Nucleophilic Additions of Arylzinc Compounds
J . Org. Chem., Vol. 65, No. 4, 2000 1035
(d, J ) 4 Hz, 1H), 6.9 (d, J ) 4 Hz, 1H), 7.4-7.9 (m, 4H); 13C
NMR δ 76.6, 113.8, 122.1, 124.9, 127.4, 129.0, 129.1, 133.5,
139.6, 147.0, 168.3. Anal. Calcd for C12H7BrO2S: C, 48.83; H,
2.39. Found: C, 48.53; H, 2.72.
7.9 (m, 4H); 13C NMR δ 15.8, 18.7, 32.5, 85.7, 122.2, 125.8,
126.9, 129.1, 133.9, 149.0, 176.1.
3-(ter t-Bu t yl)-1(3H )-isob en zofu r a n on e (7a ): oil;17 IR
(CDCl3) 1766 cm-1; 1H NMR δ 1.0 (s, 9H), 5.6 (s, 1H), 7.6-7.9
(m, 4H); 13C NMR δ 25.5, 35.7, 88.6, 123.4, 125.6, 127.2, 129.0,
133.4, 148.0, 170.5.
Meth od B. CrCl3 (143 mg, 1.1 mmol) was dried by air-gun
heating for 5 min under vacuum (1 mmHg). To the solid were
successively added 2b (131 mg, 1.0 mmol), a 0.75 M TMU
solution of 1c (1.33 mL, 1.0 mmol), and TMSCl (0.38 mL, 3.0
mmol) at room temperature under nitrogen and stirred for 8
h at the temperature. The resulting mixture was quenched
by addition of aqueous HCl. Workup by extraction with ether,
washing with water, drying with MgSO4, and evaporation of
the solvent afforded a crude product, which was chromato-
graphed on silica gel with hexane/ethyl acetate (19/1) as eluent
to afford 184 mg of 4-[(2-fluorophenyl)hydroxymethyl]ben-
3-Eth yl-1(3H)-isoben zofu r a n on e (7c): oil;16 IR (CDCl3)
1
1760 cm-1; H NMR δ 1.0 (t, J ) 8 Hz, 3H), 1.7-2.2 (m, 2H),
5.4 (dd, J ) 7 and 5 Hz, 1H), 7.4-7.9 (m, 4H); 13C NMR δ 8.9,
27.8, 82.3, 121.8, 125.8, 126.4, 129.1, 134.0, 149.8, 170.6.
3-Cycloh exyl-1(3H)-isoben zofu r a n on e (7d ): mp 98-99
°C (lit.18 mp 98-99 °C); IR (CDCl3) 1760 cm-1; 1H NMR δ 1.1-
1.9 (m, 11H), 5.3 (d, J ) 4 Hz, 1H), 7.4-7.9 (m, 4H); 13C NMR
δ 25.9, 26.1, 26.2, 29.2, 42.2, 85.3, 122.2, 125.6, 126.8, 129.0,
133.8, 148.8, 170.7.
zenecarbonitrile, 4a (81%): oil; IR (CDCl3) 2228, 3606 cm-1
;
3-(P h en yleth yl)-1(3H)-isoben zofu r a n on e (7e) (∼1/1 dia-
stereomers): mp 79-80 °C; IR (CDCl3) 1760 cm-1; 1H NMR δ
1.4 (d, J ) 7 Hz, 3H), 3.1 (quint, J ) 7 Hz, 1H), 5.6 (d, J ) 7
Hz, 1H), 6.6-6.7 (m, 1H), 7.3-7.5 (m, 7H), 7.8-7.9 (m, 1H);
13C NMR δ 17.4, 45.2, 84.9, 122.8, 125.6, 126.5, 127.4, 128.2,
128.8, 129.2, 133.6, 141.8, 148.7, 170.5. Anal. Calcd for
C16H14O2: C, 80.65; H, 5.92. Found: C, 80.42; H, 5.89. mp
106.5-107 °C; IR (CDCl3) 1762 cm-1; 1H NMR δ 1.4 (d, J ) 7
Hz, 3H), 3.4-3.7 (m, 1H), 5.7 (d, J ) 4 Hz, 1H), 7.0-7.8 (m,
9H); 13C NMR δ 15.5, 43.0, 84.8, 122.7, 125.5, 127.0, 127.2,
128.4, 128.4, 129.1, 133.4, 139.1, 147.9, 170.4. Anal. Calcd for
1H NMR δ 3.1 (s, 1H), 6.1 (s, 1H), 6.9-7.5 (m, 8H); 13C NMR
δ 69.1 (d, J ) 3 Hz), 111.1, 115.6 (d, J ) 21 Hz), 118.7, 124.6
(d, J ) 3 Hz), 127.0 (d, J ) 2 Hz), 127.7 (d, J ) 4 Hz), 129.7
(d, J ) 8 Hz), 130.1 (d, J ) 13 Hz), 132.2, 148.2, 159.7 (d, J )
247 Hz). Anal. Calcd for C14H10FNO: C, 74.00; H, 4.44; N, 6.16.
Found: C, 74.12; H, 4.54; N, 6.31.
(4-Br om op h en yl)(4-n itr op h en yl)m eth a n -1-ol (4b): mp
158-159 °C; IR (Nujol) 1341, 1505, 3492 cm-1 1H NMR
;
(DMSO-d6) δ 5.9 (d, J ) 4 Hz, 1H), 6.3 (d, J ) 4 Hz, 1H), 7.4
(d, J ) 9 Hz, 2H), 7.5 (d, J ) 9 Hz, 2H), 7.7 (d, J ) 9 Hz, 2H),
8.2 (d, J ) 9 Hz, 2H); 13C NMR (DMSO-d6) δ 72.9, 120.4, 123.6,
C
16H14O2: C, 80.65; H, 5.92. Found: C, 80.60; H, 5.99.
127.4, 128.7, 131.3, 144.0, 146.6, 152.8. Anal. Calcd for C13H10
-
3-(Meth ylp r op yl)-1(3H)-isoben zofu r a n on e (∼4/5: dia-
stereomeric mixture) (7f): oil; IR (CDCl3) 1760 cm-1; 1H NMR
δ 0.6-2.0 (m, 9H), 5.4-5.5 (m, 1H), 7.4-7.9 (m, 4H); 13C NMR
δ 11.7, 11.8, 12.3, 14.9, 23.5, 26.3, 38.9, 84.1, 85.2, 121.9, 122.4,
125.6, 125.6, 126.7, 127.0, 129.0, 129.0, 133.8, 133.9, 148.7,
149.3, 170.7, 170.9; HRFAB-MS calcd for C12H15O2 191.1072,
found (M + H)+ 191.1058.
BrO3: C, 50.67; H, 3.27; N, 4.55. Found: C, 50.72; H, 3.20; N,
4.74.
4-[(3-Ch lor op h e n yl)h yd r oxym e t h yl]b e n ze n e ca r b o-
1
n itr ile (4c): mp 74-75 °C; IR (CDCl3) 2240, 3460 cm-1; H
NMR δ 2.9 (s, 1H), 5.8 (s, 1H), 7.2-7.7 (m, 8H); 13C NMR δ
75.0, 111.5, 118.7, 124.8, 126.8, 127.1, 128.4, 130.1, 132.4,
134.8, 144.8, 148.3. Anal. Calcd for C14H10ClNO: C, 69.00; H,
4.14; N, 5.75. Found: C, 68.85; H, 4.13; N, 5.77.
Meth od C w ith TMSCl. CrCl3 (130 mg, 1.0 mmol) was
dried by air-gun heating for 5 min under vacuum (1 mmHg).
To the solid was added 0.60 M TMU solution of 1f (1.67 mL,
1.0 mmol) at 10 °C under nitrogen and stirred for 8 h at the
temperature. To the resulting solution were successively added
6c (0.072 mL, 1.0 mmol) and TMSCl (0.25 mL, 2.0 mmol) at
room temperature and stirred overnight at the temperature.
The resulting mixture was quenched by addition of aqueous
HCl. Workup by extraction with ether, washing with water,
drying with MgSO4, and evaporation of the solvent afforded a
crude product, which was chromatographed on silica gel with
hexane/ethyl acetate (19/1) as eluent to afford 160 mg of
methyl 3-(1-hydroxypropyl)benzoate, 8a (82%): oil; IR (CDCl3)
Met h yl 3-[(4-cya n op h en yl)h yd r oxym et h yl]b en zoa t e
1
(4d ): mp 105-106 °C; IR (CDCl3) 1720, 2228, 3602 cm-1; H
NMR δ 3.3 (d, J ) 3 Hz, 1H), 3.9 (s, 3H), 5.9 (d, J ) 3 Hz, 1H),
7.3-8.0 (m, 8H); 13C NMR δ 52.3, 75.1, 111.3, 118.7, 127.1,
127.7, 128.9, 129.2, 130.6, 131.1, 132.3, 143.4, 148.6, 166.8.
Anal. Calcd for C16H13NO3: C, 71.90 H; 4.90; N, 5.24. Found:
C, 71.53; H, 4.90; N, 5.20.
Met h yl 4-[(4-cya n op h en yl)h yd r oxym et h yl]b en zoa t e
(4e): mp 152-153 °C; IR (Nujol) 1718, 2225, 3532 cm-1 1H
;
NMR δ 3.1 (d, J ) 3 Hz, 1H), 3.9 (s, 3H), 5.9 (d, J ) 3 Hz, 1H),
7.4 (d, J ) 9 Hz, 2H), 7.5 (d, J ) 6 Hz, 2H), 7.6 (d, J ) 6 Hz,
2H), 8.0 (d, J ) 9 Hz, 2H); 13C NMR δ 52.2, 75.2, 111.5, 118.7,
126.5, 127.2, 129.8, 130.1, 132.4, 147.7, 148.4, 166.8. Anal.
Calcd for C16H13NO3: C, 71.90; H, 4.90; N, 5.24. Found: C,
71.85; H, 4.88; N, 5.31.
1
1718, 3614 cm-1; H NMR δ 0.9 (t, J ) 7 Hz, 3H), 1.7 (quint,
J ) 7 Hz, 2H), 3.0 (s, 1H), 3.9 (s, 3H), 4.6 (t, J ) 7 Hz, 1H),
7.3-8.0 (m, 4H); 13C NMR δ 9.9, 31.9, 52.0, 75.3, 127.1, 128.3,
128.5, 130.1, 130.5, 145.2, 167.1; HRFAB-MS calcd for C11H15O3
195.1021, found (M + H)+ 195.1036.
4-(Hyd r oxyp h en yl)m eth ylp h en yl p h en yl k eton e (4f):
oil; IR (CDCl3) 1659, 3610 cm-1; 1H NMR δ 2.8 (s, 1H), 5.8 (s,
1H), 7.2-7.8 (m, 14H); 13C NMR δ 75.8, 126.2, 126.6, 127.8,
128.2, 128.6, 129.9, 130.2, 132.3, 136.5, 137.6, 143.3, 148.4,
196.4; HRFAB-MS calcd for C20H17O2 289.1229, found (M +
H)+ 289.1236.
Meth yl 3-(1-h yd r oxy-2-m eth ylp r op yl)ben zoa te (8b): oil;
IR (CDCl3) 1720, 3610 cm-1; 1H NMR δ 0.8 (d, J ) 7 Hz, 3H),
1.0 (d, J ) 7 Hz, 3H), 1.6-2.2 (m, 2H), 3.9 (s, 3H), 4.5 (d, J )
7 Hz, 1H), 7.3-7.6 (m, 2H), 7.9-8.0 (m, 2H); 13C NMR δ 18.0,
19.1, 35.4, 52.2, 79.5, 127.8, 128.3, 128.7, 130.2, 131.1, 144,2,
167.2; HRFAB-MS calcd for C12H17O3 209.1178, found (M +
H)+ 209.1137.
1-(4-Br om op h en yl)-2-m eth yl-1-bu ta n ol (∼3/5: diastereo-
meric mixture) (8c): oil; IR (CDCl3) 3614 cm-1; 1H NMR δ 0.7-
1.8 (m, 9H), 2.0 (s, 1H), 4.4 (t, J ) 7 Hz, 1H), 7.2 (d, J ) 8 Hz,
2H), 7.4 (d, J ) 8 Hz, 2H); 13C NMR δ 11.4, 11.7, 13.8, 15.1,
24.8, 25.9, 41.8, 42.1, 77.3, 78.2, 121.0, 121.2, 128.2, 128.5,
131.3, 141.6, 143.0. Anal. Calcd for C11H15BrO: C, 54.34; H,
6.22. Found: C, 54.33; H, 6.16.
Meth od C. CrCl3 (130 mg, 1.0 mmol) was dried by air-gun
heating for 5 min under vacuum (1 mmHg). To the solid was
added a 0.8 M TMU solution of 1a (1.25 mL, 1.0 mmol) at room
temperature under nitrogen and stirred for 6 h at the tem-
perature. To the resulting solution was added 6b (0.182 mL,
2.0 mmol) and stirred overnight at the same temperature. The
resulting mixture was quenched by addition of aqueous HCl.
Workup by extraction with ether, washing with water, drying
with MgSO4, and evaporation of the solvent afforded a crude
product, which was chromatographed on silica gel with hexane/
ethyl acetate (19/1) as eluent to afford 271 mg of 3-(methyl-
ethyl)-1(3H)-isobenzofuranone, 7b (77%): oil (lit.16 mp 36 °C);
Meth od D. CrCl3 (130 mg, 1.0 mmol) was dried by air-gun
heating for 5 min under vacuum (1 mmHg). To the solid were
successively added 2b (157 mg, 1.2 mmol) and a 0.75 M TMU
solution of 1c (1.33 mL, 1.0 mmol) at room temperature under
nitrogen and stirred for 8 h at the temperature. After 2a (0.31
1
IR (CDCl3) 1760 cm-1; H NMR δ 0.81 (d, J ) 7 Hz, 3H), 1.2
(d, J ) 7 Hz, 3H), 2.1-2.5 (m, 1H), 5.4 (d, J ) 4 Hz, 1H), 7.4-
(17) Smith, J . G.; Wikman, R. T. Tetrahedron 1974, 30, 2603.
(18) Berti, G.; Marsili, A.; Mini, V. Ann. Chim. 1960, 50, 669.
(16) Tasman, A. Rec. Trav. Chim. 1927, 46, 653.