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. 2010 Nov 2;49(45):8370-4.
doi: 10.1002/anie.201005124.

Quaternary carbon stereogenic centers through copper-catalyzed enantioselective allylic substitutions with readily accessible aryl- or heteroaryllithium reagents and aluminum chlorides

Fang Gao  1 , Yunmi Lee, Kyoko Mandai, Amir H Hoveyda
Affiliations

Quaternary carbon stereogenic centers through copper-catalyzed enantioselective allylic substitutions with readily accessible aryl- or heteroaryllithium reagents and aluminum chlorides

Fang Gao et al. Angew Chem Int Ed Engl. .
No abstract available

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Figures

Scheme 1
Scheme 1
Practical, site- and enantioselective synthesis of versatile small molecules with an allylic all-carbon quaternary stereogenic center by Cu-catalyzed allylic substitutions through the use of mono-aryl- or mono-hetero-arylmetal reagents; LG = leaving group.
Scheme 2
Scheme 2
Synthesis and in situ utilization of (2-furyl)AlEt2 in a highly group-, site- and enantioselective NHC–Cu-catalyzed enantioselective allylic substitution reaction, affording an all-carbon quaternary stereogenic center.
Scheme 3
Scheme 3
NHC–Cu-catalyzed enantioselective additions of aryl and hetero-aryl moieties to substrates that bear two alkyl substituents. All reactions performed under the conditions shown for EAS reaction leading to sporochnol, except for 15–16. [a] With 1.0 mol % NHC–AgI 2a and 2.0 mol % CuCl2•2H2O. [b] With 1.0 mol % NHC–AgI 2a and 2.0 mol % CuCl2•2H2O, −50 °C, 3 h.
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References

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    1. For Cu-free allylic alkylations with alkylmagnesium halides, affording all-carbon quaternary stereogenic centers, see: Lee Y, Hoveyda AH. J Am Chem Soc. 2006;128:15604–15605.For a closely related study with derivatives of bidentate NHC complexes originally designed in these laboratories, see: Jackowski O, Alexakis A. Angew Chem Int Ed. 2010;49:3346–3350.

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