Publication: Eight-membered Palladacycles Derived from the Insertion of Olefines into the Pd–C Bond of Ortho-palladated Pharmaceuticals Phenethylamine and Phentermine. Synthesis of Stable Heck-type Intermediates Containing Accessible β-Hydrogens and its Use in the Synthesis of 2-Styryl-phenethylamines, Tetrahydroisoquinolines and Eight-membered Cyclic Amidines
Authors
Vicente, José ; Saura-Llamas, Isabel ; García-López, José-Antonio ; Bautista, Delia
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Vicente, José
Publisher
ACS
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DOI
https://doi.org/10.1021/om100738z
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info:eu-repo/semantics/article
Description
This document is made available under the CC-BY 4.0 license http://creativecommons.org/licenses/by /4.0/This document is the Accepted Manuscript version of a Published Work that appeared in final form in Organometallics copyright © American Chemical
Society, after peer review and technical editing by the publisher. To access the
final edited and published work see https://doi.org/10.1021/om100738z
Abstract
The ortho-metalated complexes derived from phenethylamine and phentermine
[Pd(C,N-C6H4CH2CR2NH2-2)(μ-X)]2 (R = H, X = Br (A); R = Me, X = Cl (B)) react with
olefins giving (1) the product of its insertion into the Pd–C bond, [Pd{C,NCH(
R’)CH2C6H4CH2CR2NH2-2}(μ-X)]2 (olefin = CH2=CHR’; R = H, X = Cl, R’ = C(O)Me
(1a), CO2Et (1c); R = Me, X = Cl, R’ = C(O)Me (1b), CO2Et (1d)), [Pd{C,NCH(
C5H8)CHC6H4(CH2CMe2NH2)-2}(μ-Cl)]2 (olefin = norbornene, C5H8; 1e) or (2) the
decomposition products of 1, i.e., Pd(0) and the complexes containing the arylated olefin,
trans-[PdX2(NH2CR2CH2C6H4CH=CHPh-2)2] (olefin = styrene; R = H, X = Cl (3f); R = Me,
X = Br (3g)). While complexes 1c and 1d can be isolated but decompose in solution to afford
Pd(0) and the corresponding complexes 3 (R = H, X = Cl (3c); R = Me, X = Br (3d)), the
others are surprisingly stable. Neutral ligands L cleave the bridge of complexes 1 to afford
[Pd(C^N)X(L)] (2) (L = 4-methyl-pyridine (pic), NH3, NHEt2, PPh3, tBuNC, XyNC).
Complexes 3 react with 1,10-phenanthroline (phen) to give [PdX2(phen)] and the orthovinylated
arylalkylamine RCH=CHC6H4CH2CR2NH2-2 (R = H (4f), Me (4g)), which in the
case of 3c or 3d can not be isolated as it undergoes an intramolecular hydroamination process
to afford the tetrahydroisoquinoline 5c or 5d, respectively. To prepare the
tetrahydroisoquinoline 5b, it is necessary to heat a mixture of complex 1b with one equiv of
TlOTf. The eight-membered cyclic amidine 7d is obtained from thermal decomposition of
complex cis-[Pd{C,N-CH(CO2Et)CH2C6H4CH2CR2NH2-2}(CNXy)2]OTf (8d), prepared by
reaction of 2d-5 with TlOTf and XyNC. The amidinium salt 7e-HOTf is formed by refluxing
in toluene a mixture of 2e-4 and TlOTf. The crystal structures of compounds 2a·CHCl3, 2b-1,
3
2d-3·1/3CH2Cl2, 2e-4·1/2CHCl3, 3d, 3g, 6 and 7e-HOTf have been determined by X-ray
diffraction studies.
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Citation
Organometallics, 2010, 29, 4320-4338
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