R. Akiyama et al. / Journal of Organometallic Chemistry 689 (2004) 3806–3809
3809
Table 4
Effect of bromide sources in amidocarbonylation
Acknowledgements
PI Pd 7c (1 mol %)
This work was partially supported by CREST,
SORST, and ERATO, Japan Science and Technology
Agency (JST), and a Grant-in-Aid for Scientific Re-
search from Japan Society of the Promotion of Science.
O
QBr (35 mol %)
CO2H
NHAc
H2SO4 (10 mol %)
+
AcNH2
H
CO (60 atm), dioxane
120 ˚C, 15 h
3
4
5
(1.5 eq.)
Entry
Loading
(mmol/g)
QBr
Yield of 5
(%)a
Pd leaching
(%)b
References
1
2
3
4
5
6
7
a
0.118
0.820
0.113
0.820
0.113
0.820
1.04
LiBr
LiBr
84
85
83
98
56
96
72
13
20
[1] Review: M. Beller, M. Eckert, Angew. Chem., Int. Ed. 39 (2000)
1010.
Bu4NBr
Bu4NBr
BnEt3NBr
BnEt3NBr
Et4NBr
ndc
23
[2] H. Wakamatsu, J. Uda, N. Yamakami, J. Chem. Soc., Chem.
Commun. (1971) 1540.
[3] M. Beller, M. Eckert, F. Vollmuller, S. Bogdanovic, H. Geissler,
¨
ndc
ndc
ndc
Angew. Chem., Int. Ed. 36 (1997) 1494.
[4] K. Drauz, O. Burkhardt, M. Beller, M. Eckert, DE 100 12 251 A1
(1999).
Yield was determined by HPLC analysis using an internal
standard technique.
b
[5] T. Sagae, M. Sugiura, H. Hagio, S. Kobayashi, Chem. Lett. 32
(2003) 160.
Leaching of palladium was determined by XRF analysis.
No peaks corresponding to Pd were observed (detection limit = 5
c
[6] (a) B.M. Trost, J. Am. Chem. Soc. 100 (1979) 7779;
(b) Y. Uozumi, H. Danjo, T. Hayashi, Tetrahedron Lett. 38
(1997) 3557;
ppm).
(c) M. Zecca, R. Fisera, G. Palma, S. Lora, M. Hronec, M.
´
Kralik, Chem. Eur. J. 6 (2000) 1980;
(d) C.A. Parrish, S.L. Buchwald, J. Org. Chem. 66 (2001)
3820;
Table 5
PI Pd catalyzed amidocarbonylation
(e) Y. Niu, L.K. Yeung, R.M. Crooks, J. Am. Chem. Soc.
123 (2001) 6840;
PI Pd 7ca (1 mol %)
(f) A.M. Jansson, M. Grøti, K.M. Halkes, M. Meldal, Org.
Lett. 4 (2002) 27;
BnEt3NBr (35 mol %)
HO2C
R1
O
O
H2SO4 (10 mol %)
O
(g) C. Ramarao, S.V. Ley, S.C. Smith, I.M. Shirley, N.
DeAlmedia, Chem. Commun. (2002) 1132;
(h) S.V. Ley, C. Ramarao, R.S. Gordon, A.B. Holmes, A.J.
Morrison, I.F. McConvey, I.M. Shirley, S.C. Smith, M.D.
Smith, Chem. Commun. (2002) 1134.
[7] (a) R. Akiyama, S. Kobayashi, J. Am. Chem. Soc. 125 (2003)
3412;
+
H2N
R2
N
H
R2
R1
(1.5 eq.)
H
CO (60 atm), dioxane
120 ˚C, 15 h
Entry
R1
R2
Yield (%)b
1
2
c-Hex
c-Hex
c-Hex
c-Hex
Me
(CH2)4Me
Ph
Quant (96)c,d
75c
20c
20c,e
49c,f
67
(b) K. Okamoto, R. Akiyama, S. Kobayashi, J. Org. Chem. 69
(2004) 2871;
3
4
NHMe
Me
Me
(c) K. Okamoto, R. Akiyama, S. Kobayashi, Org. Lett.
[8] (a) S. Kobayashi, S. Nagayama, J. Am. Chem. Soc. 120 (1998)
2985;
5
PhCH2CH2
i-Pr
t-Bu
6
7
Me
Me
55
(b) S. Nagayama, M. Endo, S. Kobayashi, J. Org. Chem. 63
(1998) 6094;
8
Ph
78
9
p-CF3C6H4
p-MeOC6H4
a-Naph
b-Naph
Me
Me
46g
38
(c) S. Kobayashi, M. Endo, S. Nagayama, J. Am. Chem. Soc. 121
(1999) 11229;
10
11
12
Me
Me
58g
44h
(d) S. Kobayashi, T. Ishida, R. Akiyama, Org. Lett. 3 (2001)
2649;
a
Unless otherwise noted, the loading level of the palladium was
1.04 mmol/g.
(e) R. Akiyama, S. Kobayashi, Angew. Chem., Int. Ed. 40 (2001)
3469;
b
Isolated yields.
Yield was determined by HPLC analysis.
(f) R. Akiyama, S. Kobayashi, Angew. Chem., Int. Ed. 41 (2002)
2602;
c
d
e
f
The loading level of the palladium was 0.820 mmol/g.
The product was identified as 8 [11].
The reaction mixture was stirred at rt for 6 h before introducing
(g) T. Ishida, R. Akiyama, S. Kobayashi, Adv. Synth. Catal. 345
(2003) 576.
[9] K. Okamoto, R. Akiyama, H. Yoshida, T. Yoshida, S. Kobaya-
shi, unpublished results.
[10] (a) M. Beller, M. Eckert, F. Vollmuller, J. Mol. Catal. A: Chem.
¨
CO.
g
The loading level of the palladium was 0.629 mmol/g.
The reaction was performed for 24 h.
h
135 (1998) 23;
(b) M. Beller, W.A. Moradi, M. Eckert, H. Neumann, Tetrahe-
dron Lett. 40 (1999) 4523.
O
[11] The synthesis of substituted hydantoins using palladium-catalyzed
amidocarbonylation was reported, see: M. Beller, M. Eckert,
W.A. Moradi, H. Neumann, Angew. Chem., Int. Ed. 38 (1999)
1454.
NMe
N
O
H
8