Synthesis of esters of diaminotruxillic bis-amino acids by Pd-mediated photocycloaddition of analogs of the Kaede protein chromophore
The stereoselective synthesis of truxillic bis-amino esters from polyfunctional oxazolones is reported. The reaction of 4-((Z)-arylidene)-2-(E)-styryl-5(4H)-oxazolones 2 with Pd(OAc)2 resulted in ortho-palladation and the formation of a dinuclear open-book complexes 3 with carboxylate bridges, where...
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doaj-fee42e17edf94f3799c87cf965ce4dcd2021-04-02T11:33:03ZengBeilstein-InstitutBeilstein Journal of Organic Chemistry1860-53972020-05-011611111112310.3762/bjoc.16.981860-5397-16-98Synthesis of esters of diaminotruxillic bis-amino acids by Pd-mediated photocycloaddition of analogs of the Kaede protein chromophoreEsteban P. Urriolabeitia0Pablo Sánchez1Alexandra Pop2Cristian Silvestru3Eduardo Laga4Ana I. Jiménez5Carlos Cativiela6Instituto de Síntesis Química y Catálisis Homogénea, ISQCH (CSIC - Universidad de Zaragoza), Pedro Cerbuna 12, E-50009 Zaragoza, SpainInstituto de Síntesis Química y Catálisis Homogénea, ISQCH (CSIC - Universidad de Zaragoza), Pedro Cerbuna 12, E-50009 Zaragoza, SpainSupramolecular Organic and Organometallic Chemistry Centre, Departament of Chemistry, Faculty of Chemistry and Chemical Engineering, Babeş-Bolyai University, Str. Arany Janos 11, RO-400028 Cluj−Napoca, RomaniaSupramolecular Organic and Organometallic Chemistry Centre, Departament of Chemistry, Faculty of Chemistry and Chemical Engineering, Babeş-Bolyai University, Str. Arany Janos 11, RO-400028 Cluj−Napoca, RomaniaInstituto de Síntesis Química y Catálisis Homogénea, ISQCH (CSIC - Universidad de Zaragoza), Pedro Cerbuna 12, E-50009 Zaragoza, SpainInstituto de Síntesis Química y Catálisis Homogénea, ISQCH (CSIC - Universidad de Zaragoza), Pedro Cerbuna 12, E-50009 Zaragoza, SpainInstituto de Síntesis Química y Catálisis Homogénea, ISQCH (CSIC - Universidad de Zaragoza), Pedro Cerbuna 12, E-50009 Zaragoza, SpainThe stereoselective synthesis of truxillic bis-amino esters from polyfunctional oxazolones is reported. The reaction of 4-((Z)-arylidene)-2-(E)-styryl-5(4H)-oxazolones 2 with Pd(OAc)2 resulted in ortho-palladation and the formation of a dinuclear open-book complexes 3 with carboxylate bridges, where the Pd atom is C^N bonded to the oxazolone. In 3 the two exocyclic C=C bonds of the oxazolone are in a face-to-face arrangement, which is optimal for their [2 + 2] photocycloaddition. Irradiation of dimers 3 in CH2Cl2 solution with blue light (465 nm) promoted the chemo- and stereoselective [2 + 2] photocycloaddition of the exocyclic C=C bonds and the formation of cyclobutane-containing ortho-palladated complexes 4. Treatment of 4 with CO in a MeOH/NCMe mixture promoted the methoxycarbonylation of the palladated carbon and the release of the corresponding ortho-functionalized 1,3-diaminotruxillic bis-amino esters 5 as single isomers.https://doi.org/10.3762/bjoc.16.98amino acidsc–h activationkaede proteinoxazolonesphotocycloaddition |
collection |
DOAJ |
language |
English |
format |
Article |
sources |
DOAJ |
author |
Esteban P. Urriolabeitia Pablo Sánchez Alexandra Pop Cristian Silvestru Eduardo Laga Ana I. Jiménez Carlos Cativiela |
spellingShingle |
Esteban P. Urriolabeitia Pablo Sánchez Alexandra Pop Cristian Silvestru Eduardo Laga Ana I. Jiménez Carlos Cativiela Synthesis of esters of diaminotruxillic bis-amino acids by Pd-mediated photocycloaddition of analogs of the Kaede protein chromophore Beilstein Journal of Organic Chemistry amino acids c–h activation kaede protein oxazolones photocycloaddition |
author_facet |
Esteban P. Urriolabeitia Pablo Sánchez Alexandra Pop Cristian Silvestru Eduardo Laga Ana I. Jiménez Carlos Cativiela |
author_sort |
Esteban P. Urriolabeitia |
title |
Synthesis of esters of diaminotruxillic bis-amino acids by Pd-mediated photocycloaddition of analogs of the Kaede protein chromophore |
title_short |
Synthesis of esters of diaminotruxillic bis-amino acids by Pd-mediated photocycloaddition of analogs of the Kaede protein chromophore |
title_full |
Synthesis of esters of diaminotruxillic bis-amino acids by Pd-mediated photocycloaddition of analogs of the Kaede protein chromophore |
title_fullStr |
Synthesis of esters of diaminotruxillic bis-amino acids by Pd-mediated photocycloaddition of analogs of the Kaede protein chromophore |
title_full_unstemmed |
Synthesis of esters of diaminotruxillic bis-amino acids by Pd-mediated photocycloaddition of analogs of the Kaede protein chromophore |
title_sort |
synthesis of esters of diaminotruxillic bis-amino acids by pd-mediated photocycloaddition of analogs of the kaede protein chromophore |
publisher |
Beilstein-Institut |
series |
Beilstein Journal of Organic Chemistry |
issn |
1860-5397 |
publishDate |
2020-05-01 |
description |
The stereoselective synthesis of truxillic bis-amino esters from polyfunctional oxazolones is reported. The reaction of 4-((Z)-arylidene)-2-(E)-styryl-5(4H)-oxazolones 2 with Pd(OAc)2 resulted in ortho-palladation and the formation of a dinuclear open-book complexes 3 with carboxylate bridges, where the Pd atom is C^N bonded to the oxazolone. In 3 the two exocyclic C=C bonds of the oxazolone are in a face-to-face arrangement, which is optimal for their [2 + 2] photocycloaddition. Irradiation of dimers 3 in CH2Cl2 solution with blue light (465 nm) promoted the chemo- and stereoselective [2 + 2] photocycloaddition of the exocyclic C=C bonds and the formation of cyclobutane-containing ortho-palladated complexes 4. Treatment of 4 with CO in a MeOH/NCMe mixture promoted the methoxycarbonylation of the palladated carbon and the release of the corresponding ortho-functionalized 1,3-diaminotruxillic bis-amino esters 5 as single isomers. |
topic |
amino acids c–h activation kaede protein oxazolones photocycloaddition |
url |
https://doi.org/10.3762/bjoc.16.98 |
work_keys_str_mv |
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