Synthesis of Highly Substituted Symmetrical 1,3-Dienes via Organocuprate Oxidation

Abstract

Oxidation of alkenyl organocuprates formed from alkenyl halides allows the formation of highly substituted symmetrical 1,3-dienes. Cuprates formed from organolithiums and Grignard reagents can be tolerated and the reaction proceeds with retention of alkenyl geometry.

Key words

cuprates - oxidation - 1,3-diene - homocoupling - alkenyl halides

References and Notes

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13

Oxidant-derived by-products can be easily removed by passage through a plug of silica gel or an aqueous acid wash.

16

In Et₂O the yield dropped to ca. 5%.

17

Typical Procedure for Alkenyl Halide Homocoupling: Alkenyl halide (1 equiv) was dissolved in THF (4 mL) and the mixture was cooled to -78 ˚C. t-Butyllithium (1.7 M in pentane, 2 equiv) was added dropwise and the solution was stirred at -78 ˚C for 30 min, and then allowed to warm to r.t. over 10 min. The resultant solution was transferred via cannula onto a precooled suspension of CuBr˙SMe₂ (0.5 equiv) in THF (2 mL) at -78 ˚C and was stirred for 30 min. A solution of oxidant 5 (1 equiv) in THF (4 mL) was then added and the solution was stirred at -78 ˚C for 30 min and at r.t. for 1 h. The resultant solution was filtered through a plug of silica eluting with PE-Et₂O (1:1) and the solvent was removed in vacuo. The residue was purified by flash column chromatography.

18

Selected data for compound 7: clear oil; R _f 0.13 (PE-CH₂Cl₂, 5:1). IR (CDCl₃): 2930, 2857, 1427, 1105, 1088, 986, 692 cm^-¹. ^¹H NMR (400 MHz, CDCl₃): δ = 7.67-7.70 (m, 8 H), 7.36-7.43 (m, 12 H), 6.03 (m, 2 H), 5.57 (m, 2 H), 3.71 (t, J = 6.8 Hz, 4 H), 2.34 (app q, J = 6.8 Hz, 4 H), 1.07 (s, 18 H). ^¹³C NMR (125 MHz, CDCl₃): δ = 135.6 (CH), 134.0 (C), 132.2 (CH), 129.5 (CH), 128.8 (CH), 127.6 (CH), 63.7 (CH₂), 36.0 (CH₂), 26.8 (Me), 19.2 (C). HRMS (ESI):
m/z [M + Na]⁺ calcd for C₄₀H₅₀O₂Si₂Na: 641.3242; found: 641.3250.

19

Selected data for compound 6: white amorphous solid;
R _f 0.08 (PE-EtOAc, 10:1). IR (CDCl₃): 3063, 2927, 2861, 1464, 1426, 1390, 1363, 1103, 1037, 735, 757 cm^-¹. ^¹H NMR (500 MHz, CDCl₃): δ = 7.65-7.67 (m, 8 H), 7.37-7.45 (m, 12 H), 6.08 (m, 2 H), 5.81 (d, J = 2.5 Hz, 2 H), 3.56 (t,
J = 6.8 Hz, 4 H), 2.49 (app t, J = 6.8 Hz, 4 H), 1.21 (s, 18 H). ^¹³C NMR (125 MHz, CDCl₃): δ = 143.0 (C), 136.1 (CH), 134.2 (C), 131.6 (CH₂), 129.1 (CH), 127.6 (CH), 61.3 (CH₂), 40.0 (CH₂), 28.6 (Me), 18.4 (C). HRMS (ESI): m/z [M + Na + 2 H]⁺ calcd for C₄₀H₅₂O₂Si₂Na: 643.3398; found: 643.3396.