(EtO)₃SiH-Promoted Palladium-Catalyzed Isomerization of Olefins: Convenient Synthesis of Internal Alkenes from Terminal Alkenes

Abstract

The catalytic activity of an in situ forming palladium catalyst system generated from PdCl₂(PPh₃)₂ and hydrosilane [(EtO)₃SiH] was revealed in the one-carbon migration and isomerization of 4,4-biaryl-substituted 1-butenes, in which the (EtO)₃SiH plays a key role in the palladium-catalyzed one-carbon migration and subsequent isomerization of terminal alkenes. This catalytic protocol is applied in the synthesis of a key building block of cassumunin C in high yield and promising selectivity.

Key words

olefin - palladium - isomerization - cassumunin - organosilicon

• References and Notes


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• 20 Typical Procedure for the Palladium-Catalyzed Isomerization 4,4-Diarylbut-1-enes (0.5 mmol), (EtO)₃SiH (0.1 mmol, 18.5 μL, 0.2 equiv) and a catalytic amount of Pd(Ph₃P)₂Cl₂ (0.005 mmol, 1 mol%) were added to a dry tube, and then the mixture was solved with dry THF (1 mL). The resulting mixture was stirred at 60 °C for 10 h. The mixture was then cooled to r.t., quenched by the addition of H₂O, and extracted by the addition of CH₂Cl₂. The organic layer was washed with H₂O, dried over Na₂SO₄, and concentrated. The residue was purified by flash column chromatography to give corresponding 4,4-diarylbut-1-enes. All the products were confirmed by GC–MS, NMR and IR spectrosopy. These data are provided in the Supporting Information. Analytical Data for 1-Methyl-2-(1-phenylbut-2-enyl)benzene (3a) ¹H NMR (400 MHz, CDCl₃): δ = 7.32 (t, J = 6.8 Hz, 2 H), 7.23 (J = 6.8 Hz, 3 H), 7.14 (d, J = 6.8 Hz, 2 H), 6.87 (d, J = 6.8 Hz, 2 H), 5.94 (dd, J = 13.6, 7.6 Hz, 1 H), 5.74–5.68 (m, 0.14 H), 5.47 (dq, J = 14.8, 6.4 Hz, 0.88 H), 5.02 (d, J = 9.6 Hz, 0.14 H), 4.66 (d, J = 7.2 Hz, 0.86 H), 3.81 (s, 3 H), 1.77 (d, J = 6.4 Hz, 3 H) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 158.0, 144.6, 136.5, 133.9, 129.5, 128.5, 128.3, 126.7, 126.1, 113.8, 55.3, 53.3, 18.0 ppm. GC–MS: m/z calcd for C₁₇H₁₈ [M]⁺: 222.3; found: 222.1. IR (KBr): ν_max = 3412, 3059, 3025, 3000, 2957, 2931, 2853, 2835, 1653, 1608, 1510, 1493, 1448, 1302, 1250, 1178, 1150, 1034, 971, 830, 700, 560 cm^–1.