Organic Letters
Letter
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product 3a with water as the only byproduct. In contrast, the
oxygen atom of the solvent (1,4-dioxane or DMSO) fully
coordinates to calcium and might result in catalyst
deactivation. In addition, the carbocation process, especially
for the 1,3-diaryl alcohols, can not be completely ruled out. For
instance, the regioselectivity is poor and four isomers (α,γ-
selectivity and syn/anti isomers) can be detected by H NMR
when (E)-3-(4-fluorophenyl)-1-phenylprop-2-en-1-ol was se-
lected as the substrate.
In summary, we have developed a dehydrative cross-
coupling transition-metal- and halogen-free allylic alkylation
protocol. The developed calcium catalytic system can directly
and reliably incorporate allylic alcohols at room temperature,
thus enabling this reaction to proceed in an environmentally
benign manner while producing only water as a byproduct.
The all-carbon quaternary centers with different allylic
substituents can be isolated in good to excellent yields, and a
wide-spectrum of functional groups is tolerated. This
investigation also sheds light on alkaline-earth metal catalysis
with respect to the dehydrative cross-coupling process,
although at this stage, only the MBH alcohols and some
activated versions can be used.
1
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ASSOCIATED CONTENT
* Supporting Information
■
S
The Supporting Information is available free of charge at
Experimental procedures, screening reaction conditions,
analytical data for all new compounds, and NMR spectra
́
(7) (a) Xia, Z.; Corce, V.; Zhao, F.; Przybylski, C.; Espagne, A.;
AUTHOR INFORMATION
Corresponding Authors
■
̀
Jullien, L.; Le Saux, T.; Gimbert, Y.; Dossmann, H.; Mouries-Mansuy,
V.; Ollivier, C.; Fensterbank, L. Nat. Chem. 2019, 11, 797.
(b) Kothandaraman, P.; Rao, W.; Zhang, X.; Chan, P. W. H.
Tetrahedron 2009, 65, 1833.
(8) (a) Helmchen, G.; Dahnz, A.; Dubon, P.; Schelwies, M.;
̈
ORCID
Weihofen, R. Chem. Commun. 2007, 675. (b) Takeuchi, R.; Kashio,
M. J. Am. Chem. Soc. 1998, 120, 8647. (c) Yamashita, Y.;
Gopalarathnam, A.; Hartwig, J. F. J. Am. Chem. Soc. 2007, 129,
7508. (d) Roggen, M.; Carreira, E. M. J. Am. Chem. Soc. 2010, 132,
11917. (e) Lafrance, M.; Carreira, E. M. Angew. Chem., Int. Ed. 2012,
51, 3470. (f) Roggen, M.; Carreira, E. M. Angew. Chem., Int. Ed. 2011,
50, 5568. (g) Roggen, M.; Carreira, E. M. Angew. Chem., Int. Ed. 2012,
51, 8652. (h) Hamilton, J. Y.; Sarlah, D.; Carreira, E. M. J. Am. Chem.
Soc. 2013, 135, 994.
(9) Lee, D.-H.; Kwon, K.-H.; Yi, C. S. Science 2011, 333, 1613.
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Int. Ed. 2016, 55, 1098. (b) Bernhard, Y.; Thomson, B.; Ferey, V.;
Sauthier, M. Angew. Chem., Int. Ed. 2017, 56, 7460.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We gratefully acknowledge the financial support from the
National Natural Science Foundation of China (21702108),
the Natural Science Foundation of Jiangsu Province, China
(BK20160977), the Six Talent Peaks Project in Jiangsu
Province (YY-033), the grant from Ministry of Education of
Singapore MOE2016-T1-002-043 (RG111/16), and Nanjing
Tech University (39837101).
(11) (a) Shibuya, R.; Lin, L.; Nakahara, Y.; Mashima, K.; Ohshima,
T. Angew. Chem., Int. Ed. 2014, 53, 4377. (b) Das, K.; Shibuya, R.;
Nakahara, Y.; Germain, N.; Ohshima, T.; Mashima, K. Angew. Chem.,
Int. Ed. 2012, 51, 150. (c) Mora, G.; Piechaczyk, O.; Houdard, R.;
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