Stereodefined Skipped Dienes through Iridium‐Catalyzed Formal Addition of Tertiary Allylic C−H Bonds to Alkynes

Preparation of skipped dienes with a quaternary carbon center at the C‐3 position remains a synthetic challenge. We report here an iridium‐catalyzed formal addition of tertiary sp3 C−H bond to alkyne for the facile preparation of skipped dienes. The tertiary allylic C−H bond is cleaved regioselectiv...

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Bibliographic Details
Published in:Angewandte Chemie 2022-06, Vol.134 (26), p.n/a
Main Authors: Wang, Zi‐Xuan, Gao, Peng‐Chao, Lin, En‐Ze, Li, Bi‐Jie
Format: Article
Language:English
Subjects:
Alkene Isomerization
Alkynes
Allylic C−H Bond
Carbon
Chemistry
C−H Cleavage
Dienes
Enantiomers
Hydrogen bonds
Iridium
Quaternary Carbon
Skipped Diene
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Summary:Preparation of skipped dienes with a quaternary carbon center at the C‐3 position remains a synthetic challenge. We report here an iridium‐catalyzed formal addition of tertiary sp3 C−H bond to alkyne for the facile preparation of skipped dienes. The tertiary allylic C−H bond is cleaved regioselectively, at the site of which a new C−C bond is formed. Enantioselective construction of acyclic quaternary carbon stereocenters is also demonstrated. An iridium‐catalyzed formal addition of allylic C−H bond to alkyne is reported. A tertiary C−H bond was cleaved at the site of which a quaternary carbon center was formed. This atom‐economical process provided a straightforward synthetic route to skipped dienes containing a C3‐quaternary carbon. Enantioselective construction of acyclic quaternary carbon stereocenters through enantio‐convergent vinylation of tertiary C−H bond was also feasible.
ISSN:0044-8249
1521-3757
DOI:10.1002/ange.202200075