One-Pot Formation and Derivatization of Di- and Triynes Based on the Fritsch−Buttenberg−Wiechell Rearrangement

Abstract

A divergent, one-pot synthesis of functionalized polyynes has been developed. Beginning with the appropriately substituted dibromoolefinic precursor, a carbenoid Fritsch-Buttenberg-Wiechell (FBW) rearrangement is used to generate the lithium acetylide of a conjugated polyyne framework, and subsequent trapping with carbon-based electrophiles provides for in situ formation of a wide range of di- and triynes. The lithium acetylide formed from the FBW reaction can also undergo transmetalation to provide the corresponding zinc, copper, tin, or platinum acetylides, leading to the divergent formation of symmetrical and unsymmetrical conjugated acetylenes, as well as ynones.

Synthesis of extended polyynes: Toward carbyne

“…An alternative route to hexayne formation using an FBW rearrangement utilizes a one-pot procedure (Scheme 11) [70]. In this case, formation of a Liacetylide from a previously desilylated dibromoolefinic precursor is accomplished through reaction with two equivalents of BuLi in toluene.…”

Nitro resin supported copper nanoparticles: An effective heterogeneous catalyst for C N cross coupling and oxidative C C homocoupling

“…Synthesis of conjugated diynes has been reported by couplings like Elington, cadiot-chodkiewikz, sonagashira and hay-glaser etc. Lately, salts of many transition metals like Ag, Au, Ni, Pd and Cu have been used to catalyze this coupling reaction as homogeneous and heterogeneous catalysts [49][50][51]. However, there are only a few reports of nanoparticles as catalysts in this oxidative coupling reaction [52][53][54].…”

Tolane liquid crystals with piperidine, 3,3,4,4,5,5-hexafluoropiperidine as end group: Synthesis and properties

“…These include the Fritsch-Buttenberg-Wiechell rearrangement [19], the 1,2-dibromo-1,2-diarylethane dehydrobromination reaction [20], and the Sonogashira coupling reaction [21]. The Sonogashira coupling reaction has been extensively used in recent years.…”