Catalytic, stereospecific syn-dichlorination of alkenes

Alexander J. Cresswell, Stanley T- C. Eey, Scott E. Denmark

Research output: Contribution to journalArticle

105 Citations (Scopus)

Abstract

As some of the oldest organic chemical reactions known, the ionic additions of elemental halogens such as bromine and chlorine to alkenes are prototypical examples of stereospecific reactions, typically delivering vicinal dihalides resulting from anti-addition. Although the invention of enantioselective variants is an ongoing challenge, the ability to overturn the intrinsic anti-diastereospecificity of these transformations is also a largely unsolved problem. Here, we describe the first catalytic, syn-stereospecific dichlorination of alkenes, employing a group transfer catalyst based on a redox-active main group element (selenium). With diphenyl diselenide (PhSeSePh) (5amol%) as the pre-catalyst, benzyltriethylammonium chloride (BnEt 3 NCl) as the chloride source and an N-fluoropyridinium salt as the oxidant, a wide variety of functionalized cyclic and acyclic 1,2-disubstituted alkenes, including simple allylic alcohols, deliver syn-dichlorides with exquisite stereocontrol. This methodology is expected to find applications in streamlining the synthesis of polychlorinated natural products such as the chlorosulfolipids.

Original languageEnglish
Pages (from-to)146-152
Number of pages7
JournalNature Chemistry
Volume7
Issue number2
Early online date12 Jan 2015
DOIs
Publication statusPublished - 1 Feb 2015

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