Organometallics
Communication
formation of [3]cumulenols without definition of the stereochemistry,
see ref 2d.
In conclusion, we have succeeded in developing zirconocene-
mediated coupling reactions of silyl- or tert-butyl-substituted
1,3-butadiynes with aldehydes under mild reaction conditions,
which provides an efficient and general route to cis-
[3]cumulenic diols with moderate to high stereoselectivity.
The silyl substituents at the butadiyne terminus show
remarkable influence on the stereoselectivity. This is the first
report on addition of two molecules of aldehyde to metal-
coordinated butadiyne complexes. Further studies to elucidate
the reaction mechanism and to extend the scope of synthetic
utility are in progress in our laboratory.
(5) For the coupling reactionof 1,4-bis(trimethylsilyl)buta-1,3-diyne
with Rosenthal’s reagent Cp2Zr(py)(η2-Me3SiCCSiMe3) to form
the same zirconacyclocumulene, see: Rosenthal, U.; Ohff, A.;
Baumann, W.; Kempe, R.; Tillack, A.; Burlakov, V. V. Angew. Chem.,
Int. Ed. 1994, 33, 1605.
(6) For the formation of metallacycloallenes from metal alkyne
complexes, see: (a) Zhang, S.; Zhang, W.-X.; Zhao, J.; Xi, Z. J. Am.
Chem. Soc. 2010, 132, 14042. (b) Kaleta, K.; Ruhmann, M.;
Theilmann, O.; Beweries, T.; Roy, S.; Arndt, P.; Villinger, A.;
Jemmis, E. D.; Schulz, A.; Rosenthal, U. J. Am. Chem. Soc. 2011, 133,
5463.
(7) Pellny, P.; Kirchbauer, F. G.; Burlakov, V. V.; Baumann, W.;
Spannenberg, A.; Rosenthal, U. J. Am. Chem. Soc. 1999, 121, 8313.
(8) For the reactions of metallacycles with aldehydes, see:
(a) Takahashi, T.; Kageyama, M.; Denisov, V.; Hara, R.; Negishi, E.
ASSOCIATED CONTENT
* Supporting Information
Text, figures, tables, and CIF files giving experimental details,
NMR spectra of all new products, crystallographic data of syn-
5b (ethanol adduct), syn-5n, 6, 7, 12n, and 13, DFT
calculations, and the calculated total energies and geometrical
coordinates. This material is available free of charge via the
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S
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Tetrahedron Lett. 1993, 34, 687. (b) Coperet, C.; Negishi, E.; Xi, Z.;
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(9) (a) For the formation of cis-[3]cumulenic diols via the reactions
of α-alkynylzirconacyclopentenes with ketones, see ref 4b. (b) For
insertion of two molecules of CO2 into zirconacyclopentatriene with
Cp* as the ligand, see ref 7.
AUTHOR INFORMATION
Corresponding Author
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ACKNOWLEDGMENTS
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We thank the National Natural Science Foundation of China
(Grant Nos. 21125210, 21072208, 20732008, 20821002,
20872168), Chinese Academy of Science and the Major State
Basic Research Development Program (Grant No.
2011CB808700) for financial support.
(10) The X-ray crystal structures of compounds syn-5b (ethanol
adduct), syn-5n, 6, 7, 12n, and 13 are shown in the Supporting
Information.
(11) Reduction of cumulenone 6 prepared by DMP oxidation of syn-
5b gave the two diastereomers in 61% and 26% yields, respectively.
These isomers are identical with syn- or anti-5b formed in Zr-mediated
reactions, indicating that the minor isomer is the alcohol epimer.
(12) Miao, W.; Lu, W.; Chan, T. H. J. Am. Chem. Soc. 2003, 125,
2412.
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