Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Total synthesis of (-)-4-desacetoxy-1-oxovindoline: Single atom exchange of an embedded core heteroatom in vindoline.

ABSTRACT: A concise total synthesis of (-)-4-desacetoxy-1-oxovindoline is disclosed, bearing a single heteroatom exchange in the core structure of the natural product 4-desacetoxyvindoline. Central to the synthesis is powerful oxadiazole intramolecular [4+2]/[3+2] cycloaddition cascade that formed four C-C bonds, created three new rings, and established five contiguous stereocenters about the new formed central 6-membered ring.

SUBMITTER: Boon BA

PROVIDER: S-EPMC8117404 | biostudies-literature | 2021 May

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Total synthesis of (-)-4-desacetoxy-1-oxovindoline: Single atom exchange of an embedded core heteroatom in vindoline.

Boon Byron A BA Yu Yi-Yun YY Boger Dale L DL

Tetrahedron 20210329

A concise total synthesis of (-)-4-desacetoxy-1-oxovindoline is disclosed, bearing a single heteroatom exchange in the core structure of the natural product 4-desacetoxyvindoline. Central to the synthesis is powerful oxadiazole intramolecular [4+2]/[3+2] cycloaddition cascade that formed four C-C bonds, created three new rings, and established five contiguous stereocenters about the new formed central 6-membered ring. ...[more]

PMID: 33994597

Similar Datasets

Asymmetric total synthesis of vindoline.

Project description:A concise asymmetric total synthesis of (-)-vindoline (1) is detailed based on a tandem intramolecular [4+2]/[3+2] cycloaddition cascade of a 1,3,4-oxadiazole inspired by the natural product structure, in which the tether linking the initiating dienophile and oxadiazole bears a chiral substituent that controls the facial selectivity of the initiating Diels-Alder reaction and sets absolute stereochemistry of the remaining six stereocenters in the cascade cycloadduct. This key reaction introduces three rings and four C-C bonds central to the pentacyclic ring system setting all six stereocenters and introducing essentially all the functionality found in the natural product in a single step. Implementation of the approach also required the development of a unique ring expansion reaction to provide a six-membered ring suitably functionalized for introduction of the Delta (6, 7)-double bond found in the core structure of vindoline and defined our use of a protected hydroxymethyl group as the substituent used to control the stereochemical course of the cycloaddition cascade.

| S-EPMC2854892 | biostudies-literature

Total synthesis of (-)- and ent-(+)-vindoline.

Project description:[reaction: see text] Two exceptionally concise total syntheses of (-)- and ent-(+)-vindoline are detailed enlisting a diastereoselective tandem [4 + 2]/[3 + 2] cycloaddition of a 1,3,4-oxadiazole. The unique reaction cascade assembles the fully functionalized pentacyclic ring system of vindoline in a single step that forms four C-C bonds and three rings while introducing all requisite functionality and setting all six stereocenters within the central ring including three contiguous and four total quaternary centers.

| S-EPMC2587129 | biostudies-literature

Total synthesis of (-)- and ent-(+)-vindoline and related alkaloids.

Project description:A concise 11-step total synthesis of (-)- and ent-(+)-vindoline (3) is detailed based on a unique tandem intramolecular [4 + 2]/[3 + 2] cycloaddition cascade of a 1,3,4-oxadiazole inspired by the natural product structure, in which three rings and four C-C bonds are formed central to the characteristic pentacyclic ring system setting all six stereocenters and introducing essentially all the functionality found in the natural product in a single step. As key elements of the scope and stereochemical features of the reaction were defined, a series of related natural products of increasing complexity were prepared by total synthesis including both enantiomers of minovine (4), 4-desacetoxy-6,7-dihydrovindorosine (5), 4-desacetoxyvindorosine (6), and vindorosine (7) as well as N-methylaspidospermidine (11). Subsequent extensions of the approach provided both enantiomers of 6,7-dihydrovindoline (8), 4-desacetoxyvindoline (9), and 4-desacetoxy-6,7-dihydrovindoline (10).

| S-EPMC2531198 | biostudies-literature

Asymmetric total synthesis of vindorosine, vindoline, and key vinblastine analogues.

Project description:Concise asymmetric total syntheses of vindoline (1) and vindorosine (2) are detailed based on a unique intramolecular [4 + 2]/[3 + 2] cycloaddition cascade of 1,3,4-oxadiazoles inspired by the natural product structures. A chiral substituent on the tether linking the dienophile and oxadiazole was used to control the facial selectivity of the initiating Diels-Alder reaction and set the absolute stereochemistry of the remaining six stereocenters in the cascade cycloadduct. This key reaction introduced three rings and four C-C bonds central to the pentacyclic ring system setting all six stereocenters and introducing essentially all the functionality found in the natural products in a single step. Implementation of the approach for the synthesis of 1 and 2 required the development of a ring expansion reaction to provide a 6-membered ring suitably functionalized for introduction of the Δ(6,7)-double bond found in the core structure of the natural products. Two unique approaches were developed that defined our use of a protected hydroxymethyl group as the substituent that controls the stereochemical course of the cycloaddition cascade. In the course of these studies, several analogues of vindoline were prepared containing deep-seated structural changes presently accessible only by total synthesis. These analogues, bearing key modifications at C6-C8, were incorporated into vinblastine analogues and used to probe the unusual importance (100-fold) and define the potential role of the vinblastine Δ(6,7)-double bond.

| S-EPMC2944909 | biostudies-literature

Total synthesis and evaluation of vinblastine analogues containing systematic deep-seated modifications in the vindoline subunit ring system: core redesign.

Project description:The total synthesis of a systematic series of vinblastine analogues that contain deep-seated structural modifications to the core ring system of the lower vindoline subunit is described. Complementary to the vindoline 6,5 DE ring system, compounds with 5,5, 6,6, and the reversed 5,6 membered DE ring systems were prepared. Both the natural cis and unnatural trans 6,6-membered ring systems proved accessible, with the latter representing a surprisingly effective class for analogue design. Following Fe(III)-promoted coupling with catharanthine and in situ oxidation to provide the corresponding vinblastine analogues, their evaluation provided unanticipated insights into how the structure of the vindoline subunit contributes to activity. Two potent analogues (81 and 44) possessing two different unprecedented modifications to the vindoline subunit core architecture were discovered that matched the potency of the comparison natural products and both lack the 6,7-double bond whose removal in vinblastine leads to a 100-fold drop in activity.

| S-EPMC3554876 | biostudies-literature

Tailoring coordination environments of single-atom electrocatalysts for hydrogen evolution by topological heteroatom transfer.

Project description:The rational design of carbon-supported transition-metal single-atom catalysts requires the precise arrangement of heteroatoms within the single-atom catalysts. However, achieving this design is challenging due to the collapse of the structure during the pyrolysis. Here, we introduce a topological heteroatom-transfer strategy to prevent the collapse and accurately control the P coordination in carbon-supported single-atom catalysts. As an illustration, we have prepared self-assembled helical fibers with encapsulated cavities. Within these cavities, adjustable functional groups can chelate metal ions (Nx···Mn+···Oy), facilitating the preservation of the structure during the pyrolysis based phosphidation. This process allows for the transfer of heteroatoms from the assembly into single-atom catalysts, resulting in the precise coordination tailoring. Notably, the Co-P2N2-C catalyst exhibits electrocatalytic performance as a non-noble metal single-atom catalyst for alkaline hydrogen evolution, attaining a current density of 100 mA cm-2 with an overpotential of only 131 mV.

| S-EPMC10981667 | biostudies-literature

Direct coupling of catharanthine and vindoline to provide vinblastine: total synthesis of (+)- and ent-(-)-vinblastine.

Project description: Not available

| S-EPMC2570212 | biostudies-literature

CO Adsorption on a Single-Atom Catalyst Stably Embedded in Graphene.

Project description:Confined single metal atoms in graphene-based materials have proven to be excellent catalysts for several reactions and promising gas sensing systems. However, whether the chemical activity arises from the specific type of metal atom or is a direct consequence of the confinement itself remains unclear.

| S-EPMC11891640 | biostudies-literature

Total Synthesis of (-)-Vindoline and (+)-4-epi-Vindoline Based on a 1,3,4-Oxadiazole Tandem Intramolecular [4 + 2]/[3 + 2] Cycloaddition Cascade Initiated by an Allene Dienophile.

Project description:It is reported that an allene dienophile can initiate a tandem intramolecular [4 + 2]/[3 + 2] cycloaddition cascade of 1,3,4-oxadiazoles, that the intermediate cross-conjugated 1,3-dipole (a carbonyl ylide) can participate in an ensuing [3 + 2] dipolar cycloaddition in a remarkably effective manner, and that the reaction can be implemented to provide the core pentacyclic ring system of vindoline. Its discovery improves a previous total synthesis of (-)-vindoline and was used in a total synthesis of (+)-4-epi-vindoline and (+)-4-epi-vinblastine that additionally enlists an alternative series of late-stage transformations.

| S-EPMC4636949 | biostudies-literature

Heteroatom-embedded Mellitic Triimido COFs for efficient proton conduction.

Project description:Ionic covalent organic frameworks (iCOFs) are promising materials for energy storage devices due to their ionic functional groups, which facilitate ion transport, and their highly ordered pores of their frameworks, which provide ideal pathways for long-term ion transport under harsh electrochemical conditions. In this study, we attempted for the first time to synthesize an unprecedented iCOF using a heteroatom-embedded mellitic triimido COF framework that enables practical ion channels on the Angstrom scale. This iCOF was subsequently evaluated as an anhydrous proton-conducting material. The heterocyclic pyridine group of the 2,5-diaminopyridine (DAPy) linker plays an important role, not only as an AB stacking-inducing group but also as a proton acceptor that interacts with impregnated H3PO4. The resulting PA@MTI-DAPy-COF exhibited high proton conductivity of 3.68 × 10-2 S cm-1 at 150oC under anhydrous conditions. This work paves the way for constructing efficient proton-conducting channels by leveraging the stacking structure of COF skeletons.

| S-EPMC11833120 | 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