Acylation of Alcohols
Bi(OTf) -Ca ta lyzed Acetyla tion in Ac
J . Org. Chem., Vol. 66, No. 26, 2001 8933
3
2
O (r ep r esen ta -
was added by a syringe at 25 °C, and the reaction mixture
was stirred at the temperature for 12 h. After ethyl acetate
tive p r oced u r e). To a round-bottomed flask were added acetic
anhydride (8.4 mL, 89 mmol), 2-phenethyl alcohol (1.22 g, 10.0
3
and NaHCO aq had been added, organic and aqueous layers
mmol), and an acetic anhydride solution (1.0 mL) of Bi(OTf)
which had been prepared from Bi(OTf) (7.3 mg, 0.01 mmol,
calculated as the tetrahydrate) and Ac O (10 mL), and the
mixture was stirred at 25 °C for 10 min. After ethyl acetate
and NaHCO aq had been added, organic and aqueous layers
3
,
were separated. The aqueous layer was extracted with ethyl
acetate three times, and the organic layers were combined and
dried over MgSO . GC analysis of the crude mixture showed
4
3
2
the formation of furfuryl acetate in 97% yield.
3
DMAP -Ca ta lyzed Acetyla tion in P yr id in e (r ep r esen -
ta tive p r oced u r e). To a flame-dried round-bottomed flask
were added pyridine (3.0 mL), ethyl (S)-lactate (118.1 mg, 1.0
were separated. The aqueous layer was extracted with ethyl
acetate three times, and the organic layers were combined and
dried over MgSO
the formation of 2-phenethyl acetate in 98% yield.
Bi(OTf) -Ca ta lyzed Acetyla tion in CH Cl (r ep r esen ta -
tive p r oced u r e). A CH Cl solution (10 mL, not purified and
wet) of 2-phenethyl alcohol (1.22 g, 10.0 mmol) and Ac O (1.4
mL, 15.0 mmol) was stirred at 25 °C in the presence of Bi-
OTf) (36.4 mg, 0.5 mol %, calculated as the tetrahydrate) for
h. After ethyl acetate and NaHCO aq had been added,
4
. GC analysis of the crude mixture showed
mmol), Ac
mol %), and the reaction mixture was stirred at 25 °C for 24
h. After ethyl acetate and NaHCO aq had been added, organic
and aqueous layers were separated. The aqueous layer was
extracted with ethyl acetate three times, and the organic layers
were combined and dried over MgSO . GC analysis of the crude
4
mixture showed the formation of furfuryl acetate in quantita-
tive yield.
2
O (0.94 mL, 10.0 mmol), and DMAP (12.2 mg, 10
3
2
2
3
2
2
2
(
4
3
3
organic and aqueous layers were separated. The aqueous layer
was extracted with ethyl acetate three times, and the organic
Zn Cl
tive p r oced u r e). To a flame-dried round-bottomed flask were
added CH Cl (5.0 mL), 2-methyl-1-phenylpropan-2-ol (150.2
mg, 1.0 mmol), Ac O (0.94 mL, 10.0 mmol), and ZnCl (13.6
mg, 10.0 mol %), and the reaction mixture was stirred at 25
°C for 20 h. After ethyl acetate and NaHCO aq had been
2 2 2
-Ca ta lyzed Acetyla tion in CH Cl (r ep r esen ta -
layers were combined and dried over MgSO
4
. GC analysis of
2
2
the crude mixture showed the formation of 2-phenethyl acetate
in 92% yield.
2
2
Bi(OTf)
tive p r oced u r e). To a flame-dried round-bottomed flask were
added THF (0.5 mL), furfuryl alcohol (98.1 mg, 1.0 mmol), Ac
0.94 mL, 10.0 mmol), and Bi(OTf) (0.36 mg, 0.05 mol %,
calculated as the tetrahydrate). The mixture was stirred at
5 °C for 4 h. After ethyl acetate and NaHCO aq had been
3
-Ca ta lyzed Acetyla tion in THF (r ep r esen ta -
3
added, organic and aqueous layers were separated. The
aqueous layer was extracted with ethyl acetate three times,
and the organic layers were combined and dried over MgSO .
4
2
O
(
3
GC analysis of the crude mixture showed the formation of
2-acetoxy-2-methyl-1-phenylpropane in 92% yield.
2
3
Aceta te of 10: 1H NMR (CDCl
) δ 1.91 (s, 3H), 2.45 (s, 3H),
added, organic and aqueous layers were separated. The
aqueous layer was extracted with ethyl acetate three times,
and the organic layers were combined and dried over MgSO .
4
GC analysis of the crude mixture showed the formation of
furfuryl acetate in 93% yield.
3
Sc(OTf) -Ca ta lyzed Acetyla tion in MeCN (r ep r esen ta -
tive p r oced u r e). To a flame-dried round-bottomed flask were
added MeCN (0.5 mL) and furfuryl alcohol (98.1 mg, 1.0 mmol).
In another dried flask was prepared an acetic anhydride
3
2.90 (d, J ) 17.3 Hz, 1H), 3.08 (dd, J ) 17.3, 5.0 Hz, 1H), 4.97
(dd, J ) 10.3, 5.0 Hz, 1H), 5.05-5.10 (m, 1H), 5.20-5.30 (br,
1H), 7.15-7.30 (m, 4H), 7.33 (d, J ) 7.9 Hz, 2H), 7.81 (d, J )
7.9 Hz, 2H); 13C NMR (CDCl
) δ 20.9, 21.5, 37.4, 59.4, 74.8,
124.2, 125.0, 126.9, 127.4, 128.7, 129.9, 137.8, 138.6, 139.6,
143.9, 169.8; elemental analysis calcd (%) for C18 S: C
62.59, H 5.54, N 4.06; found C 62.48, H 5.64, N 4.03.
3
H19NO
4
1
Aceta te of 17: H NMR (CDCl ) δ 1.30-1.47 (m, 8H), 1.55-
3
solution (10 mL) of Sc(OTf)
of this solution was diluted to 10 mL by acetic anhydride. The
acetic anhydride solution (0.94 mL) of Sc(OTf) (0.25 mg, 0.05
3
(26.2 mg, 0.053 mmol), and 1 mL
1.69 (m, 2H), 1.70-1.80 (m, 2H), 2.03 (s, 3H), 4.05 (t, J ) 6.8
Hz, 2H), 4.36 (t, J ) 6.8 Hz, 2H); 13C NMR (CDCl
) δ 20.4,
3
1
25.2, 25.5, 27.8, 28.3, 28.7, 28.8, 64.1, 67.9, 114.4 ( J C-F ) 284
3
2
mol %) thus prepared was added to the former reaction vessel,
and the mixture was stirred at 25 °C for 5 h. After ethyl acetate
Hz), 157 ( J C-F ) 41 Hz), 170.7. HRMS (EI) Found: m/z
284.1228. Calcd for C12
H
19
O
4
F
3
: 284.1235.
Aceta te of 18: 1H NMR (CDCl
) δ 1.32 (s, 3H), 1.53 (s, 3H),
3
and NaHCO
3
aq had been added, organic and aqueous layers
were separated. The aqueous layer was extracted with ethyl
acetate three times, and the organic layers were combined and
2.02 (s, 3H), 2.07 (s, 6H), 4.12 (dd, J ) 5.5, 12.2 Hz, 1H), 4.42
(dd, J ) 2.9, 9.3 Hz, 1H), 4.49 (d, J ) 3.6 Hz, 1H), 4.57 (dd, J
) 2.4, 12.2 Hz, 1H), 5.17-5.26 (m, 1H), 5.35 (d, J ) 2.9 Hz,
dried over MgSO
the formation of furfuryl acetate in 67% yield.
Me SiOTf-Ca ta lyzed Acetyla tion in CH Cl
ta tive p r oced u r e). To a flame-dried round-bottomed flask
were added CH Cl (2.5 mL) and furfuryl alcohol (98.1 mg,
.0 mmol). In another dried flask was prepared an acetic
anhydride solution (10 mL) of Me SiOTf (0.26 mL, 1.4 mmol).
The acetic anhydride solution (0.14 mL) of Me SiOTf (0.0036
mL, 2.0 mol %) was added to the former reaction vessel at 0
C, and the mixture was stirred at the temperature for 4 h.
After ethyl acetate and NaHCO aq had been added, organic
4
. GC analysis of the crude mixture showed
1H), 5.93 (d, J ) 3.6 Hz, 1H); 13C NMR (CDCl
) δ 20.7 (3C),
26.2, 26.7, 63.4, 67.5, 74.7, 76.7, 83.2, 105.1, 112.5, 169.2, 169.7,
3
3
2
2
(r ep r esen -
170.6; elemental analysis calcd (%) for C15
22 9
H O : C 52.02, H
6.40; found C 51.81, H 6.69.
2
2
1
1
Aceta te of 23: H NMR (CDCl
3
) δ 0.88 (t, J ) 7.0 Hz, 3H),
1.15-1.30 (m, 18H), 1.42 (s, 6H), 1.97 (s, 3H); 13C NMR (CDCl
)
3
3
δ 13.9, 22.1, 22.5, 23.7, 25.8, 29.2, 29.4, 29.5, 29.7, 29.8, 31.8,
3
40.6, 82.1, 170.0; elemental analysis calcd (%) for C15
30 2
H O :
°
C 74.32, H 12.47; found C 74.09, H 12.71.
1
Aceta te of 26: H NMR (CDCl
3
) δ 1.05 (d, J ) 7.0 Hz, 3H),
3
and aqueous layers were separated. The aqueous layer was
extracted with ethyl acetate three times, and the organic layers
1.80 (s, 3H), 4.54 (d, J ) 11.7 Hz, 1H), 4.60 (q, J ) 7.0 Hz,
1H), 4.83 (d, J ) 11.7 Hz, 1H), 7.00-7.08 (m, 2H), 7.25-7.38
(m, 3H), 7.44-7.53 (m, 2H), 7.55-7.62 (m, 1H), 8.02 (d, J )
were combined and dried over MgSO
mixture showed the formation of furfuryl acetate in 49% yield.
Bu P -Ca ta lyzed Acetyla tion in CH Cl (r ep r esen ta tive
p r oced u r e). To a flame-dried round-bottomed flask were
added CH Cl (5.0 mL), furfuryl alcohol (98.1 mg, 1.0 mmol),
and Ac O (0.94 mL, 10.0 mmol). Bu P (20.2 mg, 10.0 mol %)
4
. GC analysis of the crude
7.3 Hz, 2H); 13C NMR (CDCl
) δ 12.7, 21.1, 44.6, 46.8, 85.3,
125.5, 127.8, 128.0, 128.2, 128.5, 132.7, 137.1, 138.7, 168.6,
3
3
2
2
3
200.4; elemental analysis calcd (%) for C19H19ClO : C 68.98,
H 5.79; found C 68.92, H 5.87.
2
2
1
Aceta te of 27: H NMR (CDCl
3
) δ 1.48 (s, 3H), 1.98 (s, 3H),
2
3
1
.97-2.07 (m, 1H), 2.10-2.23 (m, 1H), 2.53-2.75 (m, 4H), 5.11
d, J ) 11.5 Hz, 1H), 5.11 (d, J ) 15.7 Hz, 1H), 5.71-5.86 (m,
H), 7.15-7.20 (m, 3H), 7.25-7.31 (m, 2H); 13C NMR (CDCl
δ 22.1, 23.6, 29.9, 40.1, 42.7, 83.4, 118.3, 125.7, 128.3, 128.4,
133.0, 141.9, 170.2; elemental analysis calcd (%) for C15
: C 77.55, H 8.68; found C 77.26, H 8.70.
Bi(OTf) -Ca ta lyzed Ben zoyla tion of P h en eth yl Alcoh ol
1) (r ep r esen ta tive p r oced u r e). To a flame-dried round-
bottomed flask were added CH Cl (3 mL), phenethyl alcohol
(122.2 mg, 1.0 mmol), (PhCO) O (339.3 mL, 1.5 mmol), and
(
(
29) Strazzolini, P.; Giumanini, A. G.; Verardo, G. Tetrahedron 1994,
1
3
)
5
0, 217.
(
30) Kunieda, N.; Suzuki, A.; Kinoshita, M. Bull. Chem. Soc. J pn.
1
981, 54, 1143.
-
(
(
(
(
(
31) Oku, A.; Harada, T.; Kita, K. Tetrahedron Lett. 1982, 23, 681.
32) Marchon, J . C.; Ramasseul, R. Synthesis 1989, 389.
33) Baldwin, S. W.; Haut, S. A. J . Org. Chem. 1975, 40, 3885.
34) Otera, J .; Dan-oh, N.; Nozaki, H. J . Org. Chem. 1991, 56, 5307.
35) Pragnacharyulu, P. V. P.; Abushanab, E. Tetrahedron Lett.
20 2
H O
3
(
2
2
1
997, 38, 7025.
2