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Synfacts 2015; 11(8): 0831
DOI: 10.1055/s-0034-1381148
Metal-Catalyzed Asymmetric Synthesis and Stereoselective Reactions
© Georg Thieme Verlag Stuttgart · New York

Construction of Quaternary Carbon Stereogenic Centers

Contributor(s):
Hisashi Yamamoto
,
Fengtao Zhou
Turnbull BW. H, Evans PA * Queen’s University, Kingston, Canada
Enantioselective Rhodium-Catalyzed Allylic Substitution with a Nitrile Anion: Construction of Acyclic Quaternary Carbon Stereogenic Centers.

J. Am. Chem. Soc. 2015;
137: 6156-6159
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Further Information

Publication History

Publication Date:
20 July 2015 (online)

 
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Key words

rhodium - catalysis - allylic substitution - nitrile anion - quaternary carbon - stereogenic centers

Significance

The enantioselective construction of quaternary carbon stereogenic centers in acyclic systems remains one of the great challenges. A highly enantioselective rhodium-catalyzed allylic alkylation of allyl benzoate by α-substituted benzyl nitrile anions provides access to acyclic quaternary carbon stereogenic centers in good yields with excellent enantioselectivities.


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Comment

Interestingly, 15-crown-5 was used as additive to provide a significant improvement in the enantioselectivity. The protocol provides a new approach for the construction of acyclic quaternary carbon stereogenic centers. Furthermore, the nitrile products can be easily transformed into a number of important derivatives.


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