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selectivities. Aromatic cyano, chloro, and bromo func-
tionalities have proved to be tolerated by the transition
metal-free catalyst. The critical importance of sodium vs.
other s-, p-, d-, and f-block metals as well as metal-free
systems has been demonstrated. Two novel catalytically
active sodium-based intermediates were detected, which
sheds light on the reaction mechanism. This methodol-
ogy is a rare example for the catalytic use of a sodium
amide in C–C bond formation,19 and should impact the
fields of organic synthesis, main group metal chemistry,
and earth-abundant18 metal catalysis.
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ASSOCIATED CONTENT
Experimental details and characterization data.
AUTHOR INFORMATION
Corresponding Author
*uwe.schneider@ed.ac.uk
Notes
+ These authors contributed equally to this work.
The authors declare no competing financial interest.
ACKNOWLEDGEMENTS
Eli Lilly, the School of Chemistry, the University of Edin-
burgh, the Royal Society, and the EU (PCIG10–GA–2011–
304218) are greatly acknowledged for financial support.
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(23) The direct conversion 1a → 4 failed when other Na bases (NaNH2,
NaH, NaBu) were used under various conditions.
(24) The direct conversion 3aa → 5 failed (Scheme 4–i).
(25) In contrast, when the Li analogue of 4 was used (10 mol%), prod-
(7) Formally electrophilic allyl–M species: Cu(I): (a) Andras, M. B.;
Zhou, Z. J. Am. Chem. Soc. 2002, 124, 8806. (b) Zhou, Z.; Andras, M. B.
uct 3aa was obtained in only 12% yield (E:Z = >99:1; see SI).
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