Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Gas phase thermal reactions of exo-8-cyclopropyl-bicyclo[4.2.0]oct-2-ene (1-exo).

ABSTRACT: The title compound 1-exo (with minor amounts of its C8 epimer 1-endo) was prepared by Wolff-Kishner reduction of the cycloadduct of 1,3-cyclohexadiene and cyclopropylketene. The [1,3]-migration product 2-endo was synthesized by efficient selective cyclopropanation of endo-5-vinylbicyclo[2.2.2]oct-2-ene at the exocyclic ?-bond. Gas phase thermal reactions of 1-exo afforded C8 epimerization to 1-endo, [1,3]- migrations to 2-exo and 2-endo, direct fragmentation to cyclohexadiene and vinylcyclopropane, and CPC rearrangement in the following relative kinetic order: kep > k13 > kf > kCPC.

SUBMITTER: Leber PA

PROVIDER: S-EPMC6271342 | biostudies-literature | 2014 Jan

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Gas phase thermal reactions of exo-8-cyclopropyl-bicyclo[4.2.0]oct-2-ene (1-exo).

Leber Phyllis A PA Nocket Anthony J AJ Hancock-Cerutti William W Bemis Christopher Y CY Khine Wint Khant WK Mohrbacher Iii Joseph A JA Baldwin John E JE

Molecules (Basel, Switzerland) 20140127 2

The title compound 1-exo (with minor amounts of its C8 epimer 1-endo) was prepared by Wolff-Kishner reduction of the cycloadduct of 1,3-cyclohexadiene and cyclopropylketene. The [1,3]-migration product 2-endo was synthesized by efficient selective cyclopropanation of endo-5-vinylbicyclo[2.2.2]oct-2-ene at the exocyclic π-bond. Gas phase thermal reactions of 1-exo afforded C8 epimerization to 1-endo, [1,3]- migrations to 2-exo and 2-endo, direct fragmentation to cyclohexadiene and vinylcyclopropa ...[more]

PMID: 24473211

Similar Datasets

1,3,4,6-Tetra-chloro-7,7-bis-(4-chloro-phen-yl)bicyclo-[4.2.0]oct-3-ene-2,5-dione.

Project description:The title compound, C(20)H(10)Cl(6)O(2), a quinone derivative, was obtained by the irradiation of 2,3,5,6-tetra-chloro-benzo-quinone and 4,4'-(ethene-1,1-di-yl)bis-(chloro-benzene). The six- and four-membered rings are fused in a cis configuration. The dihedral angle between them is 53.4 (3)°.

| S-EPMC2959757 | biostudies-literature

Gold(I)-catalyzed formation of bicyclo[4.2.0]oct-1-enes.

Project description:Gold(I) catalysts effectively promote the Cope rearrangement of acyclic 1,5-dienes bearing a terminal cyclopropylidene. When this methodology is applied to cyclic substrates an unexpected transformation occurs, resulting in the formation of a tricyclic compound incorporating a bicyclo[4.2.0]oct-1-ene core, a portion of which is found in a number of natural products. Density functional theory calculations (M06 and M06-2X) reveal insight into the mechanism and thermodynamics of this unique transformation.

| S-EPMC3788353 | biostudies-literature

Stereoselective Alder-Ene Reactions of Bicyclo[1.1.0]butanes: Facile Synthesis of Cyclopropyl- and Aryl-Substituted Cyclobutenes.

Project description:Bicyclo[1.1.0]butanes (BCBs), strained carbocycles comprising two fused cyclopropane rings, have become well-established building blocks in organic synthesis, medicinal chemistry, and chemical biology due to their diverse reactivity profile with radicals, nucleophiles, cations, and carbenes. The constraints of the bicyclic ring system confer high p-character on the interbridgehead C-C bond, leading to this broad reaction profile; however, the use of BCBs in pericyclic processes has to date been largely overlooked in favor of such stepwise, non-concerted additions. Here, we describe the use of BCBs as substrates for ene-like reactions with strained alkenes and alkynes, which give rise to cyclobutenes decorated with highly substituted cyclopropanes and arenes. The former products are obtained from highly stereoselective reactions with cyclopropenes, generated in situ from vinyl diazoacetates under blue light irradiation (440 nm). Cyclobutenes featuring a quaternary aryl-bearing carbon atom are prepared from equivalent reactions with arynes, which proceed in high yields under mild conditions. Mechanistic studies highlight the importance of electronic effects in this chemistry, while computational investigations support a concerted pathway and rationalize the excellent stereoselectivity of reactions with cyclopropenes.

| S-EPMC10786042 | biostudies-literature

Long-Range Kinetic Effects on the Alternating Ring Opening Metathesis of Bicyclo[4.2.0]oct-6-ene-7-carboxamides and Cyclohexene.

Project description:We report an investigation of rates of ruthenium-catalyzed alternating ring opening metathesis (AROM) of cyclohexene with two different Ru-cyclohexylidene carbenes derived from bicyclo[4.2.0]oct-6-ene-7-carboxamides (A monomer) that bear different side chains. These monomers are propylbicyclo[4.2.0]oct-6-ene-7-carboxamide and N-(2-(2-ethoxyethoxy)ethanylbicyclo[4.2.0]oct-6-ene-7-carboxamide. The amide substitution of these monomers directly affects both the rate of the bicyclo[4.2.0]oct-6-ene-7-carboxamide ring opening and the rate of reaction of the resulting carbene with cyclohexene (B monomer). The resulting Ru-cyclohexylidenes underwent reversible ring opening metathesis with cyclohexene. However, the thermodynamic equilibrium disfavored cyclohexene ring opening. Utilization of triphenylphosphine forms a more stable PPh3 ligated complex, which suppresses the reverse ring closing reaction and allowed direct measurements of the forward rate constants for formation of various A-B and A-B-A' complexes through carbene-catalyzed ring-opening metathesis and thus gradient polymer structure-determining steps. The relative rate of the propylbicyclo[4.2.0]oct-6-ene-7-carboxamide ring opening is 3-fold faster than that of the N-(2-(2-ethoxyethoxy)ethanylbicyclo[4.2.0]oct-6-ene-7-carboxamide. In addition, the rate of cyclohexene ring-opening catalyzed by the propyl bicyclooctene is 1.4 times faster than when catalyzed by the ethoxyethoxy bicyclooctene. Also, the subsequent rates of bicyclo[4.2.0]oct-6-ene-7-carboxamide ring opening by propyl-based Ru-hexylidene are 1.6-fold faster than ethoxyethoxy-based Ru-hexylidene. Incorporation of the rate constants into reactivity ratios of bicyclo[4.2.0]amide-cyclohexene provides prediction of copolymerization kinetics and gradient copolymer structures.

| S-EPMC10401671 | biostudies-literature

7-Benzene-sulfonamido-3-ethenyl-8-oxo-5-thia-1-aza-bicyclo-[4.2.0]oct-2-ene-2-carboxylic acid methanol solvate.

Project description:In the title compound, C(15)H(14)N(2)O(5)S(2)·CH(4)O, the six-membered ring fused to the ?-lactam unit adopts a twisted conformation. In the crystal structure, the component mol-ecules are linked into a three-dimensional framework through inter-molecular N-H?S, N-H?O and O-H?O hydrogen bonds and C-H?O contacts.

| S-EPMC2977380 | biostudies-literature

Bicyclo-[2.2.2]oct-7-ene-2,3,5,6-tetra-carboxylic dianhydride.

Project description:In the title compound, C(12)H(8)O(6), mol-ecules are linked by weak C-H⋯O inter-actions involving all the potential donors, generating a three-dimensional network.

| S-EPMC2961621 | biostudies-literature

Porous Metal-Organic Cages Based on Rigid Bicyclo[2.2.2]oct-7-ene Type Ligands: Synthesis, Structure, and Gas Uptake Properties.

Project description:Three new ligands containing a bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxydiimide unit have been used to assemble lantern-type metal-organic cages with the general formula [Cu4 L4 ]. Functionalisation of the backbone of the ligands leads to distinct crystal packing motifs between the three cages, as observed with single-crystal X-ray diffraction. The three cages vary in their gas sorption behaviour, and the capacity of the materials for CO2 is found to depend on the activation conditions: softer activation conditions lead to superior uptake, and one of the cages displays the highest BET surface area found for lantern-type cages so far.

| S-EPMC10947411 | biostudies-literature

1-Meth-oxy-3-o-tolyl-bicyclo-[2.2.2]oct-5-ene-2,2-dicarbonitrile.

Project description:In the title compound, C(18)H(18)N(2)O, the cyclo-hexene and cyclo-hexane rings of the bicyclo-[2.2.2]oct-5-ene unit adopt distorted boat conformations. In the crystal, mol-ecules exist as C-H?N hydrogen-bonded centrosymmetric R(2) (2)(14) dimers, which are further linked by C-H?? inter-actions.

| S-EPMC2970108 | biostudies-literature

Methyl 2-diphenyl-phosphor-yloxy-2-aza-bicyclo-[2.2.1]hept-5-ene-3-exo-carboxyl-ate.

Project description:In the title compound, C(20)H(20)NO(4)P, the dihedral angle between the phenyl rings is 68.52 (7)°. In the crystal structure, the mol-ecules are linked by a weak C-H⋯π(arene) inter-action along [010] involving the phenyl CH group and the phenyl rings. There are no further significant inter-molecular inter-actions.

| S-EPMC2968096 | biostudies-literature

3-exo-Chloro-8-oxabicyclo-[3.2.1]oct-6-ene-2,4-diol chloro-form 0.33-solvate.

Project description:The title compound, 3C(7)H(9)ClO(3)·CHCl(3), crystallizes with mol-ecules of 3-exo-chloro-8-oxabicyclo-[3.2.1]oct-6-ene-2,4-diol (A) and chloro-form in a 3:1 ratio, in the space group R3m. Mol-ecules of A straddle a crystallographic mirror plane, whereas the chloro-form mol-ecules (C and H atoms) lie additionally on the threefold axis. The mol-ecules of A are linked into right- and left-helical chains by means of O-H?O hydrogen bonds, thus forming columns running along the c axis. Six inter-penetrated columns form a channel in which the solvent mol-ecules (chloro-form) are located.

| S-EPMC2969453 | 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