Fluoroalkyldistannoxane Catalysts for Transesterification in Fluorous Biphase Technology
FULL PAPERS
Transesterification in Single Fluorous Phase System (Table 2,
Entry 1)
organic layer was analyzed with GC to prove a quantitative yield of benzyl 3-
phenylpropionate. Evaporation of the FC-72 phase afforded quantitative
recovery of 1aa (86 mg).
A test tube (50 mL) charged with ethyl 3-phenylpropionate (178 mg,
1
.0 mmol), 1-octanol (130 mg, 1.0 mmol), 1aa (86 mg, 0.05 mmol, 5 mol %)
and FC-72 (5.0 mL) was placed in a stainless pressure bottle and heated at
508C for 16 h. After having been cooled, toluene (5.0 mL) was added to the
Synthesis of m-Phenoxybenzyl Dichlorochrysanthemate
1
(
Eq. 2)
reaction mixture. The toluene and FC-72 layers were separated and the
latter layer was washed with toluene (1.0 mL Â 2). The combined organic
layer was analyzed with GC to prove a quantitative yield of 1-octyl 3-
phenylpropionate. Evaporation of the organic layer followed by column
chromatography (hexane/AcOEt 10/1) furnished 1-octyl 3-phenylpropi-
onate as a colorless oil; yield: 262 mg (100%).
A test tube (50 mL) charged with methyl dichlorochrysanthemate (223 mg,
.0 mmol, E/Z 57/43), m-phenoxybenzyl alcohol (200 mg, 1.0 mmol), 1aa
172 mg, 0.1 mmol, 10 mol %) and FC-72 (5.0 mL) was placed in a stainless
1
(
pressure bottle and heated at 1658C for 24 h. After having been cooled,
toluene (5.0 mL) was added to the reaction mixture. After separation of the
toluene and FC-72, the latter layer was washed with toluene (1.0 mL Â 2).
The combined organic layer was analyzed with GC to prove a quantitative
yield of m-phenoxybenzyl dichlorochrysanthemate (E/Z 54/46).
Other reactions were conducted analogously.
1H NMR
8
-(2-Tetrahydropyranyloxy)octyl
3-phenylpropanoate:
(
500 MHz, CDCl
3
): d 1.20 ± 1.83 (m, 18H), 2.62 (t, J 7.7 Hz, 2H), 2.95
(
t, J 7.7 Hz, 2H), 3.31 ± 3.52 (m, 2H), 3.68 ± 3.88 (m, 2H), 4.05 (t, J 6.7 Hz,
13
2
2
1
H), 4.57 (s, 1H), 7.18 ± 7.32 (m, 5H); C NMR(125 MHz, CDCl
5.5, 25.8, 26.1, 28.6, 29.2, 29.3, 29.7, 30.8, 31.0, 35.9, 62.4, 64.6, 67.6, 98.9,
26.2, 128.3, 128.5, 140.6, 173.0. Anal. calcd. for C22 : C 72.89, H 9.45;
3
): d 19.7,
34 4
H O
Acknowledgements
found: C 72.91, H 9.63.
-tert-Butyldimethylsilyloxyoctyl
500 MHz, CDCl
): d 0.05 (s, 6H), 0.89 (s, 9H), 1.28 ± 1.60 (m, 12H), 2.62
t, J 7.8 Hz, 2H), 2.95 (t, J 7.8 Hz, 2H), 3.60 (t, J 6.6 Hz, 2H), 4.05 (t,
8
3-phenylpropanoate:
1H NMR
The authors are very grateful to Sumitomo Chemical for supplying samples of
chrysanthemates.
(
(
3
1
3
J 6.6 Hz, 2H), 7.18 ± 7.31 (m, 5H); C NMR(125 MHz, CDCl
3
): d À 5.3,
1
1
3
8.4, 25.7, 25.8, 26.0, 28.6, 29.2, 29.3, 31.0, 32.8, 35.9, 63.2, 64.6, 126.2, 128.3,
28.5, 140.6, 173.0; HRMS (EI): calcd. for C23
40 3
H O Si: 392.2747; found:
References and Notes
92.2767.
[
1] T. Horv a¬ th, Acc. Chem. Res. 1998, 31, 641; D. P. Curran, Angew.
Chem. Int. Ed. 1998, 37, 1174; E. G. Hope, A. M. Stuart, J. Fluorine
Chem. 1999, 100, 75.
Transesterification Catalyzed in FC-72/Toluene Binary
System (Table 3, Entry 8)
[
2] D. P. Curran, S. Hadida, S.-Y. Kim, Z. Luo, J. Am. Chem. Soc. 1999,
1
21, 6607; M. Larhed, M. Hoshino, S. Hadida, D. P. Curran, A.
Hallberg, J. Org. Chem. 1997, 62, 5583; D. P. Curran, S. Hadida, M.
He, J. Org. Chem. 1997, 62, 6714; B. Bucher, D. P. Curran,
Tetrahedron Lett. 2000, 41, 9617.
A test tube (50 mL) charged with ethyl 3-phenylpropionate (178 mg,
1
.0 mmol), geraniol (201 mg, 1.3 mmol), 1aa (86 mg, 0.05 mmol, 5 mol %),
FC-72 (5.0 mL) and toluene (5.0 mL) was placed in a stainless pressure
bottle and heated at 1508C for 16 h. After having been cooled, the reaction
mixture was separated and the FC-72 layer was washed with toluene (1.0 mL
 2). The combined organic layer was analyzed with GC to prove a
quantitative yield of geranyl 3-phenylpropionate. Evaporation of the
organic layer followed by column chromatography (hexane/AcOEt 10/
[
3] J. Otera in Advances in Detailed Reaction Mechanism, Vol. 3, (Ed.:
J. M. Coxon), JAI Press Inc., Greenwich, Conn., 1994, pp. 167.
4] J. Otera, S. Ioka, H. Nozaki, J. Org. Chem. 1989, 54, 4013.
5] J. Xiang, A. Orita, J. Otera, J. Organomet. Chem. submitted.
6] J. Otera, Chem. Rev. 1993, 93, 1449.
7] Transesterification of b-keto esters was carried out using reactants in
a 1:1 ratio, yet yields were not perfect (50 ± 97%): S. P. Chavan, P. K.
Zubaidha, S. W. Dantale, A. Keshavaraja, A. V. Ramaswamy, T.
Ravindranathan, Tetrahedron Lett. 1996, 37, 233; B. S. Balaji, M.
Sasidharan, R. Kumar, B. Chanda, Chem. Commun. 1996, 707; D. E.
Ponde, V. H. Deshpande, V. J. Bulbule, A. Sudalai, A. S. Gajare, J.
Org. Chem. 1998, 63, 1058; B. P. Bandgar, V. S. Sadavarte, L. S.
Uppalla, Chem. Lett. 2001, 894.
[
[
[
[
1
) furnished geranyl 3-phenylpropionate as a colorless oil; yield: 286 mg
(
100%).
Fluorous Biphasic Transesterification in FC-72/Alcohol
Binary System (Table 4, Entry 1)
[
8] For a preliminary report on this protocol, see: J. Xiang, S. Toyoshima,
A. Orita, J. Otera, Angew. Chem. Int. Ed. 2001, 40, 3670.
A test tube (50 mL) charged with ethyl 3-phenylpropionate (356 mg,
2
(
1
.0 mmol), methanol (2 mL), 1aa (172 mg, 0.1 mmol, 5 mol %) and FC-72
4.0 mL) was placed in a stainless pressure bottle and heated at 1508C for
6 h. After having been cooled, toluene (5.0 mL) was added to the reaction
[9] Although any fluorocarbon solvents are employable, FC-72 is the
solvent of our choice in this study because it is cheapest among them.
[10] J. Otera, T. Yano, R. Okawara, Organometallics 1986, 5, 1167.
[11] We have no data about the solubility of alcohols in FC-72 at elevated
temperatures due to difficulties of measurement.
[12] M. Elliott, A. W. Farnham, N. F. Janes, P. H. Needham, D. A.
Pullman, J. H. Stevenson, Nature 1973, 246, 169.
[13] J. Izumi, I. Shiina, T. Mukaiyama, Chem. Lett. 1995, 141.
[14] K. Wakasugi, T. Misaki, K. Yamada, Y. Tanabe, Tetrahedron Lett.
mixture. After separation of the organic layers from FC-72, the FC-72 layer
was washed with toluene (1.0 mL Â 2). The combined organic layer was
analyzed with GC to prove a quantitative yield of methyl 3-phenylpropi-
onate. Evaporation of the organic layer followed by column chromatog-
raphy (hexane/AcOEt 10/1) furnished methyl 3-phenylpropionate as a
colorless oil; yield: 328 mg (100%).
2
001, 41, 5249.
[
[
[
15] G. V. Subbaraju, D. Rajasekhar, Indian J. Chem. Sect. B 1996, 35, 615.
16] G. Vernin, J. Essent. Oil Res. 1993, 5, 563.
17] S. Takahashi, L. A. Cohen, H. K. Miller, E. G. Peake, J. Org. Chem.
Transesterification in Single Organic Solvent System
(
Table 5, Entry 1)
1
971, 36, 1205.
[
18] R. C. Lloyd, M. Dickman, J. B. Jones, Tetrahedron: Asymmetry 1998,
9, 551.
Methyl 3-phenylpropionate (164 mg, 1.0 mmol), benzyl alcohol (130 mg,
.2 mmol), 1aa (86 mg, 0.05 mmol, 5 mol %) and toluene (5.0 mL) were
added into a 50-mL, two-necked flask equipped with a condenser. The
reaction mixture was heated at reflux for 6 h. After having been cooled, the
reaction mixture was extracted with FC-72 (5 mL Â 2). The combined
1
[19] K. Saitoh, I. Shiina, T. Mukaiyama, Chem. Lett. 1998, 679.
[20] G. Appendino, G. Cravotto, P, Gariboldi, B. Gabetta, E. Bombardelli,
Gazz. Chim. Ital. 1994, 124, 1.
[21] M. Tavares, R. Ramasseul, J. C. Marchon, Catal. Lett. 1990, 4, 163.
Adv. Synth. Catal. 2002, 344, 84 ±90
89