Clemens Cziegler , Benjamin Baumert , Christoffel P. S. Badenhorst , Karsten Siems , Uwe T. Bornscheuer
In this study, a selective C−H‐oxyfunctionalization using an unspecific peroxygenase (UPO) enabled an efficient biosynthetic route for the synthesis of grevillic acid (GA), a natural antioxidant. The route commenced with the release of o‐coumaric acid (oCA) from trans‐2‐coumaric acid glucoside (trans‐CAG) using commercially available β‐glucosidase from almonds. In addition, a cis‐to‐trans photoisomerization of cis‐CAG was implemented to increase the synthetic access of oCA. The key step, the para‐hydroxylation relative to the existing hydroxyl group of oCA, was accomplished by an UPO with full conversion and 93% isolated yield. Despite its name, the UPO turned out to exhibit excellent regioselectivity in this C−H functionalization, requiring only H2O2 as a cosubstrate.
{"title":"Selective Enzymatic C−H‐Oxyfunctionalization for the Efficient Synthesis of Grevillic Acid","authors":"Clemens Cziegler , Benjamin Baumert , Christoffel P. S. Badenhorst , Karsten Siems , Uwe T. Bornscheuer","doi":"10.1002/adsc.202401421","DOIUrl":"10.1002/adsc.202401421","url":null,"abstract":"<div><div>In this study, a selective C−H‐oxyfunctionalization using an unspecific peroxygenase (UPO) enabled an efficient biosynthetic route for the synthesis of grevillic acid (GA), a natural antioxidant. The route commenced with the release of <em>o</em>‐coumaric acid (oCA) from <em>trans</em>‐2‐coumaric acid glucoside (<em>trans</em>‐CAG) using commercially available <em>β‐</em>glucosidase from almonds. In addition, a <em>cis</em>‐to‐<em>trans</em> photoisomerization of <em>cis</em>‐CAG was implemented to increase the synthetic access of oCA. The key step, the <em>para</em>‐hydroxylation relative to the existing hydroxyl group of oCA, was accomplished by an UPO with full conversion and 93% isolated yield. Despite its name, the UPO turned out to exhibit excellent regioselectivity in this C−H functionalization, requiring only H<sub>2</sub>O<sub>2</sub> as a cosubstrate.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"367 3","pages":"Article e202401421"},"PeriodicalIF":4.4,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/adsc.202401421","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142753422","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ruthenium‐catalyzed and K2S2O8‐mediated synthesis of diverse sulfonylated 5‐aroyl‐2‐arylpyridines was developed through one‐pot stepwise annulation of two molecules of β‐ketosulfones and N,N‐dimethylformamide (DMF) under the sealed tube conditions. In the overall process, DMF acts as the synthon of one carbon and one imino moiety in the construction of pyridine skeleton via cascade formation of single (C−C/C−N) and double (C=C/C=N) bonds under refluxing DMF conditions. Plausible reaction mechanism is proposed and discussed.
{"title":"One‐Pot Synthesis of Sulfonylated 5‐Aroyl‐2‐Arylpyridines via Ruthenium‐Catalyzed and K2S2O8‐Mediated Domino Annulation of β‐Ketosulfones with DMF","authors":"Meng‐Yang Chang , Chi‐Ru Yang , Yeh‐Long Chen","doi":"10.1002/adsc.202401116","DOIUrl":"10.1002/adsc.202401116","url":null,"abstract":"<div><div>Ruthenium‐catalyzed and K<sub>2</sub>S<sub>2</sub>O<sub>8</sub>‐mediated synthesis of diverse sulfonylated 5‐aroyl‐2‐arylpyridines was developed through one‐pot stepwise annulation of two molecules of β‐ketosulfones and <em>N</em>,<em>N</em>‐dimethylformamide (DMF) under the sealed tube conditions. In the overall process, DMF acts as the synthon of one carbon and one imino moiety in the construction of pyridine skeleton via cascade formation of single (C−C/C−N) and double (C=C/C=N) bonds under refluxing DMF conditions. Plausible reaction mechanism is proposed and discussed.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"367 3","pages":"Article e202401116"},"PeriodicalIF":4.4,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142374547","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}
Adam Cieśliński , Artur Przydacz , Lesław Sieroń , Anna Skrzyńska , Łukasz Albrecht
[10+2]‐Hetero‐higher‐order cycloaddition between tropone hydrazides (acting as 10π‐components) and 3‐alkylidene oxindoles (acting as 2π‐components) has been established. Under Brønsted base catalysis the reaction proceeded in a fully peri‐ and diastereoselective manner with the stereochemical outcome governed mainly by electronic interactions. Following such a strategy, a series of structurally diverse tetrahydropyridazines were prepared in 30–70% yields. Furthermore, the potential of the obtained cycloadducts has been confirmed in selected chemoselective transformations.
{"title":"Tropone Hydrazides in [10+2]‐Hetero‐Higher‐Order Cycloaddition for the Synthesis of Tetrahydropyridazine Derivatives","authors":"Adam Cieśliński , Artur Przydacz , Lesław Sieroń , Anna Skrzyńska , Łukasz Albrecht","doi":"10.1002/adsc.202401033","DOIUrl":"10.1002/adsc.202401033","url":null,"abstract":"<div><div>[10+2]‐Hetero‐higher‐order cycloaddition between tropone hydrazides (acting as 10π‐components) and 3‐alkylidene oxindoles (acting as 2π‐components) has been established. Under Brønsted base catalysis the reaction proceeded in a fully peri‐ and diastereoselective manner with the stereochemical outcome governed mainly by electronic interactions. Following such a strategy, a series of structurally diverse tetrahydropyridazines were prepared in 30–70% yields. Furthermore, the potential of the obtained cycloadducts has been confirmed in selected chemoselective transformations.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"367 3","pages":"Article e202401033"},"PeriodicalIF":4.4,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/adsc.202401033","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142385066","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Camphorsultam was utilized for the optical resolution of P‐chiral phosphorous compounds. After chromatographic separation of diastereomeric RP‐ and SP‐phosphonamidate intermediates, subsequent substitution reactions with phenol derivatives yielded P‐chiral phosphonic acid aryl esters with excellent enantioselectivities. In these processes, chiral sulfonamide of camphorsultam demonstrated superior abilities as an optical‐resolving agent and a good leaving group. This method was applied to the synthesis of P‐chiral phosphinic esters, phosphonamidates, and thiophosphonate diesters.
{"title":"Phosphonamidates of Camphorsultam: Versatile Building Blocks for the Synthesis of P‐Chiral Phosphorous(V) Compounds","authors":"Yasutomo Yamamoto , Yurika Kambara , Ayase Matsumoto , Miku Murata , Mizuki Nakamoto , Tomoe Ishiura , Sakura Nakai , Hideyasu China , Kenji Watanabe , Akari Miyawaki , Junpei Matsuoka","doi":"10.1002/adsc.202401268","DOIUrl":"10.1002/adsc.202401268","url":null,"abstract":"<div><div>Camphorsultam was utilized for the optical resolution of <em>P</em>‐chiral phosphorous compounds. After chromatographic separation of diastereomeric <em>R</em><sub>P</sub>‐ and <em>S</em><sub>P</sub>‐phosphonamidate intermediates, subsequent substitution reactions with phenol derivatives yielded <em>P</em>‐chiral phosphonic acid aryl esters with excellent enantioselectivities. In these processes, chiral sulfonamide of camphorsultam demonstrated superior abilities as an optical‐resolving agent and a good leaving group. This method was applied to the synthesis of <em>P</em>‐chiral phosphinic esters, phosphonamidates, and thiophosphonate diesters.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"367 3","pages":"Article e202401268"},"PeriodicalIF":4.4,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142718303","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}
Different catalysts are presented to overcome or augment a substrate's innate regioselectivity. Rhodium was found to overcome the innate C3‐selectivity via chelation‐assisted rhodation. Conversely, palladium was found to enhance the innate C5‐selectivity via electrophilic palladation. These reactions allow for the formation of a diverse range of synthetically versatile C3‐ and C5‐alkynylated products from 2‐pyridylthiophenes. Notably, this strategy was successfully employed in the straightforward synthesis of π‐extended functionalized 2‐pyridylthiophenes, which could be converted into more valuable compounds.
{"title":"Catalyst‐Controlled Regiodivergent C−H Alkynylation of 2‐Pyridylthiophenes","authors":"Yuting Gui , Yaokun Zhao , Xingchi Li , Taoyuan Liang , Shuangliang Zhao , Zhuan Zhang","doi":"10.1002/adsc.202400856","DOIUrl":"10.1002/adsc.202400856","url":null,"abstract":"<div><div>Different catalysts are presented to overcome or augment a substrate's innate regioselectivity. Rhodium was found to overcome the innate C3‐selectivity <em>via</em> chelation‐assisted rhodation. Conversely, palladium was found to enhance the innate C5‐selectivity <em>via</em> electrophilic palladation. These reactions allow for the formation of a diverse range of synthetically versatile C3‐ and C5‐alkynylated products from 2‐pyridylthiophenes. Notably, this strategy was successfully employed in the straightforward synthesis of π‐extended functionalized 2‐pyridylthiophenes, which could be converted into more valuable compounds.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"367 3","pages":"Article e202400856"},"PeriodicalIF":4.4,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142374470","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}
Haibo Mei , Yucheng Zhang , Jiang Liu , Jorge Escorihuela , Loránd Kiss , Jianlin Han
An electrochemical cascade radical cyclization of 2‐aryl‐N‐acryloyl indoles with sodium trifluoromethanesulfinate as a coupling partner has been explored, which afforded the unexpected bis‐trifluoromethylated indole[2,1‐a]isoquinolines as products. Experimental results and DFT calculations disclose that this reaction involves trifluoromethylation‐triggered cyclization and the second trifluoromethylation as the key steps. This strategy does not need any transition‐metal catalysts or oxidants with a readily available trifluoromethylating reagent enabling facile synthesis of bis‐trifluoromethylated indole‐fused tricycles.
{"title":"Electrochemical Dual Trifluoromethylation/Cyclization of 2‐Aryl‐N‐Acryloyl Indoles Enabling Assembly of Indole[2,1‐a]isoquinolines","authors":"Haibo Mei , Yucheng Zhang , Jiang Liu , Jorge Escorihuela , Loránd Kiss , Jianlin Han","doi":"10.1002/adsc.202401225","DOIUrl":"10.1002/adsc.202401225","url":null,"abstract":"<div><div>An electrochemical cascade radical cyclization of 2‐aryl‐<em>N</em>‐acryloyl indoles with sodium trifluoromethanesulfinate as a coupling partner has been explored, which afforded the unexpected bis‐trifluoromethylated indole[2,1‐<em>a</em>]isoquinolines as products. Experimental results and DFT calculations disclose that this reaction involves trifluoromethylation‐triggered cyclization and the second trifluoromethylation as the key steps. This strategy does not need any transition‐metal catalysts or oxidants with a readily available trifluoromethylating reagent enabling facile synthesis of bis‐trifluoromethylated indole‐fused tricycles.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"367 3","pages":"Article e202401225"},"PeriodicalIF":4.4,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142735602","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}
Bin Xiao , Kangping Wu , Mianling Zhang , Haixiang Hu , Xiaochong Guo
The chromium‐catalysed Nozaki‐Hiyama‐Kishi (NHK) reaction is a very dependable technique for alcohol synthesis and is extensively used in the complete synthesis of natural compounds. The majority of these reactions occur via a reductive‐radical‐polar crossover (RRPCO) mechanism, which is crucial for the transformation of reactive radical intermediates. The production of radicals using photoinduced catalytic reactions is now among the most effective approaches. The photoinduced chromium‐catalysed addition reaction to carbonyl compounds is an effective technique for alcohol synthesis that integrates the benefits of photocatalysis with chromium catalysis. Photocatalysis significantly enhances the diversity of radical production, hence broadening the substrate scope in the chromium‐catalysed NHK reaction. This paper primarily examines the photoredox chromium dual‐catalysed carbonyl addition process for alcohol synthesis, including numerous methods for radical generation.
铬催化Nozaki - Hiyama - Kishi （NHK）反应是一种非常可靠的醇合成技术，广泛用于天然化合物的完全合成。这些反应大多通过还原-自由基-极性交叉（RRPCO）机制发生，这对于活性自由基中间体的转化至关重要。利用光诱导催化反应产生自由基是目前最有效的方法之一。光诱导铬催化羰基化合物加成反应是一种有效的醇合成技术，它综合了光催化和铬催化的优点。光催化显著增强了自由基生成的多样性，从而拓宽了铬催化NHK反应的底物范围。本文主要研究了光氧化还原铬双催化羰基加成工艺用于酒精合成，包括多种自由基生成方法。
{"title":"Recent Advances in Photoredox/Chromium Dual‐Catalyzed Carbonyl Addition Reactions: A Review","authors":"Bin Xiao , Kangping Wu , Mianling Zhang , Haixiang Hu , Xiaochong Guo","doi":"10.1002/adsc.202401315","DOIUrl":"10.1002/adsc.202401315","url":null,"abstract":"<div><div>The chromium‐catalysed Nozaki‐Hiyama‐Kishi (NHK) reaction is a very dependable technique for alcohol synthesis and is extensively used in the complete synthesis of natural compounds. The majority of these reactions occur via a reductive‐radical‐polar crossover (RRPCO) mechanism, which is crucial for the transformation of reactive radical intermediates. The production of radicals using photoinduced catalytic reactions is now among the most effective approaches. The photoinduced chromium‐catalysed addition reaction to carbonyl compounds is an effective technique for alcohol synthesis that integrates the benefits of photocatalysis with chromium catalysis. Photocatalysis significantly enhances the diversity of radical production, hence broadening the substrate scope in the chromium‐catalysed NHK reaction. This paper primarily examines the photoredox chromium dual‐catalysed carbonyl addition process for alcohol synthesis, including numerous methods for radical generation.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"367 3","pages":"Article e202401315"},"PeriodicalIF":4.4,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142804923","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}
We, herein, report a base free, photocatalytic decyanation of α‐aminonitriles. A range of amides and lactams were obtained in 52–95% yields. Control experiments indicate O2 as an amide/lactam oxygen source and the reaction (lactam formation) follows radical pathway via dioxetanimine species. This methodology also applied for α‐ester/aldehyde substituted pyrrolidines in the presence of a base, probably via decarboxylation pathway.
{"title":"Photocatalytic Oxidation of α‐Substituted Amines to Lactams/Amides","authors":"Manish Kumar , Pawan Kumar , Utpal Das","doi":"10.1002/adsc.202400871","DOIUrl":"10.1002/adsc.202400871","url":null,"abstract":"<div><div>We, herein, report a base free, photocatalytic decyanation of <em>α</em>‐aminonitriles. A range of amides and lactams were obtained in 52–95% yields. Control experiments indicate O<sub>2</sub> as an amide/lactam oxygen source and the reaction (lactam formation) follows radical pathway via dioxetanimine species. This methodology also applied for <em>α</em>‐ester/aldehyde substituted pyrrolidines in the presence of a base, probably via decarboxylation pathway.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"367 3","pages":"Article e202400871"},"PeriodicalIF":4.4,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142317233","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}
Xiao‐Qing Xie , Zi‐Qiong Li , Wei Zhou , Chaozhihui Cheng , Jiang Bai , Haixin Ding , Xian‐Rong Song , Mu‐Jia Luo , Qiang Xiao
Herein, an electroreductive aryl radical enabled 5‐exo‐dig cyclization of N‐cyano‐2‐halobenzamides is presented, providing a convenient route for the synthesis of a variety of 3‐iminoisoindolin‐1‐ones in 30–75% yields. Simply by employing zinc plate instead of graphite rod anode, the products of the electrosynthesis are switched to diverse 3‐aminoisoindolin‐1‐ones through aryl‐radical‐mediated 5‐exo‐dig cyclization and subsequent reductive hydrogenation. Furthermore, this anode material determined divergent 5‐exo‐dig cyclization features mild electrochemical conditions, excellent substrate scopes, and good functional group tolerance.
{"title":"Anode Material Determined Divergent 5‐exo‐dig Cyclization of N‐Cyano‐2‐Halobenzamides Toward 3‐Iminoisoindolin‐1‐ones and 3‐Aminoisoindolin‐1‐ones","authors":"Xiao‐Qing Xie , Zi‐Qiong Li , Wei Zhou , Chaozhihui Cheng , Jiang Bai , Haixin Ding , Xian‐Rong Song , Mu‐Jia Luo , Qiang Xiao","doi":"10.1002/adsc.202401276","DOIUrl":"10.1002/adsc.202401276","url":null,"abstract":"<div><div>Herein, an electroreductive aryl radical enabled 5‐<em>exo</em>‐<em>dig</em> cyclization of <em>N</em>‐cyano‐2‐halobenzamides is presented, providing a convenient route for the synthesis of a variety of 3‐iminoisoindolin‐1‐ones in 30–75% yields. Simply by employing zinc plate instead of graphite rod anode, the products of the electrosynthesis are switched to diverse 3‐aminoisoindolin‐1‐ones through aryl‐radical‐mediated 5‐<em>exo</em>‐<em>dig</em> cyclization and subsequent reductive hydrogenation. Furthermore, this anode material determined divergent 5‐<em>exo</em>‐<em>dig</em> cyclization features mild electrochemical conditions, excellent substrate scopes, and good functional group tolerance.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"367 3","pages":"Article e202401276"},"PeriodicalIF":4.4,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142589016","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}
Jordan Diaz , Yongsheng Zhang , James Theodore Merrett , Wai Tsun Or , Philip Wai Hong Chan
A synthetic method to prepare δ–κ‐chloroketones, ‐esters and ‐amides that relies on the copper(I)‐mediated chlorination at the unactivated tertiary δ–κ‐C(sp3)−H bond of ketones, carboxylic esters, and amides by dichloramine‐T is presented. By exploiting the ability of the N‐chloramide to act as both the hydrogen atom transfer (HAT) and chlorination reagent, the reactions were shown to be site‐selective with halogenation only occurring at the unactivated tertiary carbon center situated four to ten C−C bond distances away from the carbonyl functional group in the substrate. The site‐selectivity of the chlorination protocol was further exemplified by the installing of the C−Cl bond at the distal position of one example containing two tertiary carbon centers and the late‐stage functionalization of two drug molecules.
{"title":"Copper(I)‐Mediated Site‐Selective Tertiary δ–κ‐C(sp3)−H Bond Chlorination of Ketones and Carboxylic Esters and Amides by Dichloramine‐T","authors":"Jordan Diaz , Yongsheng Zhang , James Theodore Merrett , Wai Tsun Or , Philip Wai Hong Chan","doi":"10.1002/adsc.202401324","DOIUrl":"10.1002/adsc.202401324","url":null,"abstract":"<div><div>A synthetic method to prepare <em>δ</em>–<em>κ</em>‐chloroketones, ‐esters and ‐amides that relies on the copper(I)‐mediated chlorination at the unactivated tertiary <em>δ</em>–<em>κ</em>‐C(<em>sp</em><sup>3</sup>)−H bond of ketones, carboxylic esters, and amides by dichloramine‐T is presented. By exploiting the ability of the <em>N</em>‐chloramide to act as both the hydrogen atom transfer (HAT) and chlorination reagent, the reactions were shown to be site‐selective with halogenation only occurring at the unactivated tertiary carbon center situated four to ten C−C bond distances away from the carbonyl functional group in the substrate. The site‐selectivity of the chlorination protocol was further exemplified by the installing of the C−Cl bond at the distal position of one example containing two tertiary carbon centers and the late‐stage functionalization of two drug molecules.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"367 3","pages":"Article e202401324"},"PeriodicalIF":4.4,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142776927","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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