Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Allylation of C‐, N‐, and O‐Nucleophiles via a Mechanochemically‐Driven Tsuji–Trost Reaction Suitable for Late‐Stage Modification of Bioactive Molecules

ABSTRACT:

SUBMITTER: Templ J

PROVIDER: S-EPMC10953357 | biostudies-literature | 2023 Nov

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

Allylation of C-, N-, and O-Nucleophiles via a Mechanochemically-Driven Tsuji-Trost Reaction Suitable for Late-Stage Modification of Bioactive Molecules.

Project description:We present the first solvent-free, mechanochemical protocol for a palladium-catalyzed Tsuji-Trost allylation. This approach features exceptionally low catalyst loadings (0.5 mol %), short reaction times (<90 min), and a simple setup, eliminating the need for air or moisture precautions, making the process highly efficient and environmentally benign. We introduce solid, nontoxic, and easy-to-handle allyl trimethylammonium salts as valuable alternative to volatile or hazardous reagents. Our approach enables the allylation of various O-, N-, and C-nucleophiles in yields up to 99 % even for structurally complex bioactive compounds, owing to its mild conditions and exceptional functional group tolerance.

| S-EPMC10952285 | biostudies-literature

Atroposelective desymmetrization of 2-arylresorcinols via Tsuji-Trost allylation.

Project description:Palladium-catalyzed asymmetric allylic alkylation has proven to be a powerful method for the preparation of a wide variety of chiral molecules. However, the catalytic and atroposelective allylic alkylation is still rare and challenging, especially for biaryl substrates. Herein, we report the palladium-catalyzed desymmetric and atroposelective allylation, in which the palladium complex with a chiral phosphoramidite ligand enables desymmetrization of nucleophilic 2-arylresorcinols in a highly enantioselective manner. With the aid of the secondary kinetic resolution effect, a wide variety of substrates containing a hydroxymethyl group at the bottom aromatic ring are able to provide O-allylated products up to 98:2 er. Computational studies show an accessible quadrant of the allylpalladium complex and provide three plausible transition states with intra- or intermolecular hydrogen bonding. The energetically favorable transition state is in good agreement with the observed enantioselectivity and suggests that the catalytic reaction would proceed with an intramolecular hydrogen bond.

| S-EPMC9968306 | biostudies-literature

Catalytic Asymmetric Synthesis of Diketopiperazines by Intramolecular Tsuji-Trost Allylation.

Project description:We report the intramolecular Tsuji-Trost reaction of Ugi adducts to give spiro-diketopiperazines in high yield and with high enantioselectivity. This approach allows the catalytic asymmetric construction of a broad range of these medicinally important heterocycles under mild conditions, in two steps from cheap, commercially available starting materials.

| S-EPMC6760471 | biostudies-literature

Palladium-catalyzed Tsuji-Trost-type reaction of benzofuran-2-ylmethyl acetates with nucleophiles.

Project description:The palladium-catalyzed benzylic-like nucleophilic substitution of benzofuran-2-ylmethyl acetate with N, S, O and C soft nucleophiles has been investigated. The success of the reaction is dramatically influenced by the choice of catalytic system: with nitrogen based nucleophiles the reaction works well with Pd2(dba)3/dppf, while with sulfur, oxygen and carbo-nucleophiles [Pd(η3-C3H5)Cl]2/XPhos is more efficient. The regiochemical outcome shows that the nucleophilic substitution occurs only on the benzylic position of the η3-(benzofuryl)methyl complex. The high to excellent yields and the simplicity of the experimental procedure make this protocol a versatile synthetic tool for the preparation of 2-substituted benzo[b]furans.

| S-EPMC8693365 | biostudies-literature

Diastereoselective Synthesis of β-Lactams by Ligand-Controlled Stereodivergent Intramolecular Tsuji-Trost Allylation.

Project description:The diastereoselective synthesis of highly substituted β-lactams by intramolecular Tsuji-Trost allylation is reported. Judicious selection of the ligand on palladium allows selective access to either the trans isomer (in generally good to excellent yield with very high diastereomeric excess) or cis isomer (with yields and diastereoselectivity ranging from modest to excellent depending on the substrate). The reaction proceeds under exceedingly mild conditions (rt, no additives) with a broad range of substrates, which are readily accessible by the Ugi reaction.

| S-EPMC7418107 | biostudies-literature

Asymmetric three-component Tsuji-Trost allylation reaction enabled by chiral aldehyde/palladium combined catalysis.

Project description:Despite the long-standing exploration of the catalytic asymmetric Tsuji-Trost allylation reaction since the mid-20th century, most reported instances have adhered to a two-component approach. Here, we present a remarkably efficient three-component asymmetric allylation reaction enabled by the collaborative action of chiral aldehyde and palladium. A diverse array of NH2-unprotected amino acid esters, aryl or alkenyl iodides, and allyl alcohol esters exhibit robust participation in this reaction, resulting in the synthesis of structurally diverse non-proteinogenic α-amino acid esters with favorable experimental outcomes. Mechanistic investigations reveal the dominance of the allylation/Heck coupling cascade in reactions involving electron-rich aryl iodides, while the Heck coupling/allylation cascade emerges as the dominant pathway in reactions involving electron-deficient aryl iodides. This chiral aldehyde/palladium combining catalytic system precisely governs the chemoselectivity of C-allylation and N-allylation, the regioselectivity of linear and branched allylation, and the enantioselectivity of C-allylation products.

| S-EPMC11220596 | biostudies-literature

Bidirectional Synthesis of the IJK Fragment of Ciguatoxin CTX3C by Sequential Double Ring-Closing Metathesis and Tsuji-Trost Allylation.

Project description:A novel four-step bidirectional strategy has been used to synthesize the IJK fragment of the marine polyether natural product CTX3C from a simple monocyclic precursor in a concise and efficient manner. The four-step bidirectional sequence involves ring-closing metathesis, alcohol oxidation, enol carbonate formation, and palladium-mediated Tsuji-Trost allylation.

| S-EPMC7304930 | biostudies-literature

Synthesis of the A-F Fragment of the Pacific Ciguatoxin CTX3C by Iterative Ring-Closing Metathesis and Tsuji-Trost Allylation.

Project description:The fully functionalized A-F fragment of the Pacific ciguatoxin CTX3C has been synthesized from a derivative of D-glucal, which serves as the B-ring. Rings A and C were introduced to either side of ring B by ring-closing diene and enyne metathesis (RCM). The seven-membered D-ring and eight-membered E-ring were assembled by iterative use of a six-step reaction sequence in which RCM was used for ring construction and Tsuji-Trost allylation was employed for subsequent stereoselective functionalization. The nine-membered F-ring was formed by use of an RCM reaction and bears the functionality required for attachment of the I-M fragment and subsequent closure of rings G and H.

| S-EPMC10946863 | biostudies-literature

Stereoselective Synthesis of Fused Vinylcyclopropanes by Intramolecular Tsuji-Trost Cascade Cyclization.

Project description:A stereoselective intramolecular Tsuji-Trost cascade cyclization of (homo)allylic vicinal diacetates with a pendant β-ketoamide or related carbon nucleophile to give γ-lactam-fused vinylcyclopropanes is reported. In addition to two new rings, the products contain three new C-C stereocenters (two of which are quaternary) with a 9:1 dr. Moreover, the reaction proceeds in >94% enantiospecificity with optically enriched starting materials, using an inexpensive carbohydrate as the source of chirality.

| S-EPMC6218879 | biostudies-literature

Enantioselective Heck/Tsuji-Trost reaction of flexible vinylic halides with 1,3-dienes.

Project description:The enantioselective domino Heck/cross-coupling has emerged as a powerful tool in modern chemical synthesis for decades. Despite significant progress in relative rigid skeleton substrates, the implementation of asymmetric Heck/cross-coupling cascades of highly flexible haloalkene substrates remains a challenging and and long-standing goal. Here we report an efficient asymmetric domino Heck/Tsuji-Trost reaction of highly flexible vinylic halides with 1,3-dienes enabled by palladium catalysis. Specifically, the Heck insertion as stereodetermining step to form ƞ3 allyl palladium complex and in situ trapping with nucleophiles enable efficient Heck/etherification in a formal (4 + 2) cycloaddition manner. Engineering the Sadphos bearing androgynous non-C2-symmetric chiral sulfinamide phosphine ligands are vital component in achieving excellent catalytic reactivity and enantioselectivity. This strategy offers a general, modular and divergent platform for rapidly upgrading feedstock flexible vinylic halides and dienes to various value-added molecules and is expected to inspire the development of other challenging enantioselective domino Heck/cross-couplings.

| S-EPMC11754474 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data