Beesu and Periasamy
JOCArticle
NMR δ 8.03-8.01 (m, 2H), 7.61-7.55 (m, 3H), 2.66 (s, 3H); 13
C
(M - 1). Anal. Calcd for C14H16O2Si: C 68.81, H 6.60. Found: C
68.75, H 6.64.
NMR δ 198.4 (C, CdO), 196.9 (C, CdO), 193.7 (C), 191.3 (C),
133.5 (CH), 129.5 (2 ꢀ CH), 128.6 (2 ꢀ CH), 128.5 (C), 12.5
(CH3); MS (EI) m/z 173 (M þ 1). Anal. Calcd for C11H8O2: C
76.73, H 4.68. Found: C 76.66, H 4.70.
2d. TLC (10% EtOAc/hexanes Rf = 0.40); mp 64-66 °C
(lit.12e mp 62 °C); IR (KBr) νmax 1778, 1755 cm-1; 1H NMR δ
8.01-7.99 (m, 2H), 7.62-7.54 (m, 3H), 3.08 (q, J = 7.6 Hz, 2H),
1.43 (t, J=7.6 Hz, 3H); 13C NMR δ 198.7 (C, CdO), 198.3 (C,
CdO), 197.5 (C), 190.3 (C), 133.5 (CH), 129.5 (2 ꢀ CH), 128.5
(2 ꢀ CH), 128.4 (C), 21.1 (CH2), 10.3 (CH3); MS (EI) m/z 187
(M þ 1). Anal. Calcd for C12H10O2: C 77.40, H 5.41. Found: C
77.51, H 5.42.
2l. TLC (10% EtOAc/hexanes Rf=0.40); mp 99-101 °C; IR
(KBr) νmax 1763 cm-1 1H NMR δ 7.92-7.89 (m, 1H),
;
7.57-7.52 (m, 1H), 7.13-7.09 (m, 1H), 7.02(d, j=8.4 Hz, 1H),
3.89 (s, 3H), 0.34 (s, 9H); 13C NMR δ 205.4 (C, CdO), 201.4 (C,
CdO), 198.3 (C), 196.8 (C), 156.4 (C), 134.7 (CH), 130.3 (CH),
120.9 (CH), 118.5 (C), 111.2 (CH), 55.2 (CH3, Ar-OCH3),
-1.72 (3 ꢀ CH3, SiMe3); MS (EI) m/z 261 (M þ 1), Anal. Calcd
for C14H16O3Si C 64.58, H 6.19. Found: C 64.51, H 6.22.
2m. TLC (10% EtOAc/hexanes Rf=0.40); mp 102-104 °C
1
(lit.23c mp 114-115 °C); IR (KBr) νmax 1768, 1751 cm-1; H
NMR δ 7.97(d, J = 8 Hz, 2H), 7.04 (d, J = 8 Hz, 2H), 3.90 (s,
3H), 0.45 (s, 9H); 13C NMR δ 200.2 (C, CdO), 198.9 (C, CdO),
198.4 (C), 197.7 (C), 164.1 (C), 131.9 (2 ꢀ CH), 121.9 (C), 114.8
(2 ꢀ CH), 55.6 (CH3, Ar-OCH3), -1.79 (3 ꢀ CH3, SiMe3); MS
(EI) m/z 261 (M þ 1).
2e. TLC (10% EtOAc/hexanes Rf=0.45); mp 60-62 °C; IR
(KBr) νmax 1766 cm-1 1H NMR δ 8.03-8.01 (m, 2H),
;
7.61-7.55 (m, 3H), 3.05 (t, J = 7.2 Hz, 2H), 1.95-1.89 (m,
2H), 1.08 (t, J=7.6 Hz, 3H); 13C NMR δ 198.5 (C, CdO), 197.9
(C, CdO), 197.4 (C), 190.8 (C), 133.5 (CH), 129.5 (2 ꢀ CH),
128.5 (C), 128.4 (2 ꢀ CH), 29.7 (CH2), 19.7 (CH2, CH2CH3) 14.5
(CH3); MS (EI) m/z 201 (M þ 1). Anal. Calcd for C13H12O2:C
77.98, H 6.04. Found: C 77.96, H 6.03.
2n. TLC (10% EtOAc/hexanes Rf=0.57); mp 96-98 °C; IR
(KBr) νmax 1759 cm-1 1H NMR δ 7.93-7.92 (m, 1H),
;
7.83-7.81 (m, 1H), 7.59-7.55 (m, 1H), 7.52-7.48 (m, 1H),
0.47 (s, 9H); 13C NMR δ 204.1 (C, CdO), 199.9 (C, CdO), 197.8
(C), 197.1 (C), 135.4 (C), 133.2 (CH), 130.6 (CH), 130.5 (C),
129.1 (CH), 127.3 (CH), -1.84 (3 ꢀ CH3, SiMe3); MS (EI) m/z
265 (M þ 1), Anal. Calcd for C13H13ClO2Si: C 58.97, H 4.95.
Found: C 58.85, H 4.91.
2f. TLC (10% EtOAc/hexanes Rf=0.50); mp 49-51 °C ; IR
(KBr) νmax 1768 cm-1 1H NMR δ 8.01-7.99(m, 2H),
;
7.57-7.55 (m, 3H), 3.04 (t, J = 7.2 Hz, 2H), 1.86-1.81 (m,
2H), 1.50-1.44 (m, 2H) 0.97 (t, J=6.8 Hz, 3H); 13C NMR δ
198.5 (C, CdO), 198.1 (C, CdO), 197.4 (C), 190.6 (C), 133.5
(CH), 129.5 (2 ꢀ CH), 128.5 (C), 128.4 (2 ꢀ CH), 28.1 (CH2),
27.5 (CH2), 23.1 (CH2), 13.7 (CH3); MS (EI) m/z 215 (M þ 1).
Anal. Calcd for C14H14O2:C 78.48, H 6.59. Found: C 78.48, H
6.55.
2o. TLC (10% EtOAc/hexanes Rf=0.50); mp 100-102 °C; IR
(KBr) νmax 1768 cm-1 1H NMR δ 8.05-7.80 (m, 3H),
;
7.62-7.53 (m, 4H), 0.34 (s, 9H); 13C NMR δ 207.9 (C, CdO),
203.8 (C, CdO), 200.6 (C), 197.4 (C), 133.6 (C), 132.5 (CH),
129.6 (C), 128.7 (CH), 127.4 (CH), 127.1 (C), 127.0 (CH), 126.9
(CH), 125.4 (CH), 124.9 (CH), -2.0 (3 ꢀ CH3, SiMe3); MS (EI)
m/z 281 (M þ 1). Anal. Calcd for C17H16O2Si: C 72.82%, 5.75.
Found: C 72.88, H 5.71.
2g. TLC (10% EtOAc/hexanes Rf=0.45); mp 116-118 °C; IR
(KBr) νmax 2189, 1778, 1765 cm-1; 1H NMR δ 8.29-7.45 (m, 10
H); 13C NMR; δ 198.1 (C, CdO), 192.8 (C, CdO), 187.9 (C),
172.9 (C), 134.6 (CH), 132.4 (2 ꢀ CH),131.4 (CH), 130.9 (2 ꢀ
CH), 129.4 (2 ꢀ CH), 129.1 (2 ꢀ CH), 128.8 (C), 124.7 (C), 120.7
(C), 78.3 (C); MS (EI) m/z 259 (M þ 1). Anal. Calcd for
C18H10O2:C 83.71, H 3.90. Found: C 83.63, H 3.92.
2p. TLC (10% EtOAc/hexanes Rf = 0.50); IR (neat) νmax
1779 cm-1; 1H NMR δ 2.42 (s, 3H), 0.33 (s, 9H); 13C NMR δ
208.7 (C, CdO), 207.2 (C, CdO), 201.2 (C), 200.1 (C), 13.1
(CH3), -2.31(3 ꢀ CH3, SiMe3); MS (EI) m/z 169 (M þ 1).23a
2q. TLC (10% EtOAc/hexanes Rf = 0.42); IR (neat) νmax
1766 cm-1; 1H NMR δ 2.69 (q, J = 7.6 Hz, 4H), 1.22 (t, J = 7.6
Hz, 6H); 13C NMR δ 203.1 (2 ꢀ C, CdO), 199.5 (2 ꢀ C), 19.9
(2 ꢀ CH2), 10.3 (2 ꢀ CH3); MS (EI) m/z 139 (M þ 1).23d
2r. TLC (10% EtOAc/hexanes Rf = 0.50); IR (neat) νmax
1768 cm-1; 1H NMR δ 2.67 (t, J=6 Hz, 4H), 1.67-1.62 (m, 4H),
1.36-1.31 (m, 4H), 0. 89 (t, J=8 Hz, 6H); 13C NMR δ 202.9 (2 ꢀ
C, CdO), 199.7 (2 ꢀ C), 28.0 (2 ꢀ CH2), 26.2 (2 ꢀ CH2), 22.7
(2 ꢀ CH2), 13.5 (2 ꢀ CH3); MS (EI) m/z 193 (M - 1).23b
Preparation of Acyloxyferrole Complex 7. Fe(CO)5 (2.9 g, 15
mmol) was added dropwise to a solution of anhydrous t-BuOK
(1.68 g, 15 mmol) in THF (70 mL) at 25 °C under dry nitrogen.
Then the reaction mixture was stirred for another 2 h at 70 °C
and brought slowly to room temperature. Diphenylacetylene
(0.44 g, 2.5 mmol) was added and further stirred for 2 h at room
temperature. Then Et3N (2.1 mL, 15 mmol) and CH3COCl
(1 mL, 15 mmol) were added, and the contents were further stirred
for 10 h. Ether (100 mL) was added, and the reaction mixture
was washed successively with H2O (40 mL) and brine (2 ꢀ 50
mL), dried over Na2SO4, and concentrated under reduced
pressure. The residue was subjected to column chromatography
(silica gel, hexane-EtOAc). Ethyl acetate (2.5%) in hexane
eluted the ferroyl complex 7. This complex is relatively stable
but long time standing or exposure to an atmosphere leads to
decomposition. TLC (10% EtOAc/hexanes Rf = 0.45); mp
140-142 °C (dec); IR (KBr) νmax 2077, 2038, 2000, 1780
cm-1; 1H NMR δ 7.21-6.83 (m, 10 H), 2.20 (s, 3 H), 2.09 (s, 3
H); 13C NMR δ 212.1 (3 ꢀ C, CdO), 209.0 (C, CdO), 204.5 (C,
CdO), 204.2 (C, CdO), 178.5 (C), 167.4 (C, O-CdO), 167.0 (C,
O-CdO), 159.4 (C), 147.7 (C), 134.3 (C), 131.6 (C), 129.6 (CH),
128.5 (CH), 128.0 (CH), 127.7 (CH), 127.5 (CH), 126.2 (CH),
2h. TLC (10% EtOAc/hexanes Rf = 0.45); IR (neat) νmax
1
1784 cm-1; H NMR δ 9.24 (s, 1H), 2.73 (t, J=7.2 Hz, 2H),
1.68-1.61 (m, 2H), 1.34-1.23 (m, 6H), 0.80 (t, J=7.2 Hz, 3H);
13C NMR δ 208.3 (C, CdO), 200.0 (C, CdO), 196.7 (C), 184.9
(CH), 31.1 (CH2), 28.8 (CH2), 27.4 (CH2), 25.7(CH2), 22.2
(CH2), 13.8 (CH3); MS (EI) m/z 167 (M þ 1).
2i. TLC (10% EtOAc/hexanes Rf=0.50); IR (neat) νmax 1786
cm-1; 1H NMR δ 9.29 (s, 1H), 2.80 (t, J=7.6 Hz, 2H), 1.76-1.69
(m, 2H), 1.40-1.28 (m, 10H), 0.88 (t, J=6.8 Hz, 3H); 13C NMR
δ 208.3 (C, CdO), 200.0 (C, CdO), 196.6 (C), 184.9 (CH),
31.6 (CH2), 29.2 (CH2), 29 (CH2), 28.9 (CH2), 27.4 (CH2),
25.9 (CH2), 22.5 (CH2), 13.9 (CH3); MS (EI) m/z 195
(M þ 1).
2j. TLC (10% EtOAc/hexanes Rf =0.55); mp 101-102 °C
(lit.11a mp 102.8-103.2 °C); IR (KBr) νmax 1774, 1766 cm-1; 1H
NMR δ 7.96-7.94 (m, 2H), 7.60-7.55 (m, 3H), 0.46 (s, 9H); 13
C
NMR δ 202.6 (C, CdO), 200.4 (C, CdO), 199.3 (C), 197.9 (C),
133.6 (CH), 129.5 (2 ꢀ CH), 129.3 (2 ꢀ CH), 129.1 (C), -1.83
(3 ꢀ CH3, SiMe3); MS (EI) m/z 231 (M þ 1).
2k. TLC (10% EtOAc/hexanes Rf = 0.55); mp 80-82 °C
(lit.23c mp 89-90 °C); IR (KBr) νmax 1761 cm-1; H NMR δ
1
7.88(d, J = 8 Hz, 2H), 7.37 (d, J=8 Hz, 2H), 2.46 (s, 3H), 0.46 (s,
9H); 13C NMR δ 201.1 (C, CdO), 200.5 (C, CdO), 199.0 (C),
198.2 (C), 144.9 (C), 130.1 (2 ꢀ CH), 129.7 (2 ꢀ CH), 126.5 (C),
22.01(CH3, Ar-CH3), -1.8 (3 ꢀ CH3, SiMe3); MS (EI) m/z 243
(23) (a) Allen, A. D.; Lai, W. Y.; Ma, J.; Tidwell, T. T. J. Am. Chem. Soc.
1994, 116, 2625. (b) D. J. Moore, H. W. J. Org. Chem. 1989, 54, 5444.
(c) Ronghua, L.; Thomas, T. J. Chem. Soc., Perkin Trans. 2 1996, 2757.
(d) Parker, M. S. A.; Rizzo, C. J. Synth. Commun. 1995, 25, 2781.
548 J. Org. Chem. Vol. 76, No. 2, 2011