Preparation of Allylic Germanes with Tri(2-furyl)germane via π-Allylpalladium Species

Abstract

The reaction of various allylic esters with tri(2-furyl)germane in the presence of Pd(Ph₃P)₄ affords the corresponding allylic germanes in good yields at room temperature.

germanium - palladium - allylgermane - allylic substitution - allylpalladium

References

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<A NAME="RU07602ST-7">7</A>

Experimental Procedure: Allyl acetate (60 mg, 0.6 mmol) and tri(2-furyl)germane (137 mg, 0.5 mmol) were added to a mixture of Pd(PPh₃)₄ (29 mg, 0.025 mol) in DMF (1.5 mL). The mixture was stirred for 4.5 h at room temperature. The mixture was diluted with ether and filtered through a short pad of silica gel. Concentration of the filtrate and purification of the residue provided allyltri(2-furyl)germane (1, 151 mg, 0.48 mol) in 96% yield: IR(neat): 3115, 3080, 2976, 1634, 1549, 1454, 1362, 1205, 1150, 1101, 1005, 897, 745 cm^-1; ¹H NMR (CDCl₃): δ: 2.45 (dd, J = 8.0 Hz, 0.5 Hz, 2 H), 4.93 (dd, J = 9.6 Hz, 1.2 Hz, 1 H), 5.01 (dd, J = 17.0 Hz, 1.2 Hz, 1 H), 5.93 (m, 1 H), 6.46 (m, 3 H), 6.78 (d, J = 3.3 Hz, 3 H), 7.73 (m, 3 H); ¹³C NMR (CDCl₃): δ = 20.94, 109.79, 115.53, 121.36, 132.82, 147.47, 152.68. Found: C, 57.48; H, 4.59%. Calcd for C₁₅H₁₄O₃Ge: C, 57.22; H, 4.48%.

<A NAME="RU07602ST-8">8</A>

Hydrogen of tri(2-furyl)germane is reported to be significantly acidic, see: ref. [5e]