Browse
Submit Data
Databases
API
Help

Dataset Information

19 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Gold-Catalyzed Cycloisomerization of Sulfur Ylides to Dihydrobenzothiepines.

ABSTRACT: The metal-promoted nucleophilic addition of sulfur ylides to ?-systems is a well-established reactivity. However, the driving force of such transformations, elimination of a sulfide moiety, entails stoichiometric byproducts making them unfavorable in terms of atom economy. In this work, a new take on sulfur ylide chemistry is reported, an atom-economical gold(I)-catalyzed synthesis of dihydrobenzo[b]thiepines. The reaction proceeds under mild conditions at room temperature.

SUBMITTER: Knittl-Frank C

PROVIDER: S-EPMC7496544 | biostudies-literature | 2020 Mar

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Gold-Catalyzed Cycloisomerization of Sulfur Ylides to Dihydrobenzothiepines.

Knittl-Frank Christian C Saridakis Iakovos I Stephens Thomas T Gomes Rafael R Neuhaus James J Misale Antonio A Oost Rik R Oppedisano Alberto A Maulide Nuno N

Chemistry (Weinheim an der Bergstrasse, Germany) 20200608 48

The metal-promoted nucleophilic addition of sulfur ylides to π-systems is a well-established reactivity. However, the driving force of such transformations, elimination of a sulfide moiety, entails stoichiometric byproducts making them unfavorable in terms of atom economy. In this work, a new take on sulfur ylide chemistry is reported, an atom-economical gold(I)-catalyzed synthesis of dihydrobenzo[b]thiepines. The reaction proceeds under mild conditions at room temperature. ...[more]

PMID: 32227380

Similar Datasets

Copper-Catalyzed Formal [4+2] Cycloaddition of Enoldiazoimides with Sulfur Ylides.

Project description:Enoldiazoimides, a new subclass of enoldiazo compounds, generate enol-substituted carbonyl ylides whose reactions with sulfur ylides enable an unprecedented formal [4+2] cycloaddition. The resulting multifunctionalized indolizidinones, which incorporate sulfur, are formed in good yields under mild reaction conditions. The uniqueness of this transformation stems from the role of the silyl-protected enol, since the corresponding acetyldiazoimide failed to provide any cross-products in metal-catalyzed reactions with sulfur ylides. This copper-catalyzed cycloaddition is initiated with the generation of enol-substituted carbonyl ylides and sulfur ylides from enoldiazoimides and sulfonium salts, respectively, and proceeds through stepwise six-membered ring formation, C-O and C-S bond cleavage, and silyl and acetyl group migration.

| S-EPMC6421837 | biostudies-literature

Gold-catalyzed diastereoselective cycloisomerization of alkylidene-cyclopropane-bearing 1,6-diynes.

Project description:An unprecedented gold-catalyzed diastereoselective cycloisomerization of 1,6-diynes bearing an alkylidene cyclopropane moiety has been developed. This methodology enables rapid access to a variety of 1,2-trimethylenenorbornanes, which are important building blocks in the preparations of abiotic and sesquiterpene core structures.

| S-EPMC4120096 | biostudies-literature

Access to the protoilludane core by gold-catalyzed allene-vinylcyclopropane cycloisomerization.

Project description:Gold(I)-catalyzed allene-vinylcyclopropane cycloisomerization leads to the tricyclic framework of the protoilludanes in a single step by a reaction that involves a cyclopropane ring expansion and a Prins cyclization.

| S-EPMC3774677 | biostudies-literature

Gold-catalyzed enantioselective ring-expanding cycloisomerization of cyclopropylidene bearing 1,5-enynes.

Project description:An enantioselective ring-expanding cycloisomerization of 1,5-enynes bearing a cyclopropylidene moiety has been developed. This methodology provides a new approach to bicyclo[4.2.0]octanes, a structural motif present in many biologically active natural products.

| S-EPMC3998771 | biostudies-literature

Gold(i)-catalyzed cycloisomerization of vinylidenecyclopropane-enes via carbene or non-carbene processes.

Project description:Gold catalyzed cycloisomerization of aromatic ring tethered vinylidenecyclopropane-enes provides a divergent synthetic protocol for the construction of O-containing fused heterocycles through controllable carbene or non-carbene related processes. The carbene induced process features a new amphiphilic strategy to generate a gold carbene via a rearrangement of vinylidenecyclopropane. Whereas, the electronic effect of the ortho-substituents switches the reaction mode onto the non-carbene related process, from which five- or six-membered rings are selectively produced through allyl-migration.

| S-EPMC5949847 | biostudies-other

Mechanistic insights into the gold-catalyzed cycloisomerization of bromoallenyl ketones: ligand-controlled regioselectivity.

Project description:Through computational and experimental studies, the mechanisms of gold-catalyzed cycloisomerization of bromoallenyl ketones in toluene have been elucidated. The divergent 1,2-migrations for the Au(I)- and Au(III)-catalyzed reactions have been investigated, and the results confirmed that the regiochemistry is ligand-dependent in cases of Au(PR3)L (L = Cl, OTf, BF4, and SbF6) catalysts.

| S-EPMC2435085 | biostudies-literature

Gold-catalyzed cycloisomerization of 1,5-allenynes via dual activation of an ene reaction.

Project description:Tris(triphenylphosphinegold) oxonium tetrafluoroborate, [(Ph3PAu)3O]BF4, catalyzes the rearrangement of 1,5-allenynes to produce cross-conjugated trienes. Experimental and computational evidence shows that the ene reaction proceeds through a unique nucleophilic addition of an allene double bond to a cationic phosphinegold(I)-complexed phosphinegold(I) acetylide, followed by a 1,5-hydrogen shift.

| S-EPMC2995695 | biostudies-literature

Synthesis of (-)-Cannabimovone and Structural Reassignment of Anhydrocannabimovone through Gold(I)-Catalyzed Cycloisomerization.

Project description:The first total synthesis of cannabimovone from Cannabis sativa and anhydrocannabimovone was achieved by means of a highly stereoselective gold(I)-catalyzed cycloisomerization. The results led to reassignment of the structure of anhydrocannabimovone.

| S-EPMC5053274 | biostudies-literature

Annulative π-extension of BODIPYs made easy <i>via</i> gold(i)-catalyzed cycloisomerization.

Project description:Here we report gold(i)-catalyzed cycloisomerization as a new powerful synthetic tool for the preparation of π-extended BODIPY derivatives. The catalytic system PPhF 3AuCl/AgSbF6 enables the synthesis of [b]-[2,1]naphtho-fused-BODIPYs (2a-2c) under mild conditions, in excellent yields and short reaction times. The reaction is totally regioselective to the 6-endo-dig product and for the α-position of the BODIPY, which is both the kinetically and thermodynamically favored pathway, as supported by the free energy profile calculated by means of Density Functional Theory (DFT). Moreover, this methodology also allows the synthesis of two new families of [b]-aryl-fused-BODIPYs, namely, [3,4]phenanthro- (2e and 2f) and [1,2]naphtho-fused (2g) BODIPYs. Their molecular and electronic structures were established by NMR and UV-vis spectroscopies as well as single-crystal X-ray diffraction analysis. As can be noted from the X-ray structures, 2a, 2e and 2g present interesting structural differences at both the molecular and packing level. Interestingly, despite being isomers, the UV/vis spectra of 2a and 2g revealed significant differences in their electronic structures. The origin of this finding was studied by Time-Dependent DFT calculations. Calculated DFT Nuclear Independent Chemical Shift (NICS(0)) values also supported the different electronic structures of 2a and 2g.

| S-EPMC8162369 | biostudies-literature

Gold-catalyzed stereoselective cycloisomerization of allenoic acids for two types of common natural γ-butyrolactones.

Project description:γ-(E)-Vinylic and γ-alkylic γ-butyrolactones are two different types of lactones existing extensively in animals and plants and many of them show interesting biological activities. Nature makes alkylic γ-butyrolactones by many different enzymatic lactonization processes. Scientists have been mimicking the natural strategy by developing new catalysts. However, direct and efficient access to γ-(E)-vinylic γ-butyrolactones is still extremely limited. Here, we wish to present our modular allene approach, which provides an efficient asymmetric approach to (E)-vinylic γ-butyrolactones from allenoic acids by identifying a new gold complex as the catalyst. Based on this cycloisomerization strategy, the first syntheses of racemic xestospongiene and xestospongienes E, F, G, and H have been realized and the absolute configurations of the chiral centers in xestospongienes E and F have been revised. In addition, by applying a C-O bond cleavage-free hydrogenation, the syntheses of naturally occurring γ-alkylic γ-lactones, (R)-4-tetradecalactone, (S)-4-tetradecalactone, (R)-γ-palmitolactone, and (R)-4-decalactone, have also been achieved.

| S-EPMC5916948 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

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