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DOI: 10.1055/s-2003-39894
A Remarkable Cycloaddition of Bis(arylsulfonyl)iodonium Ylide with Norbornene Derivatives for the Direct Synthesis of Functionalized Indanes
Publication History
Publication Date:
11 June 2003 (online)
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Abstract
The reaction of bis(arylsulfonyl)iodonium ylides with a variety of norbornene derivatives 3 affords functionalized indanes 4 in good yields through an unusual cycloaddition. This diastereoselective cycloaddition provides a convenient preparative route to multicyclic structures of well defined stereochemical configuration.
Key words
ylide - [3+2]-cycloaddition - indane
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References
Representative
Experimental Procedure. Synthesis of 4a: To a suspension of
the ylide 1a (1.00 g, 2.0 mmol) and norbonene 3a (1.40 g, 15.0 mmol) in acetonitrile
(10 mL) was added a catalytic amount (0.1 mol%) of Rh2(OAc)4 and the
mixture was stirred at 20 °C for 22 h until a clear solution was
produced. The solvent was evaporated (40 °C at 10 torr) and
the residue was chromatographed on silica gel (CH2Cl2 as
eluent) to yield 419 mg (64%) of the indane derivative 4a; colorless plates, mp 140-141 °C
(lit.
[3]
140-141 °C).
IR (KBr): 3050 cm-1, 2940, 2860, 1580,
1470, 1440, 1330, 1300, 1280, 1250, 1230, 1210, 1200, 1185, 1160,
1120, 1080, 1020, 990, 940, 910, 880, 870, 840, 820. 1H
NMR (250 MHz, CDCl3) : δ = 0.82 (d, J = 10.4 Hz, 1 H), 0.93 (d, J = 10.4 Hz, 1 H), 1.24-1.29
(m, 2 H), 1.48-1.52 (m, 2 H), 2.13 (s, 1 H), 2.62 (dd, J = 1.9 Hz, 7.3 Hz, 1 H), 2.78
(d, J = 7.3 Hz, 1 H), 4.38 (d, J = 1.9 Hz, 1 H), 7.04 (d, J = 7.3 Hz, 1 H), 7.15-7.29
(m, 2 H), 7.35-7.45 (m, 3 H), 7.51-7.59 (m, 3 H). 13C
NMR (63 MHz, CDCl3) : δ = 28.1 (t),
28.9 (t), 32.7 (t), 42.7 (d), 42.9 (d), 47.8 (d), 53.6 (d), 76.2
(d), 112.6 (s), 124.5 (d), 126.1 (d), 126.8 (d), 128.6 (d), 129.2
(d), 129.5 (d), 133.4 (d), 135.5 (s), 136.7 (d), 148.2 (s).
Synthesis of 4b: A suspension of the ylide 1b (1.0 g, 1.9 mmol)and norbonene 3a (2.0 g, 21.0 mmol) in dichloromethane
(10 mL) was stirred for 240 h until a clear solution was produced.
The solvent was evaporated (40 °C at 10 torr) and the residue
was chromatographed on silica gel (CH2Cl2 as
eluent) to yield 200 mg (30%) of the indane derivative 4b; colorless plates, mp 181-182 °C.
IR (KBr): 2955cm-1, 2920, 2860, 1590,
1490, 1450, 1305, 1285, 1250, 1220, 1210, 1200, 1190, 1175, 1150,
1130, 1120, 1085, 890, 855, 830, 820. 1H NMR
(400 MHz, CDCl3) : δ = 0.83 (d, J = 10.4 Hz, 1 H), 0.91-0.94
(m, 1 H), 1.19-1.30 (m, 2 H), 1.34-1.57 (m, 2
H), 2.10 (dd, J = 3.0 Hz, 12.6
Hz, 2 H), 2.33 (s, 3 H), 2.39 (s, 3 H), 2.58 (dd, J = 2.2
Hz, 7.3 Hz, 1 H), 2.76 (d, J = 7.3
Hz, 1 H), 4.31 (d, J = 2.2 Hz,
1 H), 6.94 (d, J = 7.7 Hz, 1
H), 7.09 (d, J = 7.7 Hz, 1 H),
7.20 (d, J = 8.2 Hz, 2 H), 7.28
(s, 1 H), 7.47 (d, J = 8.2 Hz,
2 H). 13C NMR (100 MHz, CDCl3)
: δ = 21.2 (q), 21.6 (q), 28.1 (t), 29.0 (t),
32.8 (t), 42.7 (d), 53.3 (d), 76.1 (d), 124.1 (d), 126.6 (d), 129.2
(d), 129.3 (d), 130.4 (d), 134.0 (s), 135.7 (s), 136.5 (s), 144.3
(s), 145.3 (s). Anal. Calcd for C22H24O2S
(352.5): C, 74.96; H, 6.86; S, 9.10. Found: C, 74.66; H, 6.85; S,
9.11.
Synthesis of 5: To a solution
of the indane derivative 4a (118 mg, 0.36
mmol)in methanol (10 mL), was added in portions Na2HPO4 (180
mg) and 6% sodium amalgam (1.50 g) and the resulting mixture
was stirred at 20 °C for 48 h. The solvent was evaporated
(40 °C at 10 torr), the residue was dissolved in dichloromethane
(30 mL), and extracted with brine (2 × 50 mL). The organic
layer was dried over magnesium sulfate, the solvent evaporated (20 °C
at 10 torr), and the residue was purified by silica gel chromatography (CH2Cl2 as
eluent) to yield 61 mg (91%) of the indane 5 as colorless
oil. IR (Neat): 2930 cm-1, 2850, 1475,
1450, 830. 1H NMR (400 MHz, CDCl3)
: δ = 0.98-1.02 (m, 1 H), 1.11-1.15
(m, 1 H), 1.24-1.30 (m, 1 H), 1.37-1.43 (m, 1
H), 1.50-1.65 (m, 2 H), 2.10 (d, J = 3.8
Hz, 1 H), 2.29 (d, J = 3.8 Hz, 1
H), 2.36-2.41 (m, 1 H), 2.61 (dd, J = 3.8
Hz, 17.2 Hz, 1 H), 3.14 (d, J = 7.8
Hz, 1 H), 3.26 (dd, J = 10.2
Hz, 17.2 Hz, 1 H), 7.10-7.20
(m, 4 H). 13C NMR (100 MHz, CDCl3)
: δ = 28.8 (t), 29.0 (t), 32.4 (t), 39.3 (t),
43.4 (d), 43.7 (d), 44.9 (d), 55.5 (d), 124.0 (d), 124.5 (d), 126.1
(d), 126.2 (d), 144.8 (s), 146.3 (s). HRMS (EI): Calcd for C14H16 184.1252
Found: 184.1252.