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Palladium Catalysed Acid‐Free Carboxytelomerisation of 1,3‐Butadiene with Alcohols Accessing Pelargonic Acid Derivatives Including Triglycerides under Selectivity Control
Author(s) -
Vogelsang Dennis,
Vondran Johanna,
Hares Kevin,
Schäfer Kevin,
Seidensticker Thomas,
Vorholt Andreas J.
Publication year - 2020
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.201901383
Subject(s) - chemistry , chemoselectivity , palladium , selectivity , nucleophile , alcohol , catalysis , organic chemistry , pyridine
Palladium catalysed carboxytelomerisation of 1,3‐butadiene with alcohols yields unsaturated C 9 ‐pelargonic esters in an atom‐economic and straightforward way. Although carboxytelomerisation is of current interest, limitations of applicable alcohol substrates have not been fully investigated. In here, we present the transfer of the catalytic system comprising palladium acetate and tri‐ n ‐butyl phosphine in pyridine to a broad variety of 20 alcohols with vast difference in nucleophilicity and sterical demands yielding the corresponding esters in a 100% atom economic manner. Effects of nucleophilicity and sterical demands were revealed for monoalcohols, di‐ and polyols. Whilst yields, chemoselectivity and E/Z‐selectivity of the pelargonic acid derivatives were excellent with up to 99%, selectivity towards mono‐, di‐ and triesters could be controlled successfully. Finally, the reaction profile of the carboxytelomerisation glycerol was uncovered, yielding up to 97% of industrially relevant unsaturated C 9 ‐short chain fats.