PAPER
One-Pot a-Tosyloxylation of Ketones
1231
a-Tosyloxypropiophenone (2h)
1H NMR (500 MHz, CDCl3): d = 1.03 (t, J = 7.3 Hz, 3 H), 2.44 (s,
3 H), 2.51 (q, J = 7.3 Hz, 2 H), 4.49 (s, 2 H), 7.35 (d, J = 8.2 Hz, 2
H), 7.79 (dd, J = 8.4, 2.8 Hz, 2 H).
13C NMR (125 MHz, CDCl3): d = 9.34, 21.69, 29.46, 80.68, 128.46,
130.05, 145.54, 207.81.
Yield: 228 mg (75%); white solid; mp 68–69 °C (Lit.11 68–69 °C).
1H NMR (500 MHz, CDCl3): d = 1.59 (d, J = 7.0 Hz, 3 H), 2.40 (s,
3 H), 5.79 (q, J = 7.0 Hz, 1 H), 7.26 (d, J = 8.5 Hz, 2 H), 7.45 (t,
J = 7.8 Hz, 2 H), 7.59 (t, J = 7.5 Hz, 1 H), 7.75 (d, J = 8.3 Hz, 2 H),
7.88 (d, J = 8.1 Hz, 2 H).
13C NMR (125 MHz, CDCl3): d = 18.73, 21.62, 77.38, 127.95,
128.75, 129.76, 133.50, 133.74, 133.82, 145.01, 194.83.
g-Tosyloxybutanone (2p)16
Yield: 29% (NMR); yellow oil.
1H NMR (500 MHz, CDCl3): d = 1.33 (d, J = 7.0 Hz, 3 H), 2.19 (s,
3 H), 2.44 (s, 3 H), 4.74 (q, J = 7.0 Hz, 1 H), 7.35 (d, J = 8.2 Hz, 2
H), 7.79 (dd, J = 8.4, 2.8 Hz, 2 H).
13C NMR (125 MHz, CDCl3): d = 21.66, 26.53, 80.34, 128.18,
132.02, 140.12, 145.90, 207.81.
p-Chloro-a-tosyloxypropiophenone (2i)
Yield: 247 mg (73%); white solid; mp 100–101 °C (Lit.13 94–
96 °C).
1H NMR (500 MHz, CDCl3): d = 1.60 (d, J = 6.9 Hz, 3 H), 2.44 (s,
3 H), 5.70 (q, J = 7.0 Hz, 1 H), 7.29 (d, J = 8.2 Hz, 2 H), 7.43–7.46
(m, 2 H), 7.75 (d, J = 8.3 Hz, 2 H), 7.84–7.86 (m, 2 H).
a-Mesyloxyacetophenone (3a)
Yield: 45 mg (21%); red solid; mp 81–82 °C (Lit.17 80–82 °C).
13C NMR (125 MHz, CDCl3): d = 18.56, 21.64, 77.25, 127.93,
129.10, 129.81, 130.24, 132.01, 133.36, 140.41, 145.18, 193.86.
1H NMR (500 MHz, CDCl3): d = 3.30 (s, 3 H), 5.53 (s, 2 H), 7.53
(t, J = 7.8 Hz, 2 H), 7.66 (t, J = 7.4 Hz, 1 H), 7.90 (d, J = 7.8 Hz, 2
2-Tosyloxy-1-indanone (2j)
H).
Yield: 166 mg (55%); yellow solid; mp 115–116 °C (Lit.14 110–
112 °C).
13C NMR (125 MHz, CDCl3): d = 39.23, 70.19, 127.80, 129.09,
133.50, 134.46, 191.12.
1H NMR (500 MHz, CDCl3): d = 2.48 (s, 3 H), 3.29 (dd, J = 17.2,
4.8 Hz, 1 H), 3.67 (dd, J = 17.2, 8.0 Hz, 1 H), 5.15 (dd, J = 8.0, 4.7
Hz, 1 H), 7.40–7.46 (m, 4 H), 7.65–7.68 (m, 1 H), 7.75 (d, J = 7.7
Hz, 1 H), 7.94 (d, J = 8.3 Hz, 2 H).
13C NMR (125 MHz, CDCl3): d = 21.70, 33.81, 78.27, 124.60,
126.71, 128.17, 128.41, 129.91, 133.22, 133.57, 136.37, 145.24,
149.94, 197.52.
a-Mesyloxy-p-methylacetophenone (3b)
Yield: 205 mg (90%); white solid; mp 87–88 °C (Lit.17 87 °C).
1H NMR (500 MHz, CDCl3): d = 2.43 (s, 3 H), 3.27 (s, 3 H), 5.48
(s, 2 H), 7.29 (d, J = 8.2 Hz, 2 H), 7.78 (d, J = 8.2 Hz, 2 H).
13C NMR (125 MHz, CDCl3): d = 21.79, 39.22, 70.17, 127.89,
129.76, 131.00, 145.61, 190.68.
2-(a-Tosyloxyacetyl)thiophene (2k)
a-Mesyloxy-p-nitroacetophenone (3c)
Yield: 89 mg (30%); yellow solid; mp 92–93 °C (Lit.7 92–93 °C).
Yield: 73 mg (28%); yellow solid; mp 122–123 °C (Lit.17 123 °C).
1H NMR (500 MHz, CDCl3): d = 2.45 (s, 3 H), 5.10 (s, 2 H), 7.16
(dd, J = 5.0, 3.9 Hz, 1 H), 7.36 (d, J = 8.2 Hz, 2 H), 7.72–7.75 (m,
1 H), 7.79 (dd, J = 3.9, 1.0 Hz, 1 H), 7.85 (d, J = 8.3 Hz, 2 H).
13C NMR (125 MHz, CDCl3): d = 21.68, 69.89, 128.18, 128.47,
129.95, 132.43, 133.15, 135.13, 140.04, 145.44, 183.66.
1H NMR (500 MHz, CDCl3): d = 3.31 (s, 3 H), 5.53 (s, 2 H), 8.09–
8.11 (m, 2 H), 8.37–8.40 (m, 2 H).
13C NMR (125 MHz, CDCl3): d = 39.22, 69.84, 124.28, 129.06,
151.05, 190.07.
a-Mesyloxyacetone (3d)
a-Tosyloxyacetone (2l)
Yield: 46 mg (30%); black solid; mp 96–98 °C (Lit.17 98 °C).
Yield: 192 mg (84%); yellow solid; mp 35–36 °C (Lit.15 35 °C).
1H NMR (500 MHz, CDCl3): d = 2.22 (s, 3 H), 3.19 (s, 3 H), 4.79
(s, 2 H).
13C NMR (125 MHz, CDCl3): d = 25.96, 38.80, 71.75, 200.44.
1H NMR (500 MHz, CDCl3): d = 2.18 (s, 3 H), 2.44 (s, 3 H), 4.48
(s, 2 H), 7.35 (d, J = 8.2 Hz, 2 H), 7.79 (d, J = 8.4 Hz, 2 H).
13C NMR (125 MHz, CDCl3): d = 21.65, 26.49, 72.03, 128.02,
130.05, 132.31, 145.54, 201.03.
a-(Camphorsulfonyloxy)-p-nitroacetophenone (3e)
Yield: 265 mg (67%); yellow solid; mp 96–98 °C.
IR (neat): 746, 1173, 1710, 1746 cm–1.
2-Tosyloxy-3-pentanone (2m)
Yield: 159 mg (62%); black solid; mp 45–46 °C (Lit.7 45–46 °C).
1H NMR (500 MHz, CDCl3): d = 0.86 (s, 3 H), 1.07 (s, 3 H), 1.40–
1.45 (m, 1 H), 1.68–1.74 (m, 1 H), 1.91 (d, J = 18.6 Hz, 1 H), 1.99–
2.05 (m, 1 H), 2.10–2.12 (m, 1 H), 2.32–2.41 (m, 2 H), 3.25 (d,
J = 15.1 Hz, 1 H), 3.72 (d, J = 15.1 Hz, 1 H), 5.56 (d, J = 3.0 Hz, 2
H), 8.09 (d, J = 8.8 Hz, 2 H), 8.30 (d, J = 8.7 Hz, 2 H).
13C NMR (125 MHz, CDCl3): d = 19.58, 25.01, 26.84, 42.45, 42.74,
48.19, 48.48, 58.05, 70.53, 124.11, 129.20, 138.18, 150.81, 190.12,
214.39.
1H NMR (500 MHz, CDCl3): d = 0.96 (t, J = 7.3 Hz, 3 H), 1.29 (d,
J = 7.0 Hz, 3 H), 2.40 (s, 3 H), 2.53–2.57 (m, 2 H), 4.77 (q, J = 7.0
Hz, 1 H), 7.32 (d, J = 8.1 Hz, 2 H), 7.75 (d, J = 8.2 Hz, 2 H).
13C NMR (125 MHz, CDCl3): d = 6.99, 17.60, 21.66, 31.18, 80.68,
127.89, 129.99, 133.80, 145.27, 207.74.
Ethyl 2-Tosyloxyacetoacetate (2n)16
Yield: 276 mg (92%); yellow oil.
1H NMR (500 MHz, CDCl3): d = 1.12 (t, J = 7.2 Hz, 3 H), 2.20 (s,
3 H), 2.37 (s, 3 H), 4.02–4.10 (m, 2 H), 5.15 (s, 1 H), 7.29 (dd,
J = 8.2, 3.9 Hz, 2 H), 7.74 (d, J = 8.4 Hz, 2 H).
MS (ESI): m/z (%) = 396 (100) [M + 1]+.
HRMS–FAB: m/z [M + 1]+ calcd for C18H22NO7S: 396.1117;
found: 396.1109.
13C NMR (125 MHz, CDCl3): d = 6.96, 21.66, 26.55, 62.67, 80.36,
128.18, 129.98, 132.02, 145.90, 163.86, 196.98.
a-(Camphorsulfonyloxy)acetone (3f)18
Yield: 104 mg (36%); yellow oil.
a-Tosyloxybutanone (2o)16
Yield: 10% (NMR); yellow oil.
1H NMR (500 MHz, CDCl3): d = 0.88 (s, 3 H), 1.09 (s, 3 H), 1.43–
1.48 (m, 1 H), 1.70–1.77 (m, 1 H), 1.95 (d, J = 18.5 Hz, 1 H), 2.03–
© Thieme Stuttgart · New York
Synthesis 2012, 44, 1226–1232