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Scalable anti-Markovnikov hydrobromination of aliphatic and aromatic olefins

Scalable anti-Markovnikov hydrobromination of aliphatic and aromatic olefins
Scalable anti-Markovnikov hydrobromination of aliphatic and aromatic olefins
To improve access to a key synthetic intermediate we targeted a direct hydrobromination-Negishi route. Unsurprisingly, the anti-Markovnikov addition of HBr to estragole in the presence of AIBN proved successful. However, even in the absence of an added initiator, anti-Markovnikov addition was observed. Re-examination of early reports revealed that selective Markovnikov addition, often simply termed “normal” addition, is not always observed with HBr unless air is excluded, leading to the rediscovery of a reproducible and scalable initiator-free protocol.
1477-0520
5622-5626
Galli, Marzia
5bfc8a21-05e5-4f29-a573-4fa4d7938f7f
Fletcher, Catherine J.
854780b7-7315-4d29-a91e-d7f422368705
del Pozo, Marc
310b74de-62eb-4e2c-a3c3-cb39ee98c69d
Goldup, Stephen M.
27165d3a-d39f-4259-a83c-ac5fdd38ad57
Galli, Marzia
5bfc8a21-05e5-4f29-a573-4fa4d7938f7f
Fletcher, Catherine J.
854780b7-7315-4d29-a91e-d7f422368705
del Pozo, Marc
310b74de-62eb-4e2c-a3c3-cb39ee98c69d
Goldup, Stephen M.
27165d3a-d39f-4259-a83c-ac5fdd38ad57

Galli, Marzia, Fletcher, Catherine J., del Pozo, Marc and Goldup, Stephen M. (2016) Scalable anti-Markovnikov hydrobromination of aliphatic and aromatic olefins. Organic & Biomolecular Chemistry, 14 (24), 5622-5626. (doi:10.1039/C6OB00692B).

Record type: Article

Abstract

To improve access to a key synthetic intermediate we targeted a direct hydrobromination-Negishi route. Unsurprisingly, the anti-Markovnikov addition of HBr to estragole in the presence of AIBN proved successful. However, even in the absence of an added initiator, anti-Markovnikov addition was observed. Re-examination of early reports revealed that selective Markovnikov addition, often simply termed “normal” addition, is not always observed with HBr unless air is excluded, leading to the rediscovery of a reproducible and scalable initiator-free protocol.

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More information

Accepted/In Press date: 6 May 2016
e-pub ahead of print date: 9 May 2016
Published date: 28 June 2016
Organisations: Organic Chemistry: SCF

Identifiers

Local EPrints ID: 397241
URI: http://eprints.soton.ac.uk/id/eprint/397241
ISSN: 1477-0520
PURE UUID: 891643f0-45e9-4c6b-ad79-9739e6bcf092

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Date deposited: 24 Jun 2016 15:16
Last modified: 15 Mar 2024 05:41

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Contributors

Author: Marzia Galli
Author: Catherine J. Fletcher
Author: Marc del Pozo
Author: Stephen M. Goldup

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