Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Alkenenitrile Transmissive Olefination: Synthesis of the Putative Lignan "Morinol I"

ABSTRACT: Grignard reagents trigger an addition-elimination with ?'-hydroxy acrylonitriles to selectively generate Z-alkenenitriles. The modular assembly of Z-alkenenitriles from a Grignard reagent, acrylonitrile, and an aldehyde is ideal for stereoselectively synthesizing alkenes as illustrated in the synthesis of the putative lignan "morinol I."

SUBMITTER: Fleming FF

PROVIDER: S-EPMC3336159 | biostudies-literature | 2011 Dec

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Alkenenitrile Transmissive Olefination: Synthesis of the Putative Lignan "Morinol I"

Fleming Fraser F FF Liu Wang W Yao Lihua L Pitta Bhaskar B Purzycki Matthew M Ravikumar P C PC

European journal of organic chemistry 20111028 34

Grignard reagents trigger an addition-elimination with α'-hydroxy acrylonitriles to selectively generate Z-alkenenitriles. The modular assembly of Z-alkenenitriles from a Grignard reagent, acrylonitrile, and an aldehyde is ideal for stereoselectively synthesizing alkenes as illustrated in the synthesis of the putative lignan "morinol I." ...[more]

PMID: 22545004

Similar Datasets

Transmissive olefination route to putative "morinol I" lignans.

Project description:A series of morinol-type lignans were rapidly assembled using a Grignard-based transmissive olefination. In combination with palladium-catalyzed arylations, the strategy provides stereoselective access to (7Z,7'E), (7E,7'E), and (7E,7'Z) morinol diastereomers and the (7Z,8'E) and (7E,8'E) conjugated analogues. Critical for the E/Z stereoselectivity is a new, general method for converting alkenenitriles to alkenemethanols that circumvents the enal E/Z isomerization commonly encountered during conventional i-Bu(2)AlH reduction.

| S-EPMC3331789 | biostudies-literature

Total Synthesis of Lignan Lactone (-)-Hinokinin.

Project description:This research paper is aimed at studying the total synthesis of pharmacologically active lignan (-)-hinokinin. The synthesis features a three-step cascade reaction involving highly stereoselective Michael addition, anion-oxidative hydroxylation, and oxygen anion cyclization to construct the pivotal butyrolactonimidate intermediate.

| S-EPMC4607678 | biostudies-literature

N-acylsulfonamide assisted tandem C-H olefination/annulation: synthesis of isoindolinones.

Project description:A tandem C-H olefination/annulation sequence directed by N-acylsulfonamides affords a variety of isoindolinones. This transformation is compatible with aliphatic alkenes as well as conjugated alkenes. Notably, molecular oxygen can be used as the sole, eco-friendly oxidant.

| S-EPMC3045675 | biostudies-literature

Olefination with Sulfonyl Halides and Esters: Synthesis of Unsaturated Sulfonyl Fluorides.

Project description:Methanedisulfonyl fluoride, CH2(SO2F)2, transforms aromatic aldehydes into β-arylethenesulfonyl fluorides, useful substrates for the SuFEx "click"-type transformations. The reaction mimics mechanism of the Horner-Wadsworth-Emmons olefination, which runs via addition of the carbanion, followed by cyclization-fragmentation of the four-membered ring intermediate. In the absence of base, electron-rich aldehydes follow an alternative pathway of the Knoevenagel condensation to provide unsaturated 1,1-disulfonyl fluorides. We demonstrate also trapping of elusive ethene-1,1-disulfonyl fluoride, CH2═C(SO2F)2, with 4-(dimethylamino)pyridine (DMAP) that forms zwitterionic adduct, characterized with X-ray studies.

| S-EPMC9490844 | biostudies-literature

Synthesis of the Tetracyclic Framework of Polycyclic Spiro Lignan Natural Products.

Project description:Polycyclic spiro lignans are a new family of lignan natural products recently isolated from Gymnotheca involucrata. The first synthesis of two model substrates of this rare family of natural products was achieved in six steps. An efficient strategy that features Suzuki coupling and Friedel-Crafts acylation was employed to construct the ABC tricyclic fluorene framework. Subsequently, Grignard reaction followed by acid-mediated cyclization furnished the spiro cyclic ether ring D.

| S-EPMC7178799 | biostudies-literature

Synthesis of highly substituted alkenes by sulfur-mediated olefination of N-tosylhydrazones.

Project description:Tetraphenylethylenes (TPEs) are well-known for their aggregation-induced emission properties. The synthesis of TPE derivatives, as well as other highly substituted olefins, generally requires the use of hazardous reagents, such as metalorganic compounds, to overcome the high activation energies caused by the sterically congested double bond. Herein, we present an efficient and metal-free procedure for the synthesis of tetraarylethylenes via alkylidene-homocoupling of N-tosylhydrazones, derived from readily available benzophenones, in excellent yields. The method relies only on cheap and benign additives, i.e. elemental sulfur and potassium carbonate, and easily competes with other established procedures in terms of scope, yield and practicability. A mechanistic study revealed a diazo compound, a thioketone and a thiirane as key intermediates in the pathway of the reaction. Based on this, a modified method, which allows for selective alkylidene-cross-coupling, generating a broader scope of tri- and tetrasubstituted olefins in good yields, is showcased as well.

| S-EPMC10657425 | biostudies-literature

Synthesis of Chiral, Enantiopure Allylic Amines by the Julia Olefination of ?-Amino Esters.

Project description:The four-step conversion of a series of N-Boc-protected l-amino acid methyl esters into enantiopure N-Boc allylamines by a modified Julia olefination is described. Key steps include the reaction of a lithiated phenylalkylsulfone with amino esters, giving chiral ?-ketosulfones, and the reductive elimination of related ?-acetoxysulfones. The overall transformation takes place under mild conditions, with good yields, and without loss of stereochemical integrity, being in this respect superior to the conventional Julia reaction of ?-amino aldehydes.

| S-EPMC6273449 | biostudies-literature

A Wittig-olefination-Claisen-rearrangement approach to the 3-methylquinoline-4-carbaldehyde synthesis.

Project description:Efficient syntheses are described for the synthetically important 3-methylquinoline-4-carbaldehydes 6a-h from o-nitrobenzaldehydes 1a-h employing a Wittig-olefination-Claisen-rearrangement protocol. The Wittig reaction of o-nitrobenzaldehydes with crotyloxymethylene triphenylphosphorane afforded crotyl vinyl ethers 2a-h, which on heating under reflux in xylene underwent Claisen rearrangement to give 4-pentenals 3a-h. Protection of the aldehyde group of the 4-pentenals as acetals 4a-h and subsequent oxidative cleavage of the terminal olefin furnished nitroaldehydes 5a-h. Reductive cyclization of these nitroaldehydes yielded the required 3-methylquinoline-4-carbaldehydes 6a-h in excellent yields. Therefore, an efficient method was developed for the preparation of 3-methylquinoline-4-carbaldehydes from o-nitrobenzaldehydes in a simple five-step procedure.

| S-EPMC3511006 | biostudies-literature

Synthesis and antiproliferative activity of derivatives of the phyllanthusmin class of arylnaphthalene lignan lactones.

Project description:A series of arylnaphthalene lignan lactones based on the structure of the phyllanthusmins, a class of potent natural products possessing diphyllin as the aglycone, has been synthesized and screened for activity against multiple cancer cell lines. SAR exploration was performed on both the carbohydrate and lactone moieties of this structural class. These studies have revealed the importance of functionalization of the carbohydrate hydroxy groups with both acetylated and methylated analogues showing increased potency relative to those with unsubstituted sugar moieties. In addition, the requirement for the presence and position of the C-ring lactone has been demonstrated through reduction and selective re-oxidation of the lactone ring. The most potent compound in this study displayed an IC50 value of 18?nM in an HT-29 assay with several others ranging from 50 to 200?nM. In an effort to elucidate their potential mechanism(s) of action, the DNA topoisomerase IIa inhibitory activity of the most potent compounds was examined based on previous reports of structurally similar compounds, but does not appear to contribute significantly to their antiproliferative effects.

| S-EPMC5962029 | biostudies-literature

Facile synthesis of 4-vinyl- and 4-fluorovinyl-1,2,3-triazoles via bifunctional "click-olefination" reagents.

Project description:Modular synthesis of vinyl and fluorovinyl triazoles can be achieved from bifunctional propargyl and fluoropropargyl sulfones by Cu-catalyzed azide-alkyne ligation and Julia-Kocienski olefination. Competitive click reactions of the protio and fluoropropargyl sulfones show higher reactivity of the latter, and a preliminary DFT analysis was performed.

| S-EPMC3337081 | 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