Methyl Radical Initiated Kharasch and Related Reactions

Tappin, Nicholas D. C.; Renaud, Philippe (2021). Methyl Radical Initiated Kharasch and Related Reactions. Advanced synthesis & catalysis, 363(1), pp. 275-282. Wiley-VCH 10.1002/adsc.202001000

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An improved procedure to run halogen atom and related chalcogen group transfer radical additions is reported. The procedure relies on the thermal decomposition of di-tert-butylhyponitrite (DTBHN), a safer alternative to the explosive diacetyl peroxide, to produce highly reactive methyl radicals that can initiate the chain process. This mode of initiation generates byproducts that are either gaseous (N2) or volatile (acetone and methyl halide) thereby facilitating greatly product purification by either flash column chromatography or distillation. In addition, remarkably simple and mild reaction conditions (refluxing EtOAc during 30 minutes under normal atmosphere) and a low excess of the radical precursor reagent (2 equivalents) make this protocol particularly attractive for preparative synthetic applications. This initiation procedure has been demonstrated with a broad scope since it works efficiently to add a range of electrophilic radicals generated from iodides, bromides, selenides and xanthates over a range of unactivated terminal alkenes. A diverse set of radical trap substrates exemplifies a broad functional group tolerance. Finally, di-tert-butyl peroxyoxalate (DTBPO) is also demonstrated as alternative source of tert-butoxyl radicals to initiate these reactions under identical conditions which gives gaseous by-products (CO2).

Item Type:

Journal Article (Original Article)

Division/Institute:

08 Faculty of Science > Department of Chemistry, Biochemistry and Pharmaceutical Sciences (DCBP)

UniBE Contributor:

Tappin, Nicholas David Charles and Renaud, Philippe

Subjects:

500 Science > 570 Life sciences; biology
500 Science > 540 Chemistry

ISSN:

1615-4150

Publisher:

Wiley-VCH

Language:

English

Submitter:

Franziska Bornhauser-Rufer

Date Deposited:

24 Jun 2021 11:55

Last Modified:

25 Jun 2021 15:41

Publisher DOI:

10.1002/adsc.202001000

BORIS DOI:

10.48350/157102

URI:

https://boris.unibe.ch/id/eprint/157102

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