D.-M. Cui et al. / Tetrahedron Letters 44 (2003) 4007–4010
Table 3. Synthesis of chroman-4-one and thiochroman-4-onea
4009
Entry
3a/3b
Cat. (mol%)
Temp. (°C)
Time (h)
Yield (%)b
1
2
3
4
5
6
7
8
3a
3a
3a
3a
3a
3a
3a
3b
3b
3b
3b
3b
3b
Bi(NTf2)3 (1)
Ga(OTf)3 (1)
Ga(OTf)3 (1)
Sc(OTf)3 (1)
La(OTf)3 (10)
Eu(OTf)3 (1)
Eu(OTf)3 (10)
Bi(NTf2)3 (1)
In(OTf)3 (1)
Sm(OTf)3 (1)
Sm(OTf)3 (10)
Yb(OTf)3 (1)
Yb(OTf)3 (10)
180
180
180
180
180
180
180
200
200
200
200
200
200
20
4
9
20
27
20
14
7
20
9
20
20
7
80
64
58
60
83
58
98
87
46
Trace
27
24
98
9
10
11
12
13
a The reaction was performed using 0.25 mmol of carboxylic acids in 2 mL of PhCl in a sealed glass tube.
b GC yield using dodecane as an internal standard.
cyclization of 3b, while 10 mol% of Yb(OTf)3 afforded
4b quantitatively (Table 3, entries 10–13).
4. (a) Krollpfeiffer, F.; Scha¨fer, W. Ber. Dtsch. Chem. Ges.
1923, 56, 620–632; (b) Caro, Y.; Masaguer, C. F.;
Ravina, E. Tetrahedron: Asymmetry 2003, 14, 381–387.
5. (a) Snyder, H. R.; Werber, F. X. Org. Synth. Coll. Vol.
III 1955, 798–800; (b) Owton, W. M.; Brunavs, M. Synth.
Commun. 1991, 21, 981–987.
6. (a) Rao, A. V. R.; Chanda, B.; Borate, H. B. Tetrahedron
1982, 38, 3555–3561; (b) Esteban, G.; Lopez-Sanchez, M.
A.; Martinez, E.; Plumet, J. Tetrahedron 1998, 54, 197–
212.
In summary, 1-tetralones and related cyclic ketones
were efficiently synthesized by the intramolecular
Friedel–Crafts acylation reaction of 4-arylbutyricacids
and related carboxylic acids using catalytic amounts of
Lewis acids such as Bi(NTf2)3 and M(OTf)3 (M=Bi,
Ga, In and rare-earth metals).
7. Premasagar, V.; Palaniswamy, V. A.; Eisenbraun, E. J. J.
Org. Chem. 1981, 46, 2974–2976.
Acknowledgements
8. Fieser, L. F.; Hershberg, E. B. J. Am. Chem. Soc. 1939,
61, 1272–1281.
This work was financially supported by New Energy
and Industrial Technology Development Organization
(NEDO). D.C. thanks NEDO for a postdoctoral
fellowship.
9. (a) Yamato, T.; Hideshima, C.; Prakash, G. K. S.; Olah,
G. A. J. Org. Chem. 1991, 56, 3955–3957; (b) Olah, G.
A.; Mathew, T.; Farnia, M.; Prakash, G. K. S. Synlett
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Dubac, J.; Desmurs, J. R. Eur. J. Org. Chem. 1998,
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14. Typical procedure: A mixture of Bi(NTf2)3 (3 mg) and 1
(41 mg, 0.25 mmol) in toluene (2 mL) was heated at