Ni-Catalyzed Formal Carbonyl-Ene Reaction of Terminal Alkenes via Carbon Dioxide Insertion

Published as part of the Cluster C–C Activation

Abstract

Nickel catalyzes the multicomponent coupling reaction of terminal alkenes, carbon dioxide, and organoaluminum reagents, leading to the synthesis of homoallylic alcohols in moderate-to-good yields with excellent regio- and stereoselectivities.

Key words

nickel catalyst - carbon dioxide - carbonyl-ene - ketone - ­organoaluminum

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• 16 General Procedure for the Ni-Catalyzed Three-Component Coupling Reaction of Alkene, CO₂, Organoaluminum Reagent (Table 1, Entry 4) The reaction was undertaken as follows: Into a carbon dioxide purged flask with Ni(cod)₂ (13.8 mg, 0.05 mmol) and PCy₃ (28.1 mg, 0.1 mmol) were introduced successively 1,4-dioxane (4 mL), allylbenzene (59.1 mg, 0.5 mmol), and Me₃Al (1.5 mL of 1 M solution in n-hexane, 1.5 mmol) via syringe. The homogeneous mixture was stirred at 40 °C for 24 h, during which the reaction was monitored by TLC. Then the mixture was quenched by adding 2 N HCl (10 mL) and extracted with ethyl acetate three times. The combined organic extracts were washed with brine and then dried (MgSO₄) and concentrated in vacuo. The residual oil was subjected to column chromatography over silica gel (hexane/ethyl acetate = 2:1, v/v) to give 3aa (64.3 mg, 0.36 mmol, 73%) as a pale yellow oil. (E)-2-Methyl-5-phenylpent-4-en-2-ol (3aa) TLC: R_f = 0.25 (hexane/ethyl acetate = 4:1, v/v). IR (neat): 3387 (m), 3059 (m), 2970 (s), 1599 (s), 1497 (m), 1377 (s), 1140 (s), 968 (s), 692 (s) cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 1.27 (s, 6 H), 1.54 (br, 1 H), 2.39 (d, J = 7.6 Hz, 2 H), 6.28 (dt, J = 15.9, 7.6 Hz, 1 H), 6.46 (d, J = 15.9 Hz, 1 H), 7.21 (t, J = 7.3 Hz, 1 H), 7.30 (t, J = 7.3 Hz, 2 H), 7.34 (d, J = 7.3 Hz, 2 H). ¹³C NMR (100 MHz, CDCl₃): δ = 29.3, 47.4, 70.9, 125.7, 126.1, 127.2, 128.5, 133.6, 137.3. HRMS: m/z calcd for C₁₂H₁₆O: 176.1201; found: m/z (relative intensity) = 176.1203 (9) [M⁺], 118 (100). (E)-2-Methyldec-4-en-2-ol (3ha) Pale yellow oil; yield 46.0 mg (0.27 mmol, 54%); TLC: R_f = 0.50 (hexane/ethyl acetate = 4:1, v/v). IR (neat): 3361 (br), 2962 (s), 2927 (s), 2856 (m), 1497 (w), 1377 (w), 1151 (w), 972 (w) cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 0.89 (t, J = 6.8 Hz, 3 H), 1.20 (s, 6 H), 1.26–1.41 (m, 6 H), 1.50 (br, 1 H), 2.03 (q, J = 7.3 Hz, 2 H), 2.16 (d, J = 6.8 Hz, 2 H), 5.46 (dt, J = 15.1, 7.3 Hz, 1 H), 5.53 (dt, J = 15.1, 6.8 Hz, 1 H). ¹³C NMR (100 MHz, CDCl₃): δ = 14.0, 22.5, 29.0, 29.2, 31.4, 32.7, 47.0, 70.4, 125.2, 135.4. HRMS: m/z calcd for C₁₁H₂₂O: 170.1671; found: m/z (relative intensity) = 170.1668 (14) [M⁺], 155 (100).