One-Pot, Unsymmetric Cadiot-Chodkiewicz Reaction Utilizing an In Situ Ethynysilane Deprotection

Cullen, Lindsey, Joseph Furgal, Joseph Gianino, Amy Hamlin, Jonathan Lezotte, and Matthew Mio

The Cu (I)-dependant Cadiot-Chodkiewicz coupling reaction is an excellent transformation for the generation of arylbutadiynes from bromoalkyne precursors. Our group has devised a modification to this protocol that uses trimethylsilyl-protected acetylene starting materials to generate unsymmetric bisarylbutadiyne oligomer products in one-pot at room temperature. Central to the modification is the utilization of the amidine base 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) in the presence of CuI, water and organic solvent to effect in situ alkynylsilane deprotection. The advent of innovative approaches to the generation of these oligomers should allow for rapid molecular prototyping, and in turn, increase the accessibility of valuable arylethynyl structures.