1984
Y. Tao et al. / Tetrahedron Letters 51 (2010) 1982–1984
Table 4
In summary, under mild conditions the highly efficient and reg-
Catalytic allylation of N-methylaniline with allylic alcoholsa
ioselective allylic amination of allylic alcohols catalyzed by
[(Cp*Mo)3S4Pd(dba)][PF6] with H3BO3 as additive has been de-
scribed. A variety of allylic alcohols and amines are investigated.
The reaction proceeds with excellent regioselectivity, leading to
linear product for allylic alcohols bearing a methyl or a phenyl sub-
b
Entry
Allylic alcohol
Time (h)
Product
Yield (%)
Ph
OH
1
8
95
94
Ph
N
N
Ph
Ph
OH
Ph
stituent at either
a- or c-position.
2
8
Ph
Acknowledgments
OH
89
3
4
5
12
14
12
N
N
(E:Z = 7.6:1)
Ph
Ph
We are grateful to the National Natural Science Foundation of
China (No. 20676019) and the Program for Changjiang Scholars
and Innovative Research Team in University (No. IRT0711) for
the financial support of this work.
OH
93
(E:Z = 6.2:1)
90
87
OH
OH
N
Ph
N
References and notes
6
12
Ph
1. For general reviews, see: (a) Lu, Z.; Ma, S. Angew. Chem., Int. Ed. 2008, 47, 258;
(b) Trost, B. M.; van Vranken, D. L. Chem. Rev. 1996, 96, 395; (c) Trost, B. M. Acc.
Chem. Res. 1996, 29, 355.
2. For reviews on allylation reaction of allylic alcohol, see: (a) Muzart, J. Eur. J. Org.
Chem. 2007, 3077; (b) Tamaru, Y. Eur. J. Org. Chem. 2005, 2647; (c) Selander, N.;
Szabo, K. J. Dalton Trans. 2009, 6267.
7
24
24
24
40
79
85
OH
8c
N
9d
Ph
a
Reaction conditions: allylic alcohol 0.4 mmol, N-methylaniline 0.4 mmol,
3. Lu, X.; Lu, L.; Sun, J. J. Mol. Catal. 1987, 41, 245.
4. Lu, X.; Jian, X.; Tao, X. J. Organomet. Chem. 1998, 344, 109.
5. (a) Kimura, M.; Futanmata, M.; Shibata, K.; Tamaru, Y. Chem. Commun. 2003,
234; (b) Kimura, M.; Futamata, M.; Mukai, R.; Tamaru, Y. J. Am. Chem. Soc. 2005,
127, 4592.
[(Cp*Mo)3S4Pd(dba)][PF6] 0.02 mmol, H3BO3 0.2 mmol, CH2Cl2 1 mL, reflux.
b
Isolated yield.
c
1,2-Dichloroethane as solvent, 80 °C.
6. Stary, I.; Stara, I. G.; Kocovsky, P. Tetrahedron Lett. 1993, 34, 179.
7. Masuyama, Y.; Kagawa, M.; Kurusu, Y. Chem. Lett. 1995, 1121.
8. (a) Yang, S.; Hung, C. J. Org. Chem. 1999, 64, 5000; (b) Yang, S.; Tsai, Y.
Organometallics 2001, 20, 763.
9. Sakamoto, M.; Shimizu, I.; Yamamoto, A. Bull. Chem. Soc. Jpn. 1996, 69, 1065.
10. Yamashita, Y.; Gopalarathnam, A.; Hartwig, J. F. J. Am. Chem. Soc. 2007, 129,
7508.
11. Kinoshita, H.; Shinokubo, H.; Oshima, K. Org. Lett. 2004, 6, 4085.
12. Nishikata, T.; Lipshutz, B. H. Org. Lett. 2009, 11, 2377.
13. For recent reviews, see: (a) Hidai, M.; Kuwata, S. Acc. Chem. Res. 2000, 33, 46;
(b) Hernandez-Molina, R.; Sokolv, M. N.; Sykes, A. G. Acc. Chem. Res. 2001, 34,
223.
14. (a) Wakabayashi, T.; Ishii, Y.; Ishikawa, K.; Hidai, M. Angew. Chem., Int. Ed. 1996,
35, 2123; (b) Takei, I.; Wakebe, Y.; Suzuki, K.; Enta, Y.; Suzuki, T.; Mizobe, Y.;
Hidai, M. Organometallics 2003, 22, 4639.
Cp*
Mo
+
S
dba
S
Pd
Mo
Mo
S
Cp*
S
Cp*
dba
Cp*
Mo
+
S
Nu
Pd
S
OH
S
Mo
Mo
Cp*
+
15. Takei, I.; Enta, Y.; Wakebe, Y.; Suzuki, T.; Hidai, M. Chem. Lett. 2006, 35, 590.
16. Takei, I.; Suzuki, K.; Enta, Y.; Dohki, K.; Suzuki, T.; Mizobe, Y.; Hidai, M.
Organometallics 2003, 22, 1790.
17. Takei, I.; Kobayashi, K.; Dohki, K.; Nagao, S.; Mizobe, Y.; Hidai, M. Chem. Lett.
2007, 36, 546.
Cp*
+
S
H BO
H2O•
3
3
H3BO3
NuH
18. General procedure for the allylation reaction of amines with allylic alcohol: All
manipulations were carried out under Ar atmosphere by using standard
Schlenk techniques. The solvents were dried by common procedures and
distilled before use. N-Allyl-N-benzylphenylamine (Table 3, entry 2):
[(Cp*Mo)3S4Pd(dba)][PF6] (25 mg, 0.02 mmol) and boric acid (12 mg,
Cp*
Mo
+
+
Cp*
Mo
S
S
Pd
S
BH3O3
O
H
S
Mo
0.2 mmol) were added to
a 25 mL Schlenk tube, then CH2Cl2 (1 mL), N-
BH3O3
O
H
S
Pd
Mo
Mo
Cp*
benzylaniline (70 mg, 0.4 mmol), and allyl alcohol (22 mg, 0.4 mmol) were
added stepwise. The tube was sealed and heated to reflux until the appointed
time. The products (81 mg, 95% yield) were obtained by column
chromatography on silica gel (eluent: petroleum ether/EtOAc, 20:1).
19. Ozawa, F.; Okamoto, H.; Kawagishi, S.; Yamamoto, S.; Minami, T.; Yoshifuji, M.
J. Am. Chem. Soc. 2002, 124, 10968.
Mo
S
S
Cp*
S
Cp*
Cp*
Scheme 1. Proposed mechanism for allylation reaction.