Cameron H. M. Zheng, Ben E. Nadeau, Heather L. Trajano and Laurel L. Schafer
{"title":"Exploiting natural complexity for substrate controlled regioselectivity and stereoselectivity in tantalum catalysed hydroaminoalkylation†","authors":"Cameron H. M. Zheng, Ben E. Nadeau, Heather L. Trajano and Laurel L. Schafer","doi":"10.1039/D4GC01614A","DOIUrl":null,"url":null,"abstract":"<p >Naturally occurring and structurally diverse alkene-containing substrates, terpenes, provided a platform for establishing chemo-, regio-, and diastereoselective reactivity in tantalum catalysed hydroaminoalkylation. Naturally derived 1,3-butadienes revealed the unique regio- and diastereoselective (<em>Z</em>)-1,4-addition products accessible from isoprene and β-myrcene by hydroaminoalkylation. Selective terpene functionalisation, within an industrially produced turpentine mixture, demonstrates functionalisation specificity of β-pinene and limonene. Lastly, sesquiterpene functionalisation using β-caryophyllene and humulene provide rare examples of trisubstituted alkene reactivity in hydroaminoalkylation, by leveraging strain-release and stereoelectronic effects to control chemoselectivity. As a result of these reactivity studies using natural substrates, new tools for understanding alkene electronic, strain, and stereoelectronic effects on chemo- and diastereoselectivity outcomes have revealed new mechanistic insights into hydroaminoalkylation.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":null,"pages":null},"PeriodicalIF":9.3000,"publicationDate":"2024-08-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Green Chemistry","FirstCategoryId":"92","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2024/gc/d4gc01614a","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
Naturally occurring and structurally diverse alkene-containing substrates, terpenes, provided a platform for establishing chemo-, regio-, and diastereoselective reactivity in tantalum catalysed hydroaminoalkylation. Naturally derived 1,3-butadienes revealed the unique regio- and diastereoselective (Z)-1,4-addition products accessible from isoprene and β-myrcene by hydroaminoalkylation. Selective terpene functionalisation, within an industrially produced turpentine mixture, demonstrates functionalisation specificity of β-pinene and limonene. Lastly, sesquiterpene functionalisation using β-caryophyllene and humulene provide rare examples of trisubstituted alkene reactivity in hydroaminoalkylation, by leveraging strain-release and stereoelectronic effects to control chemoselectivity. As a result of these reactivity studies using natural substrates, new tools for understanding alkene electronic, strain, and stereoelectronic effects on chemo- and diastereoselectivity outcomes have revealed new mechanistic insights into hydroaminoalkylation.
期刊介绍:
Green Chemistry is a journal that provides a unique forum for the publication of innovative research on the development of alternative green and sustainable technologies. The scope of Green Chemistry is based on the definition proposed by Anastas and Warner (Green Chemistry: Theory and Practice, P T Anastas and J C Warner, Oxford University Press, Oxford, 1998), which defines green chemistry as the utilisation of a set of principles that reduces or eliminates the use or generation of hazardous substances in the design, manufacture and application of chemical products. Green Chemistry aims to reduce the environmental impact of the chemical enterprise by developing a technology base that is inherently non-toxic to living things and the environment. The journal welcomes submissions on all aspects of research relating to this endeavor and publishes original and significant cutting-edge research that is likely to be of wide general appeal. For a work to be published, it must present a significant advance in green chemistry, including a comparison with existing methods and a demonstration of advantages over those methods.