Journal of the American Chemical Society
Communication
134, 31−34. (c) Joo, J. M.; Yuan, Y.; Lee, C. J. Am. Chem. Soc. 2006,
128, 14818−14819.
case of the dimethylimine 2e, neither β- nor α-addition was
observed, presumably due to the steric hindrance.
(10) For a recent example of the use of pre-2a as the precursor of 2a,
see: Ma, T.; Fu, X.; Kee, C. W.; Zong, L.; Pan, Y.; Huang, K.-W.; Tan,
C.-H. J. Am. Chem. Soc. 2011, 133, 2828−2831.
In summary, the findings reported herein demonstrate the
rhenium-catalyzed reaction of terminal alkynes with imines to
afford allylamine derivatives. The diphenylmethyl group as the
substituent on the imine nitrogen gave the best result.
Deuterium labeling experiments revealed that the regioselective
addition of hydrogen and the N-alkylideneaminoalkyl group to
the terminal alkynes also proceeds stereoselectively. The C−C
bond forming step via the nucleophilic attack of the alkynyl β-
carbon on the imine carbon leading to the formation of a
vinylidene rhenium species appears to be involved in the
catalytic cycle.
(11) Kuninobu, Y.; Inoue, Y.; Takai, K. Chem. Lett. 2006, 35, 1376−
1377.
(12) For recent reviews on the catalytic reactions involving
vinylidene metal complxes, see: (a) Metal Vinylidenes and Allenylidenes
in Catalysis; Bruneau, C., Dixneuf, P. H., Eds.; Wiley-VCH: Weinheim,
Germany, 2008. (b) Trost, B. M.; McClory, A. Chem.Asian J. 2008,
3, 164−194.
(13) For examples where the formation of a vinylidene rhenium
complex is proposed as a key intermediate in catalytic reactions, see:
(a) Xia, D.; Wang, Y.; Du, Z.; Zheng, Q.-Y.; Wang, C. Org. Lett. 2012,
14, 588−591. (b) Yudha, S. S.; Kuninobu, Y.; Takai, K. Org. Lett. 2007,
9, 5609−5611.
ASSOCIATED CONTENT
■
S
(14) For examples of the 1,5-hydrogen shift to the vinylidene β-
carbon, see: (a) Tobisu, M.; Nakai, H.; Chatani, N. J. Org. Chem.
2009, 74, 5471−5475. (b) Odedra, A.; Datta, S.; Liu, R.-S. J. Org.
Chem. 2007, 72, 3289−3292. (c) Bajracharya, G. B.; Pahadi, N. K.;
Gridnev, I. D.; Yamamoto, Y. J. Org. Chem. 2006, 71, 6204−6210.
(d) Datta, S.; Odedra, A.; Liu, R.-S. J. Am. Chem. Soc. 2005, 127,
11606−11607.
* Supporting Information
Experimental procedures and characterization data for all new
compounds. This material is available free of charge via the
AUTHOR INFORMATION
■
(15) A similar retro-metallo-ene rearrangement of a β-amino-
alkylvinyliene metal species was proposed previously; see:
Corresponding Author
́
(a) Hyder, I.; Jimenez-Tenorio, M.; Puerta, M. C.; Valerga, P.
Notes
Organometallics 2011, 30, 726−737. (b) Ipaktschi, J.; Mohsseni-Ala, J.;
The authors declare no competing financial interest.
Dulmer, A.; Loschen, C.; Frenking, G. Organometallics 2005, 24, 977−
̈
989.
(16) The possibility of a mechanism involving the formation of a
metallacycle by the oxidative coupling of terminal alkynes, imines, and
rhenium species cannot be ruled out, although such a mechanism does
not account for the regioselectivity of the products observed here, or
the results shown in Scheme 2.
ACKNOWLEDGMENTS
■
This work was supported in part by a Grant-in-Aid for Scientific
Research (No. 22550100). Thanks are given to the
Instrumental Analysis Center, Faculty of Engineering, Osaka
University, for Assistance with HRMS and elemental analyses.
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