Browse
Submit Data
Databases
API
Help

Dataset Information

24 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

An efficient synthesis of (+/-)-grandisol featuring 1,5-enyne metathesis.

ABSTRACT: An eight-step synthesis of (+/-)-grandisol features a key sequence involving a high-yielding, microwave-assisted enyne metathesis to yield a 1-alkenylcyclobutene that is semihydrogenated to yield a silyl-protected grandisol. Metathesis catalyst screens revealed an intriguing trend whereby substrate conversion correlated strongly with the identity of the ligands on the catalyst. In addition, new reactivity of 1-alkenylcyclobutenes toward hydrogenation is described.

SUBMITTER: Graham TJ

PROVIDER: S-EPMC2798917 | biostudies-literature | 2010 Jan

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

An efficient synthesis of (+/-)-grandisol featuring 1,5-enyne metathesis.

Graham Thomas J A TJ Gray Erin E EE Burgess James M JM Goess Brian C BC

The Journal of organic chemistry 20100101 1

An eight-step synthesis of (+/-)-grandisol features a key sequence involving a high-yielding, microwave-assisted enyne metathesis to yield a 1-alkenylcyclobutene that is semihydrogenated to yield a silyl-protected grandisol. Metathesis catalyst screens revealed an intriguing trend whereby substrate conversion correlated strongly with the identity of the ligands on the catalyst. In addition, new reactivity of 1-alkenylcyclobutenes toward hydrogenation is described. ...[more]

PMID: 19957923

Similar Datasets

Application of tandem ring-closing enyne metathesis: formal total synthesis of (-)-cochleamycin A.

Project description:A tandem ring-closing metathesis of a silaketal-based dienyne substrate proceeded efficiently to provide a bicyclic siloxane, which upon removal of the silicon tether afforded an (E,Z)-1,3-dienediol. Further manipulation of this key functional motif rendered synthesis of the entire C1-C19 linear skeleton of (-)-cochleamycin A, a late-stage intermediate employed in the previous total synthesis of (+)-cochleamycin A by Roush and co-workers.

| S-EPMC2715010 | biostudies-literature

Domino ring-opening-ring-closing enyne metathesis vs enyne metathesis of norbornene derivatives with alkynyl side chains. Construction of condensed polycarbocycles.

Project description:The metathesis of norbornene derivatives with alkynyl side-chain with Grubbs' ruthenium alkylidine as catalyst has been investigated with the objective of constructing condensed polycyclic structures. This investigation demonstrated that the generally observed domino reaction course involving a ring-opening metathesis of the norbornene unit and a ring-closing enyne metathesis is influenced to a great extent by the nature of the functional group and the substrate structure and may follow a different reaction course than what is usually observed. In cases where ROM-RCEYM occurred, the resulting 1,3-diene reacts in situ with the dienophile to provide condensed tetracyclic systems.

| S-EPMC6204787 | biostudies-literature

Endo-selective enyne ring-closing metathesis promoted by stereogenic-at-Mo monoalkoxide and monoaryloxide complexes. Efficient synthesis of cyclic dienes not accessible through reactions with Ru carbenes.

Project description:Stereogenic-at-Mo monoalkoxide and monoaryloxide complexes promote enyne ring-closing metathesis (RCM) reactions, affording the corresponding endo products with high selectivity (typically >98:<2 endo:exo). All catalysts can be prepared and used in situ. Five-, six-, and seven-membered rings are obtained through reactions with enyne substrates that bear all-carbon tethers as well as those that contain heteroatom substituents. The newly developed catalytic protocols complement the related exo-selective Ru-catalyzed processes. In cases where Ru-based complexes deliver exo and endo products nondiscriminately, such as when tetrasubstituted cyclic alkenes are generated, Mo-catalyzed reactions afford the endo product exclusively. The efficiency of synthesis of N- and O-containing endo diene heterocycles can be improved significantly through structural modification of Mo catalysts. The modularity of Mo-based monopyrrolides is thus exploited in the identification of the most effective catalyst variants. Through alteration of O-based monodentate ligands, catalysts have been identified that promote enyne RCM with improved efficiency. The structural attributes of three Mo complexes are elucidated through X-ray crystallography. The first examples of catalytic enantioselective enyne RCM reactions are reported (up to 98:2 enantiomer ratio and >98% endo).

| S-EPMC2849279 | biostudies-literature

Modular Approach to Degradable Acetal Polymers Using Cascade Enyne Metathesis Polymerization.

Project description:A modular synthetic approach to degradable metathesis polymers is presented using acetal-containing enyne monomers. The monomers are prepared in a short and divergent synthetic sequence that features two points of modification to tune polymerization behavior and introduce molecular cargo. Steric and stereochemical elements are critical in the monomer design in order to provide rapid and living polymerizations capable of generating block polymers. The developed polyacetal materials readily undergo pH-dependent degradation in aqueous mixtures, and the rate of hydrolysis can be tuned through post-polymerization modification with triazolinedione click chemistry. This presents a new scaffold for responsive metathesis polymers that may find use in applications that requires controllable breakdown and release of small molecules.

| S-EPMC7265103 | biostudies-literature

Synthesis of mixed musks <i>via</i> Eschenmoser-Tanabe fragmentation, enyne metathesis and Diels-Alder reaction as key steps.

Project description:Musk analogues containing different macrocyclic ring systems as well as different annulated ring systems were synthesised by a simple and useful strategy. This strategy includes Eschenmoser-Tanabe fragmentation, enyne metathesis and Diels-Alder reaction as key steps. Starting from easily available (n) macrocyclic ketones, (n + 3) macrocyclic systems were assembled using the basic organic reactions.

| S-EPMC9092383 | biostudies-literature

An efficient synthesis of (+/-)-Lycoricidine featuring a Stille-IMDAF cycloaddition cascade.

Project description:[reaction: see text] A highly efficient total synthesis of (+/-)-Lycoricidine is described. The synthesis features the ready preparation of the Lycoricidine skeleton by a Stille-IMDAF cycloaddition cascade. The resulting cycloadduct is then used for the stereocontrolled installation of the other functionality present in the C-ring of the target molecule.

| S-EPMC2587426 | biostudies-literature

An efficient synthesis of the guaiane sesquiterpene (-)-isoguaiene by domino metathesis.

Project description:(-)-Isoguaiene was prepared from (S)-citronellal in only 9-10 steps with good overall yields. Either a trienyne or a dienediyne metathesis and highly diastereoselective organocatalytic Michael additions of aldehydes derived from (S)-citronellal served as the key transformations.

| S-EPMC6466796 | biostudies-literature

An Efficient Synthesis of Geminal-Dialkyl Dienes for Olefin Metathesis Polymerization.

Project description:A robust synthesis of gem-dialkyl acyclic diene monomers has been developed. This route is scalable, flexible, and biorenewable, allowing for the production of a wide range of diene monomers of different lengths and different gem-dialkyl substitution starting from unsaturated esters derived from seed oils. The metathesis polymerization of these monomers and the hydrogenation of the resulting polyolefins leads to telechelic gem-dialkyl polyethylenes, which can be used as elastomers in the synthesis of polyurethanes and other block polymers.

| S-EPMC8297823 | biostudies-literature

Endo-selective enyne ring-closing metathesis promoted by stereogenic-at-W mono-pyrrolide complexes.

Project description:The utility of W-alkylidene complexes for enyne ring-closing metathesis is demonstrated in a direct comparison with Mo-based analogs. Tungsten complexes lead to less alkyne oligomerization and higher levels of endo-selectivity and enantioselectivity.

| S-EPMC3039112 | biostudies-literature

Catalytic arylsulfonyl radical-triggered 1,5-enyne-bicyclizations and hydrosulfonylation of α,β-conjugates.

Project description:A catalytic bicyclization reaction of 1,5-enynes anchored by α,β-conjugates with arylsulfonyl radicals generated in situ from sulfonyl hydrazides has been established using TBAI (20 mol%) and Cu(OAc)2 (5 mol%) as co-catalysts under convenient conditions. In addition, the use of benzoyl peroxide (BPO) as the oxidant and pivalic acid (PivOH) as an additive was proven to be necessary for this reaction. The reactions occurred through 5-exo-dig/6-endo-trig bicyclizations and homolytic aromatic substitution (HAS) cascade mechanisms to give benzo[b]fluorens regioselectively. A similar catalytic process was developed for the synthesis of γ-ketosulfones. These reactions feature readily accessible starting materials and simple one-pot operation.

| S-EPMC4608173 | 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