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Highly Regioselective Addition of Allylic Zinc Halides and Various Zinc Enolates to [1.1.1]Propellane.

ABSTRACT: We report a range of highly regioselective openings of [1.1.1]propellane with various allylic zinc halides, as well as zinc enolates of ketones, esters and nitriles. The resulting zincated bicyclopentanes (BCPs) were trapped with a range of electrophiles including acyl chlorides, sulfonothioates, hydroxylamino benzoates, tosyl cyanide as well as aryl and allyl halides, generating highly functionalized BCP-derivatives. The unusually high regioselectivity of these reactions has been rationalized using DFT calculations. A bioisostere of the synthetic opioid pethidine was prepared in 95?% yield in one step using this method.

SUBMITTER: Schwarzer K

PROVIDER: S-EPMC7693202 | biostudies-literature | 2020 Nov

REPOSITORIES: biostudies-literature

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Highly Regioselective Addition of Allylic Zinc Halides and Various Zinc Enolates to [1.1.1]Propellane.

Schwärzer Kuno K Zipse Hendrik H Karaghiosoff Konstantin K Knochel Paul P

Angewandte Chemie (International ed. in English) 20200831 45

We report a range of highly regioselective openings of [1.1.1]propellane with various allylic zinc halides, as well as zinc enolates of ketones, esters and nitriles. The resulting zincated bicyclopentanes (BCPs) were trapped with a range of electrophiles including acyl chlorides, sulfonothioates, hydroxylamino benzoates, tosyl cyanide as well as aryl and allyl halides, generating highly functionalized BCP-derivatives. The unusually high regioselectivity of these reactions has been rationalized u ...[more]

PMID: 32744419

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