Rhodium-Catalyzed Enantioselective Intramolecular Hydroacylation of Trisubstituted Alkenes

We report the first examples of transition metal‐catalyzed enantioselective alkene hydroacylations with 1,1,2‐trisubstituted alkenes. DFT and mechanistic studies are consistent with a reaction pathway for these rhodium‐catalyzed processes including intramolecular alkene hydroacylation and α‐epimeriz...

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Bibliographic Details
Published in:Chemistry : a European journal 2016-10, Vol.22 (44), p.15619-15623
Main Authors: Johnson, Kirsten F., Schneider, Eugene A., Schumacher, Brian P., Ellern, Arkady, Scanlon, Joseph D., Stanley, Levi M.
Format: Article
Language:English
Subjects:
Alkenes
Architecture
asymmetric catalysis
Catalysis
Chemistry
hydroacylation
Ketones
Pathways
Rhodium
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Summary:We report the first examples of transition metal‐catalyzed enantioselective alkene hydroacylations with 1,1,2‐trisubstituted alkenes. DFT and mechanistic studies are consistent with a reaction pathway for these rhodium‐catalyzed processes including intramolecular alkene hydroacylation and α‐epimerization to generate highly enantioenriched, polycyclic architectures. This reaction sequence enables the hydroacylation of 2‐(cyclohex‐1‐en‐1‐yl)benzaldehydes to form hexahydro‐9H‐fluoren‐9‐ones in moderate to high yields (68–91 %) with high enantioselectivities (up to 99 % ee) and diastereoselectivities (typically >20:1). The first “tri”: The first examples of transition metal‐catalyzed, enantioselective hydroacylations of trisubstituted alkenes are reported. DFT studies are consistent with a sequence of intramolecular alkene hydroacylation and α‐epimerization to generate the polycylic ketone products with moderate‐to‐high yields and high enantioselectivities (up to 99 % ee).
ISSN:0947-6539
1521-3765
DOI:10.1002/chem.201603880