{"title":"mCPBA选择性B(9)-H键氧化o/m-碳硼烷。","authors":"Yi-Ge Li,Yan-Na Ma","doi":"10.1021/acs.inorgchem.5c03028","DOIUrl":null,"url":null,"abstract":"Herein, we have developed an efficient and mild synthetic protocol for the preparation of B(9)-OH-o/m-carboranes by the directly oxidation of o/m-carboranes with mCPBA in hexafluoroisopropanol (HFIP), using trifluoromethanesulfonic acid (HOTf) as a promoter. In comparison to our previously reported method using HNO3 as the oxidant, the present method demonstrates enhanced mildness, enabling the direct hydroxylation of 1,2-diaryl-o-carboranes and, for the first time, the synthesis of B(8)-hydroxylated o-carborane derivatives. The esterification of 9-OH-o-carborane was further investigated, enabling the successful incorporation of the carboranyl moiety into drug molecules. It provides a material basis for the research of carborane derivatives in coordination chemistry, materials chemistry, and medicine, especially in the field of boron neutron capture therapy (BNCT).","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"125 1","pages":""},"PeriodicalIF":4.7000,"publicationDate":"2025-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Selective B(9)-H Bond Oxidation of o/m-Carboranes with mCPBA.\",\"authors\":\"Yi-Ge Li,Yan-Na Ma\",\"doi\":\"10.1021/acs.inorgchem.5c03028\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Herein, we have developed an efficient and mild synthetic protocol for the preparation of B(9)-OH-o/m-carboranes by the directly oxidation of o/m-carboranes with mCPBA in hexafluoroisopropanol (HFIP), using trifluoromethanesulfonic acid (HOTf) as a promoter. In comparison to our previously reported method using HNO3 as the oxidant, the present method demonstrates enhanced mildness, enabling the direct hydroxylation of 1,2-diaryl-o-carboranes and, for the first time, the synthesis of B(8)-hydroxylated o-carborane derivatives. The esterification of 9-OH-o-carborane was further investigated, enabling the successful incorporation of the carboranyl moiety into drug molecules. It provides a material basis for the research of carborane derivatives in coordination chemistry, materials chemistry, and medicine, especially in the field of boron neutron capture therapy (BNCT).\",\"PeriodicalId\":40,\"journal\":{\"name\":\"Inorganic Chemistry\",\"volume\":\"125 1\",\"pages\":\"\"},\"PeriodicalIF\":4.7000,\"publicationDate\":\"2025-10-10\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Inorganic Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1021/acs.inorgchem.5c03028\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, INORGANIC & NUCLEAR\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Inorganic Chemistry","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/acs.inorgchem.5c03028","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
Selective B(9)-H Bond Oxidation of o/m-Carboranes with mCPBA.
Herein, we have developed an efficient and mild synthetic protocol for the preparation of B(9)-OH-o/m-carboranes by the directly oxidation of o/m-carboranes with mCPBA in hexafluoroisopropanol (HFIP), using trifluoromethanesulfonic acid (HOTf) as a promoter. In comparison to our previously reported method using HNO3 as the oxidant, the present method demonstrates enhanced mildness, enabling the direct hydroxylation of 1,2-diaryl-o-carboranes and, for the first time, the synthesis of B(8)-hydroxylated o-carborane derivatives. The esterification of 9-OH-o-carborane was further investigated, enabling the successful incorporation of the carboranyl moiety into drug molecules. It provides a material basis for the research of carborane derivatives in coordination chemistry, materials chemistry, and medicine, especially in the field of boron neutron capture therapy (BNCT).
期刊介绍:
Inorganic Chemistry publishes fundamental studies in all phases of inorganic chemistry. Coverage includes experimental and theoretical reports on quantitative studies of structure and thermodynamics, kinetics, mechanisms of inorganic reactions, bioinorganic chemistry, and relevant aspects of organometallic chemistry, solid-state phenomena, and chemical bonding theory. Emphasis is placed on the synthesis, structure, thermodynamics, reactivity, spectroscopy, and bonding properties of significant new and known compounds.