Organic Letters
Letter
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indicated that the first transmetalation of allenyl boronate with
zinc amide occurred to form propargylzinc species under
kinetic conditions, to afford the allenylation products, and that
the propargylzinc species isomerized to form allenylzinc species
under thermodynamic conditions to afford the propargylation
products. High reactivity of the zinc amide species is key for the
smooth transmetalation and isomerization. Further investiga-
tions into developing asymmetric allenylation and propargyla-
tion reactions of ketones are currently in progress.
ASSOCIATED CONTENT
* Supporting Information
■
S
The Supporting Information is available free of charge on the
Supporting studies, general experimental procedures,
analytical data of the products, DFT calculations, and
AUTHOR INFORMATION
Corresponding Author
■
Notes
The authors declare no competing financial interest.
(9) For selected examples, see: (a) Schneider, U.; Sugiura, M.;
Kobayashi, S. Tetrahedron 2006, 62, 496−502. (b) Kobayashi, S.;
Nishio, K. J. Am. Chem. Soc. 1995, 117, 6392−6393. (c) Wang, K. K.;
Liu, C. J. Org. Chem. 1985, 50, 2578−2580. (d) Wang, K. K.; Nikam, S.
S.; Ho, C. D. J. Org. Chem. 1983, 48, 5376−5377.
ACKNOWLEDGMENTS
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This work was partially supported by a Grant-in-Aid for
Scientific Research from the Japan Society for the Promotion of
Science (JSPS), the Japan Science and Technology Agency
(JST), and the Ministry of Education, Culture, Sports, Science
and Technology (MEXT).
(10) For selected examples of stoichiometric asymmetric allenyla-
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