Despite the formidable challenge of concurrently managing both the regiochemistry and stereochemistry of the process, organocatalytic remote stereocontrol has emerged as an appealing approach to establish stereocenters at specified locations distant from reactive functional groups. Herein, we achieved the first organocatalyzed remote stereocontrolled (4+2) annulation of 2‐(4H‐benzo[d][1,3]oxazin‐4‐yl)acrylates with 4‐methyleneisoxazol‐5(4H)‐ones. The nucleophilic attack of a suitable chiral amine to 2‐(4H‐benzo[d][1,3]oxazin‐4‐yl)acrylates generated the key amine‐dipole intermediate, followed by the enantioselective aza‐1,4‐addition of 4‐methyleneisoxazol‐5(4H)‐ones and intramolecular annulation cascade reaction to construct spiro[isoxazole‐4,3’‐quinolin]‐5‐one frameworks bearing continuous three stereocenters. More importantly, different from the well‐established reactions of MBH carbonates, this work successfully established a novel platform for the direct enantioselective synthesis of continuous three stereocenters, inclusive of an ε‐stereocenter.
{"title":"Organocatalytic Remote Stereocontrolled (4+2) Annulation of 2‐(4H‐Benzo[d][1,3]oxazin‐4‐yl)acrylates with 4‐Methyleneisoxazol‐5(4H)‐ones","authors":"Yan Liu, Xuling Chen, Pengfei Li","doi":"10.1002/adsc.202401603","DOIUrl":"https://doi.org/10.1002/adsc.202401603","url":null,"abstract":"Despite the formidable challenge of concurrently managing both the regiochemistry and stereochemistry of the process, organocatalytic remote stereocontrol has emerged as an appealing approach to establish stereocenters at specified locations distant from reactive functional groups. Herein, we achieved the first organocatalyzed remote stereocontrolled (4+2) annulation of 2‐(4H‐benzo[d][1,3]oxazin‐4‐yl)acrylates with 4‐methyleneisoxazol‐5(4H)‐ones. The nucleophilic attack of a suitable chiral amine to 2‐(4H‐benzo[d][1,3]oxazin‐4‐yl)acrylates generated the key amine‐dipole intermediate, followed by the enantioselective aza‐1,4‐addition of 4‐methyleneisoxazol‐5(4H)‐ones and intramolecular annulation cascade reaction to construct spiro[isoxazole‐4,3’‐quinolin]‐5‐one frameworks bearing continuous three stereocenters. More importantly, different from the well‐established reactions of MBH carbonates, this work successfully established a novel platform for the direct enantioselective synthesis of continuous three stereocenters, inclusive of an ε‐stereocenter.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"182 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143462929","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Many enantiopure chiral organic molecules are very important unit for drug discovery. Ready access to a wide range of enantiopure organic compounds, attached with one or more chiral centres significantly enhance the quality and diversity of chemical libraries for screening of drug discovery. The ability to control the stereochemistry of many organic reactions remains an area of interest in organic synthesis to allow the development of novel, structurally diverse 3D molecules. Asymmetric catalysis has been extensively studied for controlling the stereochemistry in modern synthetic organic chemistry. Recently, the use of light as the energy source with a chiral photocatalysts for photocatalytic asymmetric organic reactions has drawn much attentions but limited in numbers. The short lifetime of excited chiral photocatalysts and very fast reactions make the stereocontrol difficult in many reactions. However, by making a chiral photoactive metal complex with a suitable metal and ligands, this problem could be solved. As these chiral metal complexes are stable under light irradiation, versatile, having easy tuneable properties, these can provide more chiral inductions in many asymmetric organic reactions. So, in this review, we have focused on the recent development on chiral metal complexes as the standalone chiral photocatalysts for asymmetric organic reactions. We hope this review will help to understand the scopes and limitations to the research community in the field of asymmetric synthesis.
{"title":"Advances of chiral metal complexes as standalone photocatalyst for asymmetric organic transformations","authors":"Anjan Das, A. John David, Balaji Ramachandran","doi":"10.1002/adsc.202401543","DOIUrl":"https://doi.org/10.1002/adsc.202401543","url":null,"abstract":"Many enantiopure chiral organic molecules are very important unit for drug discovery. Ready access to a wide range of enantiopure organic compounds, attached with one or more chiral centres significantly enhance the quality and diversity of chemical libraries for screening of drug discovery. The ability to control the stereochemistry of many organic reactions remains an area of interest in organic synthesis to allow the development of novel, structurally diverse 3D molecules. Asymmetric catalysis has been extensively studied for controlling the stereochemistry in modern synthetic organic chemistry. Recently, the use of light as the energy source with a chiral photocatalysts for photocatalytic asymmetric organic reactions has drawn much attentions but limited in numbers. The short lifetime of excited chiral photocatalysts and very fast reactions make the stereocontrol difficult in many reactions. However, by making a chiral photoactive metal complex with a suitable metal and ligands, this problem could be solved. As these chiral metal complexes are stable under light irradiation, versatile, having easy tuneable properties, these can provide more chiral inductions in many asymmetric organic reactions. So, in this review, we have focused on the recent development on chiral metal complexes as the standalone chiral photocatalysts for asymmetric organic reactions. We hope this review will help to understand the scopes and limitations to the research community in the field of asymmetric synthesis.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"14 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143462930","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yuming Li, Yan Gou, Shuanghui Wang, Yaqi Xuan, Lulu Fu, Zhi Fan
In this paper, we reported a novel sequential reaction sequence consisting of two processes including domino [3+2]/[2+1] annulation and in situ Cloke-Wilson rearrangement reaction, which enabled synthesis of a series of structurally complex polycyclic pyrrolizine derivatives in 51-96% yields and excellent diastereoselectivities. The viability of the existing protocol was additionally illustrated by gram-scale synthesis and further modifications. In addution, some of these valuable ring-fused pyrrolizines displayed some extent of anticancer activity, demonstrating their potential application in the medicinal chemistry.
{"title":"Base-Mediated Sequential Annulation Reaction of β-Pyrrol-α,β-Unsaturated Compounds with Vinylsulfonium Salts: A New Approach to Polycyclic Pyrrolizine Derivatives","authors":"Yuming Li, Yan Gou, Shuanghui Wang, Yaqi Xuan, Lulu Fu, Zhi Fan","doi":"10.1002/adsc.202500032","DOIUrl":"https://doi.org/10.1002/adsc.202500032","url":null,"abstract":"In this paper, we reported a novel sequential reaction sequence consisting of two processes including domino [3+2]/[2+1] annulation and in situ Cloke-Wilson rearrangement reaction, which enabled synthesis of a series of structurally complex polycyclic pyrrolizine derivatives in 51-96% yields and excellent diastereoselectivities. The viability of the existing protocol was additionally illustrated by gram-scale synthesis and further modifications. In addution, some of these valuable ring-fused pyrrolizines displayed some extent of anticancer activity, demonstrating their potential application in the medicinal chemistry.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"45 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143463038","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Justyna Kowalska, Adam Cieśliński, Jose Julian Aleman Lara, Łukasz Albrecht
Pyrrolo[1,2-a]indole derivatives are widely present in bioactive alkaloids and pharmaceuticals, with pyrroloindolones, containing a γ-lactam fused to an indole scaffold, forming a significant class of heteroaromatic compounds due to their presence in numerous natural products and biologically active molecules. In this study, we explored the potential of indole-derived hydrazones as 1,2-dinucleophiles in the N-heterocyclic carbene (NHC)-catalyzed formal [3+2]-cycloaddition with α-bromo-α,β-unsaturated aldehydes. A broad substrate scope was investigated, revealing the versatility of the method with various aldehydes and hydrazones. Subsequent transformations of the cycloaddition products demonstrated the synthetic utility of the developed methodology, preserving the optical purity of the final products.
{"title":"Harnessing Indole-Derived Hydrazones for Enantioselective Synthesis of Pyrroloindolones via NHC-Catalyzed Formal [3+2]-Cycloaddition","authors":"Justyna Kowalska, Adam Cieśliński, Jose Julian Aleman Lara, Łukasz Albrecht","doi":"10.1002/adsc.202500016","DOIUrl":"https://doi.org/10.1002/adsc.202500016","url":null,"abstract":"Pyrrolo[1,2-a]indole derivatives are widely present in bioactive alkaloids and pharmaceuticals, with pyrroloindolones, containing a γ-lactam fused to an indole scaffold, forming a significant class of heteroaromatic compounds due to their presence in numerous natural products and biologically active molecules. In this study, we explored the potential of indole-derived hydrazones as 1,2-dinucleophiles in the N-heterocyclic carbene (NHC)-catalyzed formal [3+2]-cycloaddition with α-bromo-α,β-unsaturated aldehydes. A broad substrate scope was investigated, revealing the versatility of the method with various aldehydes and hydrazones. Subsequent transformations of the cycloaddition products demonstrated the synthetic utility of the developed methodology, preserving the optical purity of the final products.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"25 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143462710","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Surya Prakash, Ziyue Zhu, Jiaqi Tang, Matthew Coe, Alexander Knieb, Yijie Xu, Daniel Lin, Chao Zhang
An operationally simple protocol to access 2,2‐chlorofluoro‐, and 2,2‐bromofluorobicyclopentanes (BCPs) via commercially available, inexpensive, non‐ozone depleting, and bench stable reagents is reported. The resulting BCP products are tolerated in diverse, synthetically relevant post‐functionalization reactions. Gram‐scale reactions to prepare the BCPs are also included.
{"title":"Access to 2,2‐Halofluorobicyclo[1.1.1] pentanes via Non Ozone‐depleting Ethyl Dihalofluoroacetate","authors":"Surya Prakash, Ziyue Zhu, Jiaqi Tang, Matthew Coe, Alexander Knieb, Yijie Xu, Daniel Lin, Chao Zhang","doi":"10.1002/adsc.202401475","DOIUrl":"https://doi.org/10.1002/adsc.202401475","url":null,"abstract":"An operationally simple protocol to access 2,2‐chlorofluoro‐, and 2,2‐bromofluorobicyclopentanes (BCPs) via commercially available, inexpensive, non‐ozone depleting, and bench stable reagents is reported. The resulting BCP products are tolerated in diverse, synthetically relevant post‐functionalization reactions. Gram‐scale reactions to prepare the BCPs are also included.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"14 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143443725","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pedro Almendros, Daniel San Martín, Teresa Martínez del Campo
We report the direct and selective synthesis of oxadendralenes starting from readily available bis(α-hydroxyallenes). The designed sequence involves a hitherto unknown oxy-Cope rearrangement of allenols by supplying a site for the migration of the 1,2-diene moiety. Moreover, the so-prepared oxadendralenes were converted into valuable polyfunctionalized scaffolds through effective late-stage diversification.
{"title":"Synthesis of Oxadendralenes by Thermal Oxy-Cope Type Rearrangement of Bis(α-hydroxyallenes)","authors":"Pedro Almendros, Daniel San Martín, Teresa Martínez del Campo","doi":"10.1002/adsc.202500080","DOIUrl":"https://doi.org/10.1002/adsc.202500080","url":null,"abstract":"We report the direct and selective synthesis of oxadendralenes starting from readily available bis(α-hydroxyallenes). The designed sequence involves a hitherto unknown oxy-Cope rearrangement of allenols by supplying a site for the migration of the 1,2-diene moiety. Moreover, the so-prepared oxadendralenes were converted into valuable polyfunctionalized scaffolds through effective late-stage diversification.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"25 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143462713","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Tulshiram Dadmal, Koppadi Syam Venkata Kishore, Chandrakant Wasekar, Prashant G. Borkar, Mangesh E. Shelke, sudhakar M bansod, Sunil Kumar Nechipadappu, P. Sathya Shanker
A facile one-pot, three-component cascade cyclization has been developed for synthesis of 2-trifluoromethyl-2-ol dihydropyrroles and 4-trifluoromethyl-4-ol dihydropyrroles from various substituted amines, 3-bromo-1,1,1-trifluoropropan-2-one, and substituted β-oxoamides using K₂CO₃ as an additive. This K₂CO₃-promoted method offers a simple and efficient approach for achieving highly regioselective products through cascade bond formation and cyclization. Post functionalization of resulting products into various valuable trifluoromethylated heterocycles including triazoles, isoxazoles, Mannich bases and the products from Sonogashira coupling reactions has also been reported. Additionally, a straightforward and scalable protocol for synthesis of 4-trifluoromethylpyrrole-3-carboxamide derivatives without K₂CO₃, utilizing diverse 1,3-dicarbonyl compounds has been established. This method demonstrates broad substrate compatibility, efficient tolerance towards a wide range of functional groups, making it a versatile strategy for accessing highly substituted trifluoromethylated pyrroles.
{"title":"One-pot tandem cyclization of β-oxoamides, primary amines, and 3-bromo-1,1,1-trifluoroacetone: Synthesis of 2/4-trifluoromethyl-substituted dihydropyrrol-2/4-ols","authors":"Tulshiram Dadmal, Koppadi Syam Venkata Kishore, Chandrakant Wasekar, Prashant G. Borkar, Mangesh E. Shelke, sudhakar M bansod, Sunil Kumar Nechipadappu, P. Sathya Shanker","doi":"10.1002/adsc.202401513","DOIUrl":"https://doi.org/10.1002/adsc.202401513","url":null,"abstract":"A facile one-pot, three-component cascade cyclization has been developed for synthesis of 2-trifluoromethyl-2-ol dihydropyrroles and 4-trifluoromethyl-4-ol dihydropyrroles from various substituted amines, 3-bromo-1,1,1-trifluoropropan-2-one, and substituted β-oxoamides using K₂CO₃ as an additive. This K₂CO₃-promoted method offers a simple and efficient approach for achieving highly regioselective products through cascade bond formation and cyclization. Post functionalization of resulting products into various valuable trifluoromethylated heterocycles including triazoles, isoxazoles, Mannich bases and the products from Sonogashira coupling reactions has also been reported. Additionally, a straightforward and scalable protocol for synthesis of 4-trifluoromethylpyrrole-3-carboxamide derivatives without K₂CO₃, utilizing diverse 1,3-dicarbonyl compounds has been established. This method demonstrates broad substrate compatibility, efficient tolerance towards a wide range of functional groups, making it a versatile strategy for accessing highly substituted trifluoromethylated pyrroles.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"22 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143462712","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jun Yang, Jianyu Zhang, Tianxing Li, Yunting Liu, Hui Jin, Do Hyun Ryu, Lixin Zhang
The Friedel-Crafts reaction between indoles and ketones poses a significant challenge. In this study, we developed an efficient and environmentally friendly approach for the synthesis of bis(indolyl)methanes bearing all-carbon quaternary and tertiary centers at room temperature under "on water" conditions. Notably, the utilization of saturated lithium chloride as a solvent greatly enhances the Brønsted acid-catalyzed double additions of indoles to ketones and aldehydes by promoting hydrophobic interactions. Additionally, LiCl acts as a Lewis acid catalyst for carbonyl activation and facilitates dehydration. This methodology demonstrates compatibility with various ketone substrates such as alkyl alkyl ketones and aryl alkyl ketones, along with aldehyde substrates. Furthermore, gram-scale productions were successful, and the LiCl solutions demonstrate reusability.
{"title":"Lithium Chloride-Promoted Brønsted Acid-Catalyzed Friedel-Crafts Alkylation Reaction of Indoles with Aldehydes and Ketones \"on Water\"","authors":"Jun Yang, Jianyu Zhang, Tianxing Li, Yunting Liu, Hui Jin, Do Hyun Ryu, Lixin Zhang","doi":"10.1002/adsc.202401542","DOIUrl":"https://doi.org/10.1002/adsc.202401542","url":null,"abstract":"The Friedel-Crafts reaction between indoles and ketones poses a significant challenge. In this study, we developed an efficient and environmentally friendly approach for the synthesis of bis(indolyl)methanes bearing all-carbon quaternary and tertiary centers at room temperature under \"on water\" conditions. Notably, the utilization of saturated lithium chloride as a solvent greatly enhances the Brønsted acid-catalyzed double additions of indoles to ketones and aldehydes by promoting hydrophobic interactions. Additionally, LiCl acts as a Lewis acid catalyst for carbonyl activation and facilitates dehydration. This methodology demonstrates compatibility with various ketone substrates such as alkyl alkyl ketones and aryl alkyl ketones, along with aldehyde substrates. Furthermore, gram-scale productions were successful, and the LiCl solutions demonstrate reusability.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"209 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143462716","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A simple and efficient Ag‐catalyzed tandem selanylation/cyclization of o‐alkynyl benzylazides/o‐alkynyloxy benzylazides with diselenides has been developed. The reaction afforded a series of 3‐seleno‐8H‐[1,2,3]triazolo[5,1‐a]isoindoles and 3‐seleno‐4H,10H‐benzo[f][1,2,3]triazolo[5,1‐c][1,4]oxazepanes in moderate to good yields. The mechanistic study revealed that the intramolecular AAC reaction of an alkynyl selenium intermediate occurred. The synthesized compound 3k showed potent cancer cell‐growth inhibition activities.
{"title":"Silver‐mediated in‐situ generation of alkynyl selenium intramolecular AAC click reactions","authors":"Jian-Long Cao, Yi-Huan Zhou, Xi-Rui Gong, Mei-Lin Ren, Yan-yan Chen, Yan-Li Xu","doi":"10.1002/adsc.202500098","DOIUrl":"https://doi.org/10.1002/adsc.202500098","url":null,"abstract":"A simple and efficient Ag‐catalyzed tandem selanylation/cyclization of o‐alkynyl benzylazides/o‐alkynyloxy benzylazides with diselenides has been developed. The reaction afforded a series of 3‐seleno‐8H‐[1,2,3]triazolo[5,1‐a]isoindoles and 3‐seleno‐4H,10H‐benzo[f][1,2,3]triazolo[5,1‐c][1,4]oxazepanes in moderate to good yields. The mechanistic study revealed that the intramolecular AAC reaction of an alkynyl selenium intermediate occurred. The synthesized compound 3k showed potent cancer cell‐growth inhibition activities.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"198 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143443726","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The palladium/norbornene (Pd/NBE) cooperative catalysis, first identified by Catellani in 1997, provides an efficient approach for synthesizing highly functionalized aromatic compounds that are challenging to obtain through conventional methods. The developed synthetic approach integrates selective C‐H bond activation with sequential reactions, allowing for the targeted functionalization of both the ortho and ipso positions of aryl halides via aryl‐norbornadiene‐palladacycle (ANP), which in turn ensures high chemoselectivity and regioselectivity of the products. It is estimated that approximately 20% of all natural products are glycosylated, with the carbohydrates linked to these compounds frequently playing a critical role in their biological activity. Currently, research in carbohydrate chemistry predominantly concentrates on polysubstitutional derivatization or vicinal functionalization strategies. However, the limited availability of 1,2‐disubstituted compounds has been scarcely investigated, and previous studies often relied on directional group assistance to achieve disubstitution. Recently, significant advancements have been achieved with Pd/NBE cooperative catalysis, an area that has gained considerable importance in carbohydrate chemistry, presenting an opportunity to inspire further research interest in Catellani reactions. In this review, we provide a comprehensive analysis of the Pd/NBE strategy within the realm of sugar chemistry, encompass early research and advancement in catalytic reactions, outline synthetic potential, highlight the significant progress made, and emphasize the most recent developments and their applications in situ vicinal functionalization of carbohydrate derivatives.
{"title":"Palladium/Norbornene Cooperative Catalysis: A Modular In Situ Vicinal Functionalization Strategy for Recent Developments of Carbohydrate Chemistry","authors":"Himanshu Gangwar, Zanjila Azeem, Pintu Kumar Mandal","doi":"10.1002/adsc.202401570","DOIUrl":"https://doi.org/10.1002/adsc.202401570","url":null,"abstract":"The palladium/norbornene (Pd/NBE) cooperative catalysis, first identified by Catellani in 1997, provides an efficient approach for synthesizing highly functionalized aromatic compounds that are challenging to obtain through conventional methods. The developed synthetic approach integrates selective C‐H bond activation with sequential reactions, allowing for the targeted functionalization of both the ortho and ipso positions of aryl halides via aryl‐norbornadiene‐palladacycle (ANP), which in turn ensures high chemoselectivity and regioselectivity of the products. It is estimated that approximately 20% of all natural products are glycosylated, with the carbohydrates linked to these compounds frequently playing a critical role in their biological activity. Currently, research in carbohydrate chemistry predominantly concentrates on polysubstitutional derivatization or vicinal functionalization strategies. However, the limited availability of 1,2‐disubstituted compounds has been scarcely investigated, and previous studies often relied on directional group assistance to achieve disubstitution. Recently, significant advancements have been achieved with Pd/NBE cooperative catalysis, an area that has gained considerable importance in carbohydrate chemistry, presenting an opportunity to inspire further research interest in Catellani reactions. In this review, we provide a comprehensive analysis of the Pd/NBE strategy within the realm of sugar chemistry, encompass early research and advancement in catalytic reactions, outline synthetic potential, highlight the significant progress made, and emphasize the most recent developments and their applications in situ vicinal functionalization of carbohydrate derivatives.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"8 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435400","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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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