One-Pot Synthesis and Functionalization of Polyynes via Alkylidene Carbenoids

Abstract

A one-pot, two-step method for the synthesis of diynes and triynes is reported. The reaction of a dibromoolefinic precursor with BuLi effects a Fritsch-Buttenberg-Wiechell rearrangement and generates a lithium acetylide intermediate, which is then trapped with a variety of electrophiles to produce substituted diynes and triynes. Alternatively, transmetalation from the lithium acetylide to give a zinc acetylide provides a nucleophilic coupling partner for aryl iodides in the presence of palladium to form symmetrical or unsymmetrical diynes and triynes via the Negishi coupling.

Key words

carbenoid rearrangement - rearrangement deprotonation - polyyne - lithium acetylide - zinc acetylide

References

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1

Current address: Department of Polymer Chemistry, Graduate School of Engineering, Kyoto University, Japan.

12

Toluene was used instead of hexanes to achieve a higher temperature for reflux in the Negishi cross-coupling.