A Remarkable Cycloaddition of Bis(arylsulfonyl)iodonium Ylide with Norbornene Derivatives for the Direct Synthesis of Functionalized Indanes

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

References

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6

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.