Propargyl Radicals in Organic Synthesis. Issue 22 (15th June 2021)

• Record Type: Journal Article
• Authors: Muresan, Marcus; Subramanian, Hariharaputhiran; Sibi, Mukund P.; Green, James R.
• Is Part Of: European journal of organic chemistry. Issue 22(2021)
• Page Start: 3359
• Page End: 3375
• Publication Date: 2021-06-15
• Subjects: Alkyne -- Allene -- Propargyl -- Radicals -- Synthetic methods; Chemistry, Organic -- Periodicals; Organic compounds -- Synthesis -- Periodicals; Bioorganic chemistry -- Periodicals; Chemistry, Physical organic -- Periodicals; 547
• DOI: 10.1002/ejoc.202100367
• Languages: English
• ISSNs: 1434-193X

Abstract

Abstract: The appearance of propargyl radicals as synthetic intermediates has increased in recent years from a structural curiosity to a frequent occurrence. This minireview covers the synthetically relevant organic chemistry involving the intermediacy of propargyl radicals. The review is organized by the process employed in radical generation, including H‐atom abstraction, propargyl‐X homolyses, radical addition to enynes, reduction of polar C=X bonds, reductions of stable carbocations, and metal‐mediated coupling reactions. The relevant mechanisms of generation and reaction are discussed, as are applications in syntheses of target molecules of interest. Abstract : The chemistry of propargyl radicals is reviewed. The review is divided into sections on their fundamental principles, and their generation and fate in allenyl/propargyl‐H abstractions, propargyl‐X homolyses, radical additions to enynes, pinacol/McMurry couplings, reductions of stable carbocations, and metal mediated propargylation reactions. Mechanism of the critical transformations and the use in total synthesis are also discussed.