Cobalt‐Catalyzed Regiodivergent Ring‐Opening Dihydroboration of Arylidenecyclopropanes to Access Skipped Diboronates

Ligand‐controlled regiodivergent cobalt‐catalyzed ring‐opening dihydroboration of arylidenecyclopropanes is developed to access synthetically versatile skipped diboronates with catalysts generated in situ from Co(acac)2 and dpephos or xantphos. A variety of arylidenecyclopropanes reacted with pinaco...

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Bibliographic Details
Published in:Angewandte Chemie 2023-08, Vol.135 (32), p.n/a
Main Authors: Tan, Boon Beng, Hu, Ming, Ge, Shaozhong
Format: Article
Language:English
Subjects:
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Arylidenecyclopropane
Catalysts
Chemical reactions
Chemistry
Cobalt
Cobalt Catalysis
Functional groups
Hydroboration
Intermediates
Regiodivergence
Regioselectivity
Ring-Opening
Skipped Diboronate
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Summary:Ligand‐controlled regiodivergent cobalt‐catalyzed ring‐opening dihydroboration of arylidenecyclopropanes is developed to access synthetically versatile skipped diboronates with catalysts generated in situ from Co(acac)2 and dpephos or xantphos. A variety of arylidenecyclopropanes reacted with pinacolborane (HBpin) to form the corresponding 1,3‐ or 1,4‐diboronates in high isolated yields and with high regioselectivity. Skipped diboronate products from these reactions can undergo various transformations to allow selective installation of two different functional groups along alkyl chains. Mechanistic studies suggest that these reactions combine cobalt‐catalyzed ring‐opening hydroboration of arylidenecyclopropanes and hydroboration of homoallylic or allylic boronate intermediates. Regiodivergent cobalt‐catalyzed ring‐opening dihydroboration of arylidenecyclopropanes with pinacolborane is developed to access synthetically versatile 1,3‐ and 1,4‐diboronates. The catalysts are generated in situ from Co(acac)2/dpephos and Co(acac)2/xantphos, respectively. The ring‐opening of arylidenecyclopropanes to form single homoallylic cobalt intermediates via β‐C elimination is crucial for the obtained high regioselectivity.
ISSN:0044-8249
1521-3757
DOI:10.1002/ange.202307176