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ChemComm
2 For a singular example of a copper-catalyzed propargylic alkylation of
N,N-diethyl-1-cyclohexen-1-amine with 1-phenyl-2-propynyl benzoate
in 33% yield and with 10/1 dr and 72% ee, see: (a) P. Fang and X.-L.
Hou, Org. Lett., 2009, 11, 4612; For a singular example of a copper-
catalyzed decarboxylative propargylic alkylation of 1-phenylprop-2-yn-
1-yl 2-oxocyclohexanecarboxylate in 88% yield with 7/1 dr and 86% ee,
see: (b) F.-L. Zhu, Y. Zou, D.-Y. Zhang, Y.-H. Wang, X.-H. Hu, S. Chen,
J. Xu and X.-P. Hu, Angew. Chem., Int. Ed., 2014, 53, 1410.
3 For reviews, see: (a) C.-H. Ding and X.-L. Hou, Chem. Rev., 2011,
111, 1914; (b) Y. Nishibayashi, Synthesis, 2012, 489.
Scheme 4 Transformation of the alkylation product (2S,3R)-3aa to optically
active 2,3-dihydrofuran 5.
4 For catalytic asymmetric propargylic substitution based on Ru–
allenylidene intermediates, see: (a) Y. Nishibayashi, G. Onodera,
Y. Inada, M. Hidai and S. Uemura, Organometallics, 2003, 22, 873;
(b) Y. Inada, Y. Nishibayashi and S. Uemura, Angew. Chem., Int. Ed.,
2005, 44, 7715; (c) H. Matsuzawa, Y. Miyake and Y. Nishibayashi,
Angew. Chem., Int. Ed., 2007, 46, 6488; (d) H. Matsuzawa, K. Kanao,
Y. Miyake and Y. Nishibayashi, Org. Lett., 2007, 9, 5561;
(e) K. Fukamizu, Y. Miyake and Y. Nishibayashi, J. Am. Chem. Soc.,
2008, 130, 10498; ( f ) K. Kanao, Y. Miyake and Y. Nishibayashi,
Organometallics, 2009, 28, 2920; (g) K. Kanao, Y. Tanabe, Y. Miyake
and Y. Nishibayashi, Organometallics, 2010, 29, 2381; (h) K. Kanao,
Y. Miyake and Y. Nishibayashi, Organometallics, 2010, 29, 2126;
(i) M. Ikeda, Y. Miyake and Y. Nishibayashi, Angew. Chem., Int.
Ed., 2010, 49, 7289; ( j) M. Ikeda, Y. Miyake and Y. Nishibayashi,
Chem. – Eur. J., 2012, 18, 3321; (k) K. Motoyama, M. Ikeda, Y. Miyake
and Y. Nishibayashi, Organometallics, 2012, 31, 3426; (l) M. Ikeda,
Y. Miyake and Y. Nishibayashi, Organometallics, 2012, 31, 3810.
5 For catalytic asymmetric propargylic substitution based on
Cu–allenylidene intermediates, see: (a) R. J. Detz, M. M. E. Delville,
H. Hiemstra and J. H. van Maarseveen, Angew. Chem., Int. Ed., 2008,
47, 3777; (b) G. Hattori, H. Matsuzawa, Y. Miyake and Y. Nishibayashi,
Angew. Chem., Int. Ed., 2008, 47, 3781; (c) R. J. Detz, Z. Abiri, R. le Griel,
H. Hiemstra and J. H. van Maarseveen, Chem. – Eur. J., 2011, 17, 5921;
(d) G. Hattori, A. Yoshida, Y. Miyake and Y. Nishibayashi, J. Org. Chem.,
2009, 74, 7603; (e) G. Hattori, Y. Miyake and Y. Nishibayashi,
ChemCatChem, 2010, 2, 155; ( f ) G. Hattori, K. Sakata, H. Matsuzawa,
Y. Tanabe, Y. Miyake and Y. Nishibayashi, J. Am. Chem. Soc., 2010,
132, 10592; (g) A. Yoshida, G. Hattori, Y. Miyake and Y. Nishibayashi,
Org. Lett., 2011, 13, 2460; (h) C. Zhang, Y.-H. Wang, X.-H. Hu, Z. Zheng,
J. Xu and X.-P. Hu, Adv. Synth. Catal., 2012, 354, 2854; (i) T. Mino,
H. Taguchi, M. Hashimoto and M. Sakamoto, Tetrahedron: Asymmetry,
2013, 24, 1520; ( j) F.-Z. Han, F.-L. Zhu, Y.-H. Wang, Y. Zou, X.-H. Hu,
S. Chen and X.-P. Hu, Org. Lett., 2014, 16, 588; (k) Y. Zhou, F.-L. Zhu,
Z.-C. Duan, Y.-H. Wang, D.-Y. Zhang, Z. Cao, Z. Zheng and X.-P. Hu,
Tetrahedron Lett., 2014, 55, 2033; (l) M. Shibata, K. Nakajima and
Y. Nishibayashi, Chem. Commun., 2014, 50, 7874.
In conclusion, we have developed a highly diastereo-/enantio-
selective installment of two vicinal chiral centers via the copper-
catalyzed propargylic alkylation of acyclic ketone enamines with
propargylic esters by using a bulky and structurally rigid tridentate
ketimine P,N,N-ligand, in which excellent diastereoselectivities (up to
495/5 dr) and perfect enantioselectivities (up to 499% ee) have
been obtained for a wide range of substrates. Further development
and application of this reaction are underway.
This work was financially supported by the Dalian Institute
of Chemical Physics and the Program for Liaoning Excellent
Talents in University (LJQ 2013059).
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´
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14462 | Chem. Commun., 2014, 50, 14459--14462
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