Amino acid-derived bisphenolate palladium complexes as C-C coupling catalysts
A series of amine bisphenol (ABP) pro-ligands featuring amino acid ester pendant arms were prepared. Optimisation of the synthetic method allowed the facile incorporation of naturally occurring, chiral amino acids into the ABP scaffold with minimal racemisation. Reaction of the pro-ligands (LH 2 ) w...
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Published in | Dalton transactions : an international journal of inorganic chemistry Vol. 5; no. 47; pp. 17625 - 17634 |
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Main Authors | , , , , , |
Format | Journal Article |
Language | English |
Published |
England
Royal Society of Chemistry
07.12.2021
|
Subjects | |
Online Access | Get full text |
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Summary: | A series of amine bisphenol (ABP) pro-ligands featuring amino acid ester pendant arms were prepared. Optimisation of the synthetic method allowed the facile incorporation of naturally occurring, chiral amino acids into the ABP scaffold with minimal racemisation. Reaction of the pro-ligands (LH
2
) with Pd(OAc)
2
, in the presence of amines, led to the formation of complexes with an unprecedented pincer-like O,N,O coordination mode around the Pd
II
centre. The complexations in the presence of trialkylamines (NR
3
) afforded a mixture of LPdNR
3
and LPdNHR
2
species. The latter was shown to form
via
an ambient-temperature C-N cleavage involving unstable Pd(OAc)
2
(NHR
2
)
2
intermediates. Using pyridine as base eliminated this dealkylation and resulted in the exclusive formation of LPd(py) complexes in high yields. In total, seven novel Pd
II
ABP complexes were prepared, exhibiting distorted square-planar geometries with the asymmetric ligand moieties orientated towards the metal centre. The air- and moisture-stable LPd(py) complexes were successfully employed as catalysts in two types of C-C coupling reactions. The Suzuki-Miyaura coupling of 4′-bromoacetophenone and phenylboronic acid reached high yields (up to 81%), while a scope of further alkyl bromides was also efficiently converted using low catalyst loadings (1 mol%) and mild temperatures (40 °C). Furthermore, a Pd-pyridine complex achieved high activity in the Mizoroki-Heck coupling of styrene and 4′-bromoacetophenone.
Palladium complexes of amino acid-derived bisphenolate ligands show unprecedented pincer-like coordination and activity in C-C coupling reactions. |
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Bibliography: | Electronic supplementary information (ESI) available. CCDC 2070853 10.1039/d1dt03068j 2063653 2063654 , 2060206 2070849-2070851 For ESI and crystallographic data in CIF or other electronic format see DOI 2060147 2060200 and 2070847 2060195 2070846 ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 |
ISSN: | 1477-9226 1477-9234 |
DOI: | 10.1039/d1dt03068j |