36653-40-4

Upstream product

• 1552-12-1 1,5-cis,cis-cyclooctadiene 
• 5259-72-3 cyclo-octa-1,5-diene 
• 117468-08-3 (Z)-(1S,8R)-9-oxabicyclo[6.1.0]non-4-ene 
• 19740-90-0 (Z)-9-oxabicyclo[6.1.0]non-4-ene 

Downstream Products

• 27607-33-6 (1R,2S)-Cyclooctane-1,2-diol 
• 36653-42-6 (1R*,2S*,5S*,6R*)-cyclooctane-1,2,5,6-tetrol 
• 69926-50-7 (1S,2S)-(Z)-cyclooct-5-ene-1,2-diol 
• 203319-31-7 (Z)-(1R,2R)-cyclooct-5-ene-1,2-diol 
• 51097-60-0 (Z)-oct-4-enedial 
• 119972-81-5 2-[(1R,2S,5R)-1-((Z)-(1R,8S)-8-Hydroxy-cyclooct-4-enyloxy)-2-isopropyl-5-methyl-cyclohexyl]-1-phenyl-ethanone 

Relevant academic research and scientific papers

Permanganate Ion Oxidations. 19. Hexadecyltrimethylammonium Permanganate Oxidation of Cycloalkenes

The kinetics of hexadecyltrimethylammonium permanganate (cetyltrimethylammonium permanganate, CTAP) oxidation of cycloalkenes in dichloromethane have been studied.The relative rates of oxidation versus 13C NMR chemical shifts, vertical ionization potentials, and strain energies are discussed.A comparison of the relative rate of permanganate ion oxidation with the relative rates of addition of other reagents to carbon-carbon double bonds suggests that it may act as a 1,3-dipole.

Micro-flow photosynthesis of new dienophiles for inverse-electron-demand Diels-Alder reactions. Potential applications for pretargeted in vivo PET imaging

Pretargeted PET imaging has emerged as an effective two-step in vivo approach that combines the superior affinity and selectivity of antibodies with the rapid pharmacokinetics and favorable dosimetry of smaller molecules radiolabeled with short-lived radionuclides. This approach can be based on the bioorthogonal inverse-electron-demand Diels-Alder (IEDDA) reaction between tetrazines and trans-cyclooctene (TCO) derivatives. We aimed to develop new [18F]TCO-dienophiles with high reactivity for IEDDA reactions, and favorable in vivo stability and pharmacokinetics. New dienophiles were synthesized using an innovative micro-flow photochemistry process, and their reaction kinetics with a tetrazine were determined. In vivo stability and biodistribution of the most promising 18F-radiolabeled-TCO-derivative ([18F]3) was investigated, and its potential for in vivo pretargeted PET imaging was assessed in tumor-bearing mice. We demonstrated that [18F]3 is a suitable dienophile for IEDDA reactions and for pretargeting applications.

Regioselective Cleavage of Electron-Rich Double Bonds in Dienes to Carbonyl Compounds with [Fe(OTf)2(mix-BPBP)] and a Combination of H2O2 and NaIO4

A method for the regioselective transformation of dienes to carbonyl compounds has been developed. Electron-rich olefins react selectively to yield valuable aldehydes and ketones. The method is based on the catalyst [Fe(OTf)2(mix-BPBP)] with an oxidant combination of H2O2 (1.0 equiv.) and NaIO4 (1.5 equiv.); it uses mild conditions and short reaction times, and it outperforms other olefin cleavage methodologies. The combination of an Fe-based catalyst, [Fe(OTf)2(mix-BPBP)], and the oxidants H2O2 and NaIO4 can discriminate between electronically different double bonds and oxidatively cleave the electron-rich bond in dienes to yield aldehydes and ketones in a regioselective manner. The reaction requires mild conditions (0-50 C) and short reaction times (70 min).

Malleable and Self-Healing Covalent Polymer Networks through Tunable Dynamic Boronic Ester Bonds

Despite numerous strategies involving dynamic covalent bond exchange for dynamic and self-healing materials, it remains a challenge to be able to tune the malleability and self-healing properties of bulk materials through simple small molecule perturbations. Here we describe the use of tunable rates of boronic ester transesterification to tune the malleability and self-healing efficiencies of bulk materials. Specifically, we used two telechelic diboronic ester small molecules with variable transesterification kinetics to dynamically cross-link 1,2-diol-containing polymer backbones. The sample cross-linked with fast-exchanging diboronic ester showed enhanced malleability and accelerated healing compared to the slow-exchanging variant under the same conditions. Our report demonstrates the possibility of transferring small molecule kinetics to dynamic properties of bulk solid material and may serve as a guide for the rational design of tunable dynamic materials.

Microwave- Assisted kinetic resolution of homochiral (Z)-cyclooct-5-ene-1, 2-diol and (Z)-2- Acetoxycyclooct-4-enyl acetate using lipases

Over the last decade, the use of biocatalysts has become an attractive alternative to conventional chemical methods, especially for organic synthesis, due to their unusual properties. Among these enzymes, lipases are the most widely used, because they are cheap, easily available, cofactor-free, and have broad substrate specificity. Combined to microwave heating in non- Aqueous medium, recent results suggest that irradiation may influence the enzyme activity. This Communication reports the benefits of lipases and the microwave irradiation on the kinetic resolution of racemic homochiral (Z)-cyclooct-5-ene- 1,2-diol and (Z)-2- Acetoxycyclooct-4-enyl acetate. In order to best achieve the kinetic resolution, different parameters were studied including the type of lipase, the temperature, the impact of microwave power compared to conventional heating. Optimization of the reaction parameters lead to the obtainment of highly enriched or enantiopure diols and diesters in a clean, efficient and safe way.

High-activity, single-site mesoporous WO3-MCF materials for the catalytic epoxidation of cycloocta-1,5-diene with aqueous hydrogen peroxide

For the first time, the high-activity, single-site mesoporous WO3-MCF materials were synthesized and characterized by N2 sorption, TEM, UV-vis DRS, UV-Raman, and XPS. It was found that the dispersion and nature of the tungsten species depend strongly on the tungsten oxide content and the support characteristic. The novel catalyst remains a highly ordered mesostructure of the silica support. The catalytic performance of the materials in the epoxidation of cycloocta-1,5-diene with aqueous H2O2 was investigated. The excellent catalytic performance of WO3-MCF in the selective oxidation of cycloocta-1,5-diene was attributed to the presence of isolated tetrahedral {WO4} species and the unique pore structure. The novel catalyst can be easily recycled after reaction and reused many times with no significant loss of activity. The good stability can be attributed to the presence of isolated tungsten species anchored on the support through W{single bond}O{single bond}Si covalent bonds.

Functionalised bicyclic alcohols by enantioselective α-deprotonation-rearrangement of meso-epoxides

Enantioselective α-deprotonation-rearrangement of achiral substituted cyclooctene oxides 7, 27 and 28 and N-Boc hexahydroazonine oxide 45 using organolithiums in the presence of (-)-sparteine 3 or (-)-α-isosparteine 4 gives the functionalised bicyclo[3.3.0]octan-2-ols 9, 29, and 32 and indolizinol 47 in 50-72% yields and 83-89% ees.

Transformations of saturated and unsaturated alicyclic c8 and c12 epoxides upon their hydration

The product composition and the kinetics of hydration of cycloolefin epoxides of different nature were studied to assess the effectiveness of alternative directions in the synthesis of saturated alicyclic vicinal C8 and C12 diols. The reactivity and selectivity for the desired diol formation was estimated, depending on the structure of the epoxide used. The rate and activation parameters of hydration were determined. To ensure a high yield of saturated alicyclic vicinal C8 and C12 diols in their production from corresponding unsaturated epoxide compounds, we found it reasonable that the hydration of unsaturated epoxides and the hydrogenation of the resultant unsaturated diols be conducted as successive steps. The comparative analysis of rate parameters for double bond hydrogenation of in C8 unsaturated diol, epoxide, ketone, and cis-cyclooctene in presence of finely dispersed deposited palladium catalysts is performed. An oxygen-containing functional group was shown to facilitate the saturation of double bond in the ring, enhancing the adsorptive properties of a substrate molecule on the catalyst surface.

Synthesis of unsaturated C8 and C12 alicyclic 1,2-diols based on monoepoxides of cyclo-olefins

A study has been made of the kinetics of hydration of unsaturated C8 and C12 alicyclic epoxides (5,6-epoxy-cis-cyclo-octene and 9,10-epoxy-1,5-cis,trans-cyclododecadiene) in a heterophase liquid-liquid system with the use of hydrocarbon solvents. It has been established that the reactivity of the epoxy group during hydration is determined by features of the conformational structure of the initial molecule. On the basis of the data obtained, conditions are proposed which ensure the almost complete conversion of the epoxide into the target 1,2-diol when the process is carried out in the presence of catalysts of the acid type.

Simple Designs for the Construction of Complex Trans-Fused Polyether Toxin Frameworks. A Linear Strategy Based on Entropically Favored Oxirane Ring Enlargement in Epoxycycloalkenes Followed by Carbon-Carbon or Carbon-Oxygen Bond-Forming Cyclizations

A successful design for the construction of trans-fused medium-size cyclic ethers is described.The key features of the synthesis are as follows: (i) intramolecular oxirane ring expansion in cycloalkenes to give bridged oxabicyclic systems and (ii) linear, one- or two-directional synthetic operations which generate external oxocycles in single reaction steps.The general approach involves the intramolecular addition of a stable γ-alkoxy-substituted allylstannane to an aldehyde carbonyl group, and the entire reaction is conducted in a one-pot process which includes the following: (i) vic-diol fragmentation from the bridged oxabicyclic precursor and (ii) Lewis acid-induced cyclization of the resulting aldehyde-allylic tin system.While the present strategy was mostly developed around racemic models, the potential for adoption of enantioselective features is immediate.The versatility, scope, limitations, and potential applications of the present technology are discussed in detail.