Copper-catalyzed diastereoselective arylation of tryptophan derivatives: total synthesis of (+)-naseseazines A and B.

J Am Chem Soc

The Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, USA.

Published: April 2013

A copper-catalyzed arylation of tryptophan derivatives is reported. The reaction proceeds with high site- and diastereoselectivity to provide aryl pyrroloindoline products in one step from simple starting materials. The utility of this transformation is highlighted in the five-step syntheses of the natural products (+)-naseseazine A and B.

Download full-text PDF

Source
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC3662218PMC
http://dx.doi.org/10.1021/ja4023557DOI Listing

Publication Analysis

Top Keywords

arylation tryptophan
8
tryptophan derivatives
8
copper-catalyzed diastereoselective
4
diastereoselective arylation
4
derivatives total
4
total synthesis
4
synthesis +-naseseazines
4
+-naseseazines copper-catalyzed
4
copper-catalyzed arylation
4
derivatives reported
4

Similar Publications

Natural product biosynthesis is nature's tinkering ground for developing new enzymes that can achieve chemical transformations that are outside the purview of traditional chemical catalysis. Herein we describe a genome mining approach that leads to the discovery of a halogenase that regioselectively brominates a tryptophan side chain indole for a macrocyclic peptide substrate, enabling downstream chemical arylation by Suzuki-Miyaura coupling. The halogenase was found to prefer a macrocyclic peptide substrate over a linear peptide.

View Article and Find Full Text PDF

We introduce a novel and straightforward methodology for photoredox arylation of an indole scaffold using aryldiazonium salts under mild and metal-free conditions. Our approach enables the regioselective and chemoselective introduction of several aryl groups to the C(2) position of indoles and tryptophan, even in competition with other amino acids. This approach extends to the late-stage functionalization of peptides and lysozyme, heralding the unprecedented arylation of tryptophan residues in wild-type proteins and offering broad utility in chemical biology.

View Article and Find Full Text PDF

Thiazoloindole α-amino acids have been synthesized in four steps from tryptophan using a dual-catalytic thiolation reaction and a copper-mediated intramolecular N-arylation process. Late-stage diversification of the thiazoloindole core with electron-deficient aryl substituents produced chromophores that on one-photon excitation displayed blue-green emission, mega-Stokes shifts, and high quantum yields. The thiazoloindole amino acids could also be excited via two-photon absorption in the near-infrared, demonstrating their potential for biomedical imaging applications.

View Article and Find Full Text PDF

Side-Selective Solid-Phase Metallaphotoredox -Arylation of Peptides.

J Am Chem Soc

December 2023

Laboratory for Sustainable Organic Synthesis and Catalysis, Department of Chemistry, Federal University of São Carlos─UFSCar, Rodovia Washington Luís, km 235, SP-310, São Carlos, São Paulo 13565-905, Brazil.

Postsynthetic diversification of peptides through selective modification of endogenous amino acid side chains has enabled significant advances in peptide drug discovery while expanding the biological and medical chemistry space. However, current tools have been focused on the modification of reactive polar and ionizable side chains, whereas the decoration of aromatic systems (e.g.

View Article and Find Full Text PDF

The effect of the temperature in the synthesis of Pd nanoparticles in the metal-enzyme biohybrids is evaluated. The effect on the formation, size, and morphology of nanoparticles was evaluated using B lipase as the protein scaffold. XRD analyses confirmed the formation of crystalline Pd(0) as the metal species in all cases.

View Article and Find Full Text PDF

Want AI Summaries of new PubMed Abstracts delivered to your In-box?

Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!