Abstract
Rare alkenylalanes are prepared by Cp2TiCl2 or Cp*2ZrCl2 (Cp=η-C5H5; Cp*=η-C5Me5) catalysed addition of HAlCl2·(THF)2 to terminal alkynes (R1CCH; R1=alkyl). Use of minimum head-volume sealed vials maximises the hydroalumination yields of volatile alkynes. Facile 1,4-addition of the resultant alkenylalanes to unsaturated malonates R2CHC(CO2R3)2 (R2=alkyl, aryl, R3=alkyl) is observed providing rapid and convenient access to the addition products.
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