{"title":"简单的1,3-二烯直接催化合成功能化二烯:金属催化剂取代1,3-丁二烯、异戊二烯和2,3-二甲基-1,3-丁二烯的研究进展","authors":"Yukio Hamamoto, Yasushi Obora","doi":"10.1016/j.apcata.2025.120572","DOIUrl":null,"url":null,"abstract":"<div><div>Conjugated diene structures are important as feedstocks for many organic reactions. Therefore, development of efficient syntheses of conjugated diene compounds is desirable. This review introduces selective functionalizing reactions to 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene with various metal catalysts, ligands, and types of reactions. To overcome difficulties of controlling reactions, Heck reactions with Pd or Ni catalysts and metathesis cross couplings with Grubbs catalysts are mainly used. Focused on ligands, phosphines, 1,5-cyclooctadiene, imidazoline derivatives are frequently used. As a plausible mechanism, formation of π-allyl complexes is concerned as an initial step, especially when palladium is used. Then, as an intermediate, η<sup>2</sup>-π-allyl metal are formed. At last, reductive elimination undergoes and the desired compounds are obtained. Reaction mechanisms are concerned by labelling experiment or isolation of intermediates in most examples. In addition, in most reactions, results of substrate scope that not only 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene are used are depicted. Besides, several applications of functionalized dienes are introduced. As a result, synthesized dienes are converted into (hetero)cyclic compounds, polyenes, enyl ketones. Overall, diene is considered a useful starting material for addition reactions such as polymerization, telomerization, and annulation and functionalizing dienes is expected to facilitate the efficient synthesis of organic compounds with complex structures by upgrading simple 1,3-diene.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"708 ","pages":"Article 120572"},"PeriodicalIF":4.8000,"publicationDate":"2025-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Direct catalytic synthesis of functionalized dienes from simple 1,3-dienes: A review on substitution of 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene with metal catalysts\",\"authors\":\"Yukio Hamamoto, Yasushi Obora\",\"doi\":\"10.1016/j.apcata.2025.120572\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>Conjugated diene structures are important as feedstocks for many organic reactions. Therefore, development of efficient syntheses of conjugated diene compounds is desirable. This review introduces selective functionalizing reactions to 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene with various metal catalysts, ligands, and types of reactions. To overcome difficulties of controlling reactions, Heck reactions with Pd or Ni catalysts and metathesis cross couplings with Grubbs catalysts are mainly used. Focused on ligands, phosphines, 1,5-cyclooctadiene, imidazoline derivatives are frequently used. As a plausible mechanism, formation of π-allyl complexes is concerned as an initial step, especially when palladium is used. Then, as an intermediate, η<sup>2</sup>-π-allyl metal are formed. At last, reductive elimination undergoes and the desired compounds are obtained. Reaction mechanisms are concerned by labelling experiment or isolation of intermediates in most examples. In addition, in most reactions, results of substrate scope that not only 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene are used are depicted. Besides, several applications of functionalized dienes are introduced. As a result, synthesized dienes are converted into (hetero)cyclic compounds, polyenes, enyl ketones. Overall, diene is considered a useful starting material for addition reactions such as polymerization, telomerization, and annulation and functionalizing dienes is expected to facilitate the efficient synthesis of organic compounds with complex structures by upgrading simple 1,3-diene.</div></div>\",\"PeriodicalId\":243,\"journal\":{\"name\":\"Applied Catalysis A: General\",\"volume\":\"708 \",\"pages\":\"Article 120572\"},\"PeriodicalIF\":4.8000,\"publicationDate\":\"2025-09-15\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Applied Catalysis A: General\",\"FirstCategoryId\":\"1\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0926860X25004740\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Applied Catalysis A: General","FirstCategoryId":"1","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0926860X25004740","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Direct catalytic synthesis of functionalized dienes from simple 1,3-dienes: A review on substitution of 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene with metal catalysts
Conjugated diene structures are important as feedstocks for many organic reactions. Therefore, development of efficient syntheses of conjugated diene compounds is desirable. This review introduces selective functionalizing reactions to 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene with various metal catalysts, ligands, and types of reactions. To overcome difficulties of controlling reactions, Heck reactions with Pd or Ni catalysts and metathesis cross couplings with Grubbs catalysts are mainly used. Focused on ligands, phosphines, 1,5-cyclooctadiene, imidazoline derivatives are frequently used. As a plausible mechanism, formation of π-allyl complexes is concerned as an initial step, especially when palladium is used. Then, as an intermediate, η2-π-allyl metal are formed. At last, reductive elimination undergoes and the desired compounds are obtained. Reaction mechanisms are concerned by labelling experiment or isolation of intermediates in most examples. In addition, in most reactions, results of substrate scope that not only 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene are used are depicted. Besides, several applications of functionalized dienes are introduced. As a result, synthesized dienes are converted into (hetero)cyclic compounds, polyenes, enyl ketones. Overall, diene is considered a useful starting material for addition reactions such as polymerization, telomerization, and annulation and functionalizing dienes is expected to facilitate the efficient synthesis of organic compounds with complex structures by upgrading simple 1,3-diene.
期刊介绍:
Applied Catalysis A: General publishes original papers on all aspects of catalysis of basic and practical interest to chemical scientists in both industrial and academic fields, with an emphasis onnew understanding of catalysts and catalytic reactions, new catalytic materials, new techniques, and new processes, especially those that have potential practical implications.
Papers that report results of a thorough study or optimization of systems or processes that are well understood, widely studied, or minor variations of known ones are discouraged. Authors should include statements in a separate section "Justification for Publication" of how the manuscript fits the scope of the journal in the cover letter to the editors. Submissions without such justification will be rejected without review.