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Synfacts 2012; 8(5): 0513
DOI: 10.1055/s-0031-1290909
Metal-Catalyzed Asymmetric Synthesis and Stereoselective Reactions
© Georg Thieme Verlag Stuttgart · New York

Nickel-Catalyzed Enantioselective Synthesis of Benzobicyclo[2.2.2]octenes

Contributor(s):
Mark Lautens
,
Lei Zhang
Liu L, Ishida N, Murakami M * Kyoto University, Japan
Atom- and Step-Economical Pathway to Chiral Benzobicyclo[2.2.2]octenones through Carbon–Carbon Bond Cleavage.

Angew. Chem. Int. Ed. 2012;
51: 2485-2488
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Publication History

Publication Date:
18 April 2012 (online)

 
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Key words

phosphoramidite ligands - benzobicyclo[2.2.2]octenes - nickel

Significance

The first catalytic asymmetric strategy toward the synthesis of benzobicyclo[2.2.2]octenes from achiral substrates is reported. Derivatives of these products are known to exhibit ­biological activities. Alternatively, the benzobi­cyclo[2.2.2]octene 1 could undergo Bayer–Villiger oxidation and saponification to afford cis-substituted hydroxycarboxylic acid 2.


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Comment

Following the authors’ initial report on the achiral variant of this reaction (Chem. Commun. 2006, 4599), the notable switch of Cy3P to a chiral phosphoramidite ligand L in this report conferred high enantioselectivities. The proposed catalytic cycle involves an enantiodiscriminating oxidative cyclization step followed by β-carbon elimination.


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