Browse
Submit Data
Databases
API
Help

Dataset Information

7 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

2-Bromo-6-(chlorodiisopropylsilyl)phenyl tosylate as an efficient platform for intramolecular benzyne-diene [4 + 2] cycloaddition.

ABSTRACT: An intramolecular benzyne-diene [4 + 2] cycloaddition with broad substrate scope has been realized by using a cleavable silicon tether, allowing access to various polycyclic structures. 2-Bromo-6-(chlorodiisopropylsilyl)phenyl tosylate serves as an efficient platform for (1) rapid attachment of various arynophiles to the benzyne precursor via a Si-O bond and (2) facile generation of benzyne via halogen-metal exchange with Ph₃MgLi.

SUBMITTER: Nishii A

PROVIDER: S-EPMC6461022 | biostudies-literature | 2019 Apr

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

2-Bromo-6-(chlorodiisopropylsilyl)phenyl tosylate as an efficient platform for intramolecular benzyne-diene [4 + 2] cycloaddition.

Nishii Arata A Takikawa Hiroshi H Suzuki Keisuke K

Chemical science 20190306 13

An intramolecular benzyne-diene [4 + 2] cycloaddition with broad substrate scope has been realized by using a cleavable silicon tether, allowing access to various polycyclic structures. 2-Bromo-6-(chlorodiisopropylsilyl)phenyl tosylate serves as an efficient platform for (1) rapid attachment of various arynophiles to the benzyne precursor via a Si-O bond and (2) facile generation of benzyne via halogen-metal exchange with Ph3MgLi. ...[more]

PMID: 31015926

Similar Datasets

Enamide-benzyne-[2 + 2] cycloaddition: stereoselective tandem [2 + 2]-pericyclic ring-opening-intramolecular N-tethered [4 + 2] cycloadditions.

Project description:Benzyne-[2 + 2] cycloadditions with enamides are described. This effort led to the development of a highly stereoselective tandem [2 + 2] cycloaddition-pericyclic ring-opening-intramolecular-N-tethered-[4 + 2] cycloaddition for rapid assembly of nitrogen heterocycles.

| S-EPMC2822464 | biostudies-other

A tandem 1,3-H-shift-6?-electrocyclization-cyclic 2-amido-diene intramolecular Diels-Alder cycloaddition approach to BCD-Ring of atropurpuran.

Project description:An approach toward the BCD-ring of atropurpuran via a sequence of allenic 1,3-H shift, 6?-electron pericyclic ring closure, and intramolecular Diels-Alder cycloaddition of cyclic 2-amidodiene is described.

| S-EPMC3253247 | biostudies-literature

Total syntheses of chelidonine and norchelidonine via an enamide-benzyne-[2 + 2] cycloaddition cascade.

Project description:Total syntheses of chelidonine and norchelidonine featuring an enamide-benzyne-[2 + 2] cycloaddition initiated cascade is described. The cascade includes a pericyclic ring-opening and intramolecular Diels-Alder reaction.

| S-EPMC3366029 | biostudies-literature

Intramolecular [4 + 2] trapping of a hexadehydro-Diels-Alder (HDDA) benzyne by tethered arenes.

Project description:We report here the efficient, intramolecular trapping in a Diels-Alder (DA) sense of thermally generated benzynes by one of two pendant arene rings. A more electron-rich ring (p-methoxyphenyl) reacted substantially faster than a simple phenyl ring, which was, in turn, slightly more reactive vs a 4-carbomethoxyphenyl ring. Photoinduced di-?-methane rearrangement of the initial DA adducts gave rise to unusual isomeric polycyclic adducts.

| S-EPMC4729866 | biostudies-literature

4-Bromo-phenyl benzoate.

Project description:The structure of the title compound (4BPBA), C(13)H(9)BrO(2), is similar to that of phenyl benzoate (PBA), 4-methyl-phenyl benzoate (4MePBA) and 4-methoxy-phenyl benzoate, with somewhat different bond parameters. The dihedral angle between the phenyl and benzoyl rings in 4BPBA is 58.43 (17)°, compared with values of 55.7° in PBA and 60.17 (7)° in 4MPBA. The mol-ecules in the title compound are packed into infinite chains in the a-axis direction.

| S-EPMC2960956 | biostudies-literature

Pyridine(diimine) Iron Diene Complexes Relevant to Catalytic [2+2]-Cycloaddition Reactions.

Project description:The synthesis, characterization, and catalytic activity of pyridine(diimine) iron piperylene and isoprene complexes are described. These diene complexes are competent precatalysts for (i) the selective cross-[2+2]-cycloaddition of butadiene or (E)-piperylene with ethylene and ?-olefins and (ii) the 1,4-hydrovinylation of isoprene with ethylene. In the former case, kinetic analysis implicates the diamagnetic ?4-piperylene complex as the resting state prior to rate-determining oxidative cyclization. Variable temperature 1H NMR and EXSY experiments established that diene exchange from the diamagnetic, 18e- complexes occurs rapidly in solution at ambient temperature through a dissociative mechanism. The solid-state structure of (Me(Et)PDI)Fe(?4-piperylene) (Me(Et)PDI = 2,6-(2,6-Me2-C6H3N?CEt)2C5H3N), was determined by single-crystal X-ray diffraction and confirmed the s-trans coordination of the monosubstituted 1,3-diene. Possible relationships between ligand-controlled diene coordination geometry, metallacycle denticity, and chemoselectivity of iron-mediated cycloaddition reactions are discussed.

| S-EPMC7236768 | biostudies-literature

5-Hydroxyindoles by intramolecular alkynol-furan diels-alder cycloaddition.

Project description:A convergent approach provides a convenient access to synthetically and biologically useful 3,4-disubstituted 5-hydroxyindoles. The one-pot procedure uses microwave heating to initiate an intramolecular [4 + 2]-cycloaddition of an alkynol segment onto a furan followed by a fragmentation, aromatization, and N-Boc deprotection cascade. Yields range from 15 to 74%, with aromatic substituents providing better conversions. 4-Trimethylsilylated analogues undergo a 1,3-silatropic rearrangement to give the O-TMS ethers.

| S-EPMC3684082 | biostudies-literature

Intramolecular [1 + 4 + 1] cycloaddition: establishment of the method.

Project description:Structurally complex and physiologically active natural products often include bicyclic and polycyclic ring systems having defined relative and absolute configuration. Approaches that allow the construction of more than one carbocyclic ring at a time have proven valuable, in particular those that allow at the same time the control of an array of new stereogenic centers. One of the most general and most widely used protocols has been the intramolecular Diels-Alder [4 + 2] cycloaddition, in which a single stereogenic center between the diene and the dienophile can control the relative and absolute configuration of the product. We report a two-step [1 + 4 + 1] procedure for bicyclic and polycyclic construction, based on the cyclization of an omega-dienyl ketone. This is complementary to, and will likely be as useful as, the intramolecular Diels-Alder cycloaddition.

| S-EPMC2920606 | biostudies-literature

Regioselective intramolecular dipolar cycloaddition of azides and unsymmetrical alkynes.

Project description:Enantioenriched allenylsilanes are used in three-component propargylation reactions with aldehydes and silyl ethers to form syn-homopropargylic ethers that contain an imbedded azide. These materials then undergo thermally induced intramolecular 1,3-dipolar cycloaddition reactions, resulting in unique fused ring systems containing 1,2,3-triazoles. The ability to modify all three components of the reaction allows for expedient access to compounds containing significant structural and stereochemical variation.

| S-EPMC3164318 | biostudies-literature

4-Bromo-N-phenyl-benzamide.

Project description:The mol-ecule of the title benzamide derivative, C(13)H(10)BrNO, is twisted with the dihedral angle between the phenyl and 4-bromo-phenyl rings being 58.63?(9)°. The central N-C=O plane makes dihedral angles of 30.2?(2) and 29.2?(2)° with the phenyl and 4-bromo-phenyl rings, respectively. In the crystal, mol-ecules are linked by N-H?O hydrogen bonds into chains along [100]. C-H?? contacts combine with the N-H?O hydrogen bonds, to form a three-dimensional network.

| S-EPMC3344194 | 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