The Telomerization of 1,3‐Dienes – A Reaction Grows Up

Abstract

Telomerization is a versatile tool for synthesizing unsaturated ethers, amines and other molecules starting from 1,3‐dienes and respective nucleophiles. The homogeneously catalyzed reaction has been the subject of academic and industrial research for over 50 years, offering a broad variety of substrates, catalysts and process concepts. This Minireview presents the advances and developments in this field over the last decade. The focus was on the conversion of renewable resources, the synthesis of promising new products and the development of efficient process concepts to combine these.

The Palladium‐Catalyzed Carboxytelomerization of Butadiene with Agrobased Alcohols and Polyols

“…[4] The reaction with olefins has also been appliedt ot he conversion of agro-based polyols for the synthesis of plasticizers. [6] This carbonylative version of the telomerizationreaction [7] encompasses severala dvantagess uch as high atom-economy and the use of industrially accessible reactants (e.g.,b utadiene, CO, alcohols). Interestingly,t he carbonylative coupling reaction of 2equivalents of 1,3-butadiene followed by the nucleophilic attack of an alcohol yields alkyl nona-3,8-dienoates (Scheme 1).…”

“…Interestingly,t he carbonylative coupling reaction of 2equivalents of 1,3-butadiene followed by the nucleophilic attack of an alcohol yields alkyl nona-3,8-dienoates (Scheme 1). [6] This carbonylative version of the telomerizationreaction [7] encompasses severala dvantagess uch as high atom-economy and the use of industrially accessible reactants (e.g.,b utadiene, CO, alcohols). All of these are already produced on large scale from agro-resources, furthers trengthening the attractivenesso fs uch transformation in the context of efficient biomass upgrading.…”

Facile catalyst recycling by thermomorphic behaviour avoiding organic solvents: a reactive ionic liquid in the homogeneous Pd-catalysed telomerisation of the renewable β-myrcene

“…The dimerisation of two 1,3-diene molecules combined with the attack of a Brønsted-acidic nucleophile (Scheme 1), generally referred to as telomerisation, is a long-known reaction and part of recent reviews on the topic of telomerisation and functionalization of 1,3-dienes. [3][4][5] Mechanistic insights were given by Jolly, who investigated the telomerisation of butadiene with methanol as a nucleophile. 6 It is assumed that amines act similarly as nucleophiles in this reaction.…”

First study on telomerization of chitosan and guar hemicellulose with butadiene: Influence of reaction parameters on the substitution degree of the biopolymers

“…The telomerization reaction is an efficient method to functionalize molecules. [1][2][3] It involves the dimerization of a 1,3-diene (usually butadiene or isoprene) with the concomitant addition of a nucleophile (mainly alcohols or amines) leading to compounds having a octa-2,7-diene chain.…”

“…[20][21][22][23][24][25] Although catalyzed telomerization of these two bioresources can be clearly a straightforward way of valorization, this reaction has to the best of our knowledge never been reported. We describe here our first results on the telomerization of chitosan and hemicellulose, which possible mechanism is presented in Scheme 1 based on the adopted general mechanism [1]. Our objective was to study as much as possible a sustainable valorization and for that we privileged aqueous solvents associated with water soluble Pd complexes as catalytic system.…”