Heteroatom Chemistry
3
Me
O
H
H
OEt
H
S
MeO
O
O
O
O
Bi Tol
I
X
X
Bi Tol
I
Bi Tol
I
Bi Tol
Bi Tol
I
I
2a: X = H
5a: X = F
6a: X = H
7a: X = F
8a
10a
9a
Scheme 3: Hypervalent iodobismuthanes functionalized with a carbonyl group.
2.2. 2-Iodobenzaldehyde. Yield 99% (574 mg, 2.48 mmol),
mL). Te combined extracts were concentrated to leave
an oily residue, which was chromatographed on silica gel
with hexane–ethyl acetate (5:1) to aford the corresponding
iodobismuthane.
1
Colorless solid, mp 39–41∘C. H NMR (400 MHz, CDCl ):
3
ꢀ 7.29 (1H, dt, J = 7.6 Hz, 1.6 Hz), 7.47 (1H, t, J = 7.6 Hz), 7.89
(1H, dd, J = 7.6 Hz, 1.6 Hz), 7.96 (1H, d, J = 8.0 Hz), 10.08 (1H,
s).
2.8. (2-Acetylphenyl)iodo(4-methylphenyl)bismuthane 2a.
Yellow crystal, Yield 35% (191 mg, 0.35 mmol), mp 160–162∘C.
2.3. 4-Fluoro-2-Iodobenzaldehyde. Yield 97% (606 mg, 2.43
1H NMR (400 MHz, CDCl ): ꢀ 2.25 (3H, s), 2.69 (3H, s),
mmol), Colorless solid, mp 49–51∘C. H NMR (400 MHz,
1
3
7. 2 5 (2H, d, J = 8.0 Hz), 7.71 (1H, dt, J = 7.6 Hz, 1.2 Hz), 7.88
(1H, dt, J = 7.6 Hz, 1.2 Hz), 8.07 (2H, d, J = 8.0 Hz), 8.22 (1H,
dd, J = 7.6 Hz, 1.2 Hz), 9.41 (1H, dd, J = 7.2 Hz, 0.8 Hz). 13C
CDCl ): ꢀ 7.19 (1H, m), 7.68 (1H, m), 7.91 (1H, m), 9.99 (1H,
3
d, J = 2.4 Hz).
NMR (100 MHz, CDCl ): ꢀ 21.54, 27.08, 128.50, 132.36, 134.51,
2.4. 2-Iodo-5-Methoxybenzaldehyde. Yield 98% (642 mg,
3
2.45 mmol), Colorless solid, mp 113–116∘C. H NMR (400
1
138.01, 138.21, 138.98, 143.10, 145.55, 166.78, 172.09, 207.54. IR
(KBr): ] 3738, 3037, 1622, 1552, 1276 and 761 cm−1. HRMS
MHz, CDCl ): ꢀ 3.84 (3H, s), 6.92 (1H, dd, J = 8.4 Hz, 3.2
3
(APCI) calcd. for C H BiIO: [M–H]− 544.9832. found:
15 13
Hz), 7.43 (1H, d, J = 3.2 Hz), 7.80 (1H, d, J = 8.4 Hz), 10.02 (1H,
544.9821.
s).
2.5. 4ꢀ-Fluoro-2ꢀ-Iodoacetophenone. Yield 98% (647 mg, 2.45
2.9.
(2-Acetyl-5-fuorophenyl)iodo(4-methylphenyl)bismu-
mmol), Colorless solid, mp 45–46∘C. H NMR (400 MHz,
1
thane 5a. Yellow crystal, Yield 28% (158 mg, 0.28 mmol), mp
186–188∘C. H NMR (400 MHz, DMSO-d ): ꢀ 2.19 (3H, s),
1
CDCl ): ꢀ 2.59 (3H, s), 7.11 (1H, m), 7.52 (1H, m), 7.65 (1H, m).
6
3
2.72 (3H, s), 7.29 (2H, d, J = 7.6 Hz), 7.54 (1H, dt, J = 8.4 Hz,
2.0 Hz), 8.11 (2H, d, J = 7.6 Hz), 8.55 (1H, dd, J = 8.4 Hz, 4.8
2.6. 3-Iodothiophene-2-Carboxaldehyde. Yield 99% (589 mg,
Hz), 8.89 (1H, br-s). 13C NMR (100 MHz, DMSO-d ): ꢀ 21.13,
2.48 mmol), Colorless solid, mp 82–85∘C. H NMR (400
1
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27.48, 115.62 (d, J = 22.6 Hz), 130.94 (br-d), 132.08(×2), 137.09,
138.45, 138.85 (d, J = 8.0 Hz), 140.51, 169.52, 172.12, 207.85.
IR (KBr): ] 1620, 1575, 1558, 1358, 1299, 1262 and 1201 cm−1.
MHz, CDCl ): ꢀ 7. 28 (1H, d, J = 4.8 Hz), 7.70 (1H, dd, J = 4.8
3
Hz, 1.2 Hz), 9.83 (1H, d, J = 1.2 Hz).
HRMS (APCI) calcd. for C H BiFIO: [M–H]− 562.9730.
15 12
2.7. Typical Procedure for the Synthesis of Aryl(iodo)(4-
found: 562.9726.
methylphenyl)bismuthane. To
a
round-bottomed fask
(50 mL) equipped with a magnetic stir bar were added
bismuth(III) chloride (422 mg, 1.33 mmol) and tris(4-
methylphenyl)bismuthane (323 mg, 0.67 mmol). Afer
dry diethyl ether (6 mL) was added to the fask at room
temperature, the mixture was stirred for 1 h. To another
round-bottomed fask (50 mL) were added iodoarene (1
mmol), zinc powder (262 mg, 4 mmol), and dry DMF (5
mL). Te fask was set in an ultrasonic water bath at room
temperature (25∘C) and the resulting mixture was sonicated
for 1.5–4 h, during which time the water bath temperature
rose to 48∘C. Te sonication was stopped and unreacted
zinc powder precipitated. Te resulting supernatant solution
containing an arylzinc reagent was slowly transferred to the
suspension of dichloro(4-methylphenyl)bismuthane (ca. 2
mmol) thus formed, and the resulting mixture was stirred
for 3.5–8 h at room temperature. Te reaction was quenched
with a saturated aqueous solution of NaI (3 mL) and the
resulting mixture was extracted with ethyl acetate (3 × 50
2.10. (2-Formylphenyl)iodo(4-methylphenyl)bismuthane 6a.
Yellow crystal, Yield 56% (298 mg, 0.56 mmol), mp
143–144∘C. H NMR (400 MHz, DMSO-d ): ꢀ 2.21 (3H, s),
1
6
7. 3 0 (2H, d, J = 7.6 Hz), 7.86 (1H, t, J = 7.2 Hz), 7.95 (1H, t, J
= 7.2 Hz), 8.14 (2H, d, J = 7.6 Hz), 8.44 (1H, d, J = 7.2 Hz),
9.02 (1H, d, J = 7.2 Hz), 10.75 (1H, s). 13C NMR (100 MHz,
CDCl ): ꢀ 21.55, 128.65, 132.47, 137.58, 138.23, 138.44, 139.63,
3
143.66, 146.16, 165.99, 170.92, 199.50. IR (KBr): ] 3058, 2857,
1633, 1572, 1553, 1296 and 1207 cm−1. HRMS (APCI) calcd.
for C H BiIO: [M+H]+ 532.9808. found: 532.9810.
14 13
2.11. (2-Formyl-5-fuorophenyl)iodo(4-methylphenyl)bismu-
thane 7a. Yellow crystal, Yield 29% (195 mg, 0.29 mmol), mp
148–149∘C. H NMR (400 MHz, DMSO-d ): ꢀ 2.21 (3H, s),
1
6
7. 32 (2H, d, J = 7.6 Hz), 7.61 (1H, dt, J = 8.4 Hz, 2.4 Hz), 8.18
(2H, d, J = 7.6 Hz), 8.52 (1H, dd, J = 8.0 Hz, 5.2 Hz), 8.74 (1H,
d, J = 6.4 Hz), 10.74 (1H, s). 13C NMR (100 MHz, DMSO-d ):
6