partners. This protocol affords diverse spirocyclopentane oxindole derivatives in excellent yields (up to 94%) and good diastereoselectivities (up to 96:4 dr) under mild conditions. The transformation is facilitated by a dual catalytic system consisting of Eosin Y as photoredox catalyst and diphenyl phosphate (PA) as organocatalyst, with <i>N</i>,<i>N</i>-diisopropylethylamine (DIPEA) as a crucial additive.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"14 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2026-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147496255","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}
Thorsten Hackfort, Bernhard M. Malorny, Andreas Mix, Beate Neumann, Hans‐Georg Stammler, Dietmar Kuck
The C3v ‐symmetric framework of triptindane ( C3v ‐tribenzo[3.3.3]propellane, 1 ) was equipped with three benzylic monovalent functional groups in a C3 ‐symmetric orientation. Key reaction was the reduction of 9,10,11‐triptindanetrione ( 2 ) with lithium aluminum hydride or sodium borohydride giving the corresponding C3 ‐symmetric triol 5 in high yield and perfect diastereoselectivity. The diastereoselective reduction of 9,10‐triptindanedione 9 with LiAlH 4 was also studied for comparison. Conversion of triol 5 to the respective tribromide 13 , trichloride 14, and triiodide 15 and subsequent refunctionalization of 13 to 9,10,11‐triaminotripindane 18 via the corresponding triazide 16 was achieved with preservation of C3 ‐symmetry in each case. In contrast, the C1 ‐triazide 17 is formed along with 16 under Lewis‐acid conditions, enabling an access to the C1 ‐symmetric triamine 19 . The increased torsion about the propellane axis of tribromotriptindane 13 was determined by X‐ray crystallography. There is strong evidence that the reduction 2 → 5 occurs by fast intracomplex transfer of three hydrides from the same alanate ion. In turn, attempts to confirm this by use of an equimolar mixture of LiAlH 4 and LiAlD 4 were nonsupportive; rather, they point to a hitherto unknown fast hydride exchange occurring in etheral alanate solutions.
{"title":"Triptindane‐9,10,11‐triol: Threefold Hydride Transfer from Lithium Aluminum Hydride as the Key Step to C 3 ‐Symmetrically Trifunctionalized Tribenzo[3.3.3]propellanes","authors":"Thorsten Hackfort, Bernhard M. Malorny, Andreas Mix, Beate Neumann, Hans‐Georg Stammler, Dietmar Kuck","doi":"10.1002/ejoc.202501039","DOIUrl":"https://doi.org/10.1002/ejoc.202501039","url":null,"abstract":"The <jats:italic>C</jats:italic> <jats:sub> <jats:italic>3v</jats:italic> </jats:sub> ‐symmetric framework of triptindane ( <jats:italic>C</jats:italic> <jats:sub> <jats:italic>3v</jats:italic> </jats:sub> ‐tribenzo[3.3.3]propellane, 1 ) was equipped with three benzylic monovalent functional groups in a <jats:italic>C</jats:italic> <jats:sub>3</jats:sub> ‐symmetric orientation. Key reaction was the reduction of 9,10,11‐triptindanetrione ( 2 ) with lithium aluminum hydride or sodium borohydride giving the corresponding <jats:italic>C</jats:italic> <jats:sub>3</jats:sub> ‐symmetric triol 5 in high yield and perfect diastereoselectivity. The diastereoselective reduction of 9,10‐triptindanedione 9 with LiAlH <jats:sub>4</jats:sub> was also studied for comparison. Conversion of triol 5 to the respective tribromide 13 , trichloride 14, and triiodide 15 and subsequent refunctionalization of 13 to 9,10,11‐triaminotripindane 18 via the corresponding triazide 16 was achieved with preservation of <jats:italic>C</jats:italic> <jats:sub>3</jats:sub> ‐symmetry in each case. In contrast, the <jats:italic>C</jats:italic> <jats:sub>1</jats:sub> ‐triazide 17 is formed along with 16 under Lewis‐acid conditions, enabling an access to the <jats:italic>C</jats:italic> <jats:sub>1</jats:sub> ‐symmetric triamine 19 . The increased torsion about the propellane axis of tribromotriptindane 13 was determined by X‐ray crystallography. There is strong evidence that the reduction 2 → 5 occurs by fast intracomplex transfer of three hydrides from the same alanate ion. In turn, attempts to confirm this by use of an equimolar mixture of LiAlH <jats:sub>4</jats:sub> and LiAlD <jats:sub>4</jats:sub> were nonsupportive; rather, they point to a hitherto unknown fast hydride exchange occurring in etheral alanate solutions.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"2 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2026-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147492509","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}
Quinone compounds have been widely demonstrated as highly promising electrode materials for rechargeable batteries due to their cost‐effectiveness, eco‐friendliness, and multifunctionality. Among them, tetraamino‐benzoquinone (TABQ) has garnered significant attention as a common building block owing to its potential for large‐scale production and unique molecular design flexibility. The amino (–NH 2 ) group in TABQ not only confers its multifunctionality in batteries but also enables the construction of one‐ to three‐dimensional electrode materials. These structural advantages give TABQ‐based electrode materials significant application potential in various rechargeable batteries. This minireview first outlines the design strategies and operating principles of TABQ‐based building bloks, then delves into their significance in battery technology, and finally discusses the potential challenges of TABQ‐based materials in rechargeable batteries.
{"title":"Tetraamino‐Benzoquinone‐Based Organic Materials for Advanced Energy Conversion and Storage","authors":"Haonan Sun, Shuo Li, Yifan Tong, Jincheng Sun, Linxin Lv, Jiecong Jia, Jinglun Yang, Adan Li, Qichun Zhang, Weiwei Huang","doi":"10.1002/ejoc.202501131","DOIUrl":"https://doi.org/10.1002/ejoc.202501131","url":null,"abstract":"Quinone compounds have been widely demonstrated as highly promising electrode materials for rechargeable batteries due to their cost‐effectiveness, eco‐friendliness, and multifunctionality. Among them, tetraamino‐benzoquinone (TABQ) has garnered significant attention as a common building block owing to its potential for large‐scale production and unique molecular design flexibility. The amino (–NH <jats:sub>2</jats:sub> ) group in TABQ not only confers its multifunctionality in batteries but also enables the construction of one‐ to three‐dimensional electrode materials. These structural advantages give TABQ‐based electrode materials significant application potential in various rechargeable batteries. This minireview first outlines the design strategies and operating principles of TABQ‐based building bloks, then delves into their significance in battery technology, and finally discusses the potential challenges of TABQ‐based materials in rechargeable batteries.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"20 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2026-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147492510","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}
By leveraging the impressive ability of gold catalysts to activate unsaturated systems and the natural tendency of organosilicon reagents to undergo silyl group rearrangements, this work has led to the discovery of a variety of new transformations. These developments provide effective methods for building molecular structures that are otherwise difficult to access. In this review, we highlight recent advances in gold‐catalyzed reactions of unsaturated organosilicon reagents, with a particular focus on silyl migration mechanisms. Over the past twenty years, this rapidly growing field has expanded greatly, opening new avenues for synthetic design and applications.
{"title":"Silyl Rearrangements in Gold‐Catalyzed Transformations","authors":"Patricia García‐Martínez, Luis A. López","doi":"10.1002/ejoc.70392","DOIUrl":"https://doi.org/10.1002/ejoc.70392","url":null,"abstract":"By leveraging the impressive ability of gold catalysts to activate unsaturated systems and the natural tendency of organosilicon reagents to undergo silyl group rearrangements, this work has led to the discovery of a variety of new transformations. These developments provide effective methods for building molecular structures that are otherwise difficult to access. In this review, we highlight recent advances in gold‐catalyzed reactions of unsaturated organosilicon reagents, with a particular focus on silyl migration mechanisms. Over the past twenty years, this rapidly growing field has expanded greatly, opening new avenues for synthetic design and applications.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"27 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2026-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147492513","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}
The Mizoroki–Heck reaction is a powerful method for constructing C(sp 2 )–C(sp 2 ) bonds through the coupling of (pseudo)halide electrophiles with alkenes. In contrast, the alkyl Heck variant, particularly reactions involving unbiased alkyl electrophiles, remains comparatively underdeveloped. Most existing methods rely on palladium catalysts, although recent years have seen growing progress with earth‐abundant‐metals such as nickel (Ni), cobalt (Co), iron (Fe), and copper (Cu). This short review summarizes recent advances in alkyl Heck‐type reactions that couple unbiased alkyl electrophiles with either activated (Type III) or unactivated alkenes (Type IV) under catalysis by earth‐abundant‐metals. The review is organized according to the metal catalyst employed and also includes recent developments in alkyl Heck‐type reactions catalyzed by a main‐group metal, bismuth.
{"title":"Earth‐Abundant Metal Catalysis for Alkyl Heck‐Type Reactions With Unbiased Electrophiles","authors":"Xin Chen, Xianglu Peng, Gang‐Wei Wang","doi":"10.1002/ejoc.202501238","DOIUrl":"https://doi.org/10.1002/ejoc.202501238","url":null,"abstract":"The Mizoroki–Heck reaction is a powerful method for constructing C(sp <jats:sup>2</jats:sup> )–C(sp <jats:sup>2</jats:sup> ) bonds through the coupling of (pseudo)halide electrophiles with alkenes. In contrast, the alkyl Heck variant, particularly reactions involving unbiased alkyl electrophiles, remains comparatively underdeveloped. Most existing methods rely on palladium catalysts, although recent years have seen growing progress with earth‐abundant‐metals such as nickel (Ni), cobalt (Co), iron (Fe), and copper (Cu). This short review summarizes recent advances in alkyl Heck‐type reactions that couple unbiased alkyl electrophiles with either activated (Type III) or unactivated alkenes (Type IV) under catalysis by earth‐abundant‐metals. The review is organized according to the metal catalyst employed and also includes recent developments in alkyl Heck‐type reactions catalyzed by a main‐group metal, bismuth.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"39 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2026-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147492511","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}
Trans ‐decalin‐like sulfonium oxathiane glycosyl donors have been previously shown as a viable route to access 1,2‐ cis ‐glycosides, though these reports have indicated that donor structure has a large influence on glycosylation outcome. This work describes the synthesis of an array of methyl oxathiane donors and their subsequent use in discerning the effect of structural differences on stereoselectivity and reactivity in glycosylations. In particular, introduction of 3‐methyl groups in the oxathiane scaffold allowed kinetic tuning of the glycosyl donor without diminishing α ‐selectivity.
{"title":"Discerning Structural Influences on Stereoselectivity and Kinetics in Glycosylations With Oxathiane Donors","authors":"Matthew E. Warnes, Martin A. Fascione","doi":"10.1002/ejoc.202500641","DOIUrl":"https://doi.org/10.1002/ejoc.202500641","url":null,"abstract":"<jats:italic>Trans</jats:italic> ‐decalin‐like sulfonium oxathiane glycosyl donors have been previously shown as a viable route to access 1,2‐ <jats:italic>cis</jats:italic> ‐glycosides, though these reports have indicated that donor structure has a large influence on glycosylation outcome. This work describes the synthesis of an array of methyl oxathiane donors and their subsequent use in discerning the effect of structural differences on stereoselectivity and reactivity in glycosylations. In particular, introduction of 3‐methyl groups in the oxathiane scaffold allowed kinetic tuning of the glycosyl donor without diminishing <jats:italic>α</jats:italic> ‐selectivity.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"14 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2026-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147492512","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}
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