Enantioselective Rhodium‐Catalyzed Dimerization of ω‐Allenyl Carboxylic Acids: Straightforward Synthesis of C2‐Symmetric Macrodiolides

Herein, we report on the first enantioselective and atom‐efficient catalytic one‐step dimerization method to selectively transform ω‐allenyl carboxylic acids into C2‐symmetric 14‐ to 28‐membered bismacrolactones (macrodiolides). This convenient asymmetric access serves as an attractive route towards...

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Bibliographic Details
Published in:Angewandte Chemie 2018-05, Vol.130 (22), p.6682-6686
Main Authors: Steib, Philip, Breit, Bernhard
Format: Article
Language:English
Subjects:
Allene
Asymmetrische Katalyse
Carboxylic acids
Catalysis
Chemical synthesis
Chemistry
Dimerization
Diolide
Enantiomers
Makrolactone
Rhodium
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Summary:Herein, we report on the first enantioselective and atom‐efficient catalytic one‐step dimerization method to selectively transform ω‐allenyl carboxylic acids into C2‐symmetric 14‐ to 28‐membered bismacrolactones (macrodiolides). This convenient asymmetric access serves as an attractive route towards multiple naturally occuring homodimeric macrocyclic scaffolds and demonstrates excellent efficiency to construct the complex, symmetric core structures. By utilizing a rhodium catalyst with a modified chiral cyclopentylidene‐diop ligand, the desired diolides were obtained in good to high yields, high diastereoselectivity, and excellent enantioselectivity. Nimm zwei: Eine einstufige, hoch atomeffiziente rhodiumkatalysierte Dimerisierung von ω‐Allenylcarbonsäuren liefert C2‐symmetrische Homodiolide, ein in zahlreichen Naturstoffen vorhandenes Strukturmotiv. Bei diesem Prozess werden zwei Stereozentren hoch enantioselektiv eingeführt.
ISSN:0044-8249
1521-3757
DOI:10.1002/ange.201803369