Palladium-Catalyzed Reaction of Olefins with PhI(OAc)₂-TBAB System: An Efficient and Highly Selective Bisfunctionalization Strategy

Abstract

The palladium-catalyzed reaction of olefins with PhI(OAc)₂-TBAB system provides a novel, efficient, and highly selective bisfunctionalization strategy to introduce bromo and oxygen groups simultaneously. The substituents on the C=C bond control the regioselectivity of this reaction, which could be an effective supplement of bromohydroxylation in organic synthesis.

bisfunctionalization reactions - olefins - palladium-catalyzed reactions - selective

References and Notes

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Yu L., Ren L.-F., Xu B., Guo R. Synth. Commun. 2010, 40, in press.

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Typical Procedure for the Preparation of 2 In the presence of Pd(OAc)₂ (0.03 mmol, 6.7 mg), olefins (0.3 mmol), PhI(OAc)₂ (0.6 mmol), and TBAB (0.3 mmol) were heated in MeCN (2 mL) at 60 ˚C. The reaction was monitored by TLC. When the reaction terminated, H₂O (5 mL) was added, and the liquid was extracted by EtOAc (3 × 5 mL). The combined organic layer was dried by anhyd MgSO₄, and the solvent was evaporated under vacuum. The residue was subjected to preparative TLC (eluent: PE-EtOAc = 8:1) to give the corresponding product 2.
Data for Compound 2a
Oil. IR (film): 2952, 1751, 1639, 1494, 1446, 1366, 1218, 1084, 1013, 986, 961, 904, 750, 706 cm^-¹. ^¹H NMR (600 MHz, CDCl₃): δ = 7.52-7.53 (m, 4 H), 7.30-7.32 (m, 6 H), 3.28-3.30 (m, 2 H), 2.40-2.43 (m, 1 H), 2.25-2.28 (m, 2 H), 2.12 (s, 3 H), 1.83-1.85 (m, 1 H) ppm. ^¹³C NMR (150 MHz, CDCl₃): δ = 15.8, 22.3, 37.3, 74.4, 88.7, 127.0, 127.8, 129.7, 137.7, 168.0 ppm. MS (EI, 70 eV): m/z (%) = 278 (3) [M⁺ - Br], 183 (100). Anal. Calcd for C₁₉H₁₉BrO₂: C, 63.52; H, 5.33. Found: C, 63.20; H, 5.14.

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Procedure for the Bromohydroxylation of Compound 1f
Compound 1f (0.3 mmol) and NBS (0.3 mmol) were stirred in acetone-H₂O (2 mL; 5:1) at r.t. The reaction was monitored by TLC (eluent: PE). When the reaction terminated, the liquid was subjected to preparative TLC (eluent: PE-EtOAc = 7:1) to give the adduct 3 in 76% yield.
Data for 3 Oil. IR (film): 3060, 3029, 2971, 1493, 1448, 1425, 1332, 1279, 1226, 1163, 1062, 1032, 993, 913, 843, 750, 699 cm^-¹. ^¹H NMR (600 MHz, CDCl₃): δ = 7.25-7.43 (m, 10 H), 4.09 (s, 2 H), 3.14 (s, 1 H) ppm. ^¹³C NMR (150 MHz, CDCl₃): δ = 44.0, 76.9, 126.4, 127.7, 128.4, 143.5. MS (EI, 70 eV): m/z (%) = 276 (3) [M⁺], 105 (100). Anal. Calcd for C₁₄H₁₃BrO: C, 60.67; H, 4.73. Found: C, 60.95; H, 4.88.