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Table 3 Direct allylation of 1g with diverse allylic alcoholsa
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Entry
Allylic alcohol
Product
Yield
1b
2b
3
2b
2c
2d
2e
2f
3t
3t
3u
3v
3w
84%
80%
78%
97%
89%
4b
5
a
Reaction conditions: 1g (0.2 mmol), 2b–c (0.24 mmol), Pd(PPh3)4 (1.5
mol%), 4 A MS (50 mg), toluene (1.0 mL), 60 ꢀC, 12 h; all yields are
˚
isolated. b 3.0 mol% of Pd(PPh3)4 used.
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that the reactions of 1g with both 2b and 2c exclusively afforded
3t (entries 1 and 2) in similar yields, which indicate that both
reactions proceeded via the same p-allyl-Pd intermediate.5
Remarkably, allylic alcohol 2f bearing highly steric hindrance is
also suitable for the process, the reaction afforded 3w in 89%
yield smoothly.
In conclusion, we have developed an efficient direct allylic
alkylation of azlactones with simple allylic alcohols using
Pd(PPh3)4 alone as catalyst under neutral conditions by
substrate self-assisted activation strategy. The approach can be
easily extended to gram scale in almost quantitative yield, which
provides a practical synthetic approach to quaternary allylic
amino acids.8 Further applications of the practical method, as
well as the asymmetric variant of this reaction are under
investigation in our laboratory and will be reported in due
course.
4 (a) J. P. Takahara, Y. Masuyama and Y. Kurusu, J. Am. Chem.
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Am. Chem. Soc., 2013, 135, 12536.
5 (a) I. Kadota, A. Shibuya, Y. S. Gyoung and Y. Yamamoto, J.
Am. Chem. Soc., 1998, 120, 10262; (b) N. T. Patil and
Y. Yamamoto, Tetrahedron Lett., 2004, 45, 3101; (c)
K. Manabe and S. Kobayashi, Org. Lett., 2003, 5, 3241; (d)
G. Jiang and B. List, Adv. Synth. Catal., 2011, 353, 1667, For
direct asymmetric allylic alkylation with allylic alcohols by
using chiral phosphoric acids, see: ; (e) G. Jiang and B. List,
Angew. Chem., Int. Ed., 2011, 50, 9471; (f) Z.-L. Tao,
W.-Q. Zhang, D.-F. Chen, A. Adele and L.-Z. Gong, J. Am.
Chem. Soc., 2013, 135, 9255, Another recent notable
example for the direct allylation of a-branched aromatic
aldehydes with allylic alcohols catalyzed by dual-catalytic
strategy, see: ; (g) S. Krautwald, D. Sarlah, M. A. Schafroth
and E. M. Carreira, Science, 2013, 340, 1065, Recently, Beller
et al. reported a Pd-catalyzed carbonylation of allylic alcohol
in the presence of TFA, in which in situ formation of
Acknowledgements
Financial supports from Hundred Talent Program of Chinese
Academy of Sciences (CAS) and the National Natural Science
Foundation of China (21202175) are gratefully acknowledged.
Notes and references
1 For reviews, see: (a) J. Tsuji, Transition Metal Reagents and
Catalysts, Wiley, New York, 2000; (b) B. M. Trost and
M. L. Crawley, Chem. Rev., 2003, 103, 2921; (c) U. Kazmaier,
Curr. Org. Chem., 2003, 7, 317; (d) W. Zhang and D. Liu, in
Chiral Ferrocenes in Asymmetric Catalysis: Synthesis and
25598 | RSC Adv., 2014, 4, 25596–25599
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