57794-08-8

Usage

Uses

Used in Chemical Synthesis:
(1S,2S)-TRANS-1,2-CYCLOHEXANEDIOL is used as a key intermediate in the synthesis of various organic compounds. It is particularly useful in the preparation of (1S,2S)-1,2-cyclohexanediyl bis(4-vinylbenzoate) by reacting with 4-vinylbenzoyl chloride. This reaction can lead to the formation of complex molecular structures with potential applications in materials science and pharmaceuticals.
Used in Chiral Ligand Applications:
(1S,2S)-TRANS-1,2-CYCLOHEXANEDIOL is also used as a chiral ligand in the preparation of non-racemic hydroxy phosphonates via titanium alkoxide-catalyzed addition of dimethyl phosphite to the corresponding aldehydes. This application highlights the importance of chirality in the development of pharmaceuticals and other specialty chemicals, as the stereochemistry of a molecule can significantly impact its biological activity and efficacy.
Used in Pharmaceutical Industry:
In the pharmaceutical industry, (1S,2S)-TRANS-1,2-CYCLOHEXANEDIOL may be utilized as a building block for the development of new drugs or as a chiral auxiliary in the synthesis of enantiomerically pure compounds. (1S,2S)-TRANS-1,2-CYCLOHEXANEDIOL's unique stereochemistry can be exploited to create molecules with specific biological targets, potentially leading to more effective and selective medications.
Used in Materials Science:
(1S,2S)-TRANS-1,2-CYCLOHEXANEDIOL can be employed in the development of novel materials with unique properties, such as improved mechanical strength, thermal stability, or chemical resistance. (1S,2S)-TRANS-1,2-CYCLOHEXANEDIOL's ability to form complex molecular structures through chemical reactions can contribute to the advancement of materials science and the creation of innovative products.

Purification Methods

The enantiomers have been recrystallised from *C6H6 or EtOAc. The (±) diol has been resolved via the distrychnine salt of the hemisulfate [Hayward et al. J Chem Soc Perkin Trans 1 2413 1976], or the 1-menthoxy acetates. {l-trans-diastereoisomer has m 64o, []D -91.7o (c 1.4 EtOH) from pet ether or aqueous EtOH and yields the (-)-trans-diol } and {d-trans-diastereoisomer has m 126-127o, []D -32.7o (c 0.8 EtOH) from pet ether or aqueous EtOH and yields the (+)-trans diol}. The bis-4-nitrobenzoate has m 126.5o []D (-) and (+) 25.5o (c 1.1 CHCl3), and the bis-3,5-dinitrobenzoate has m 160o []D ± 83.0o (c 1.8 CHCl3) [Wilson & Read J Chem Soc 1269 1935]. [Beilstein 6 III 4060.]

Upstream product

• 1792-81-0 cis-1,2-cyclohexane 
• 105663-25-0 (1S,2S)-trans-1,2-cyclohexanediol diacetate 
• 85761-38-2 (+)-(R,R)-benzylcyclohexan-1,2-diol 
• 53439-93-3 (S)-α-hydroxycyclohexanone 
• 62921-46-4 trans-2-acetoxy-1-cyclohexanol 
• 286-20-4 cyclohexane-1,2-epoxide 
• 76035-73-9 (1S,2S)-2-hydroxycyclohexyl α-D-glucopyranoside 
• 765-87-7 cyclohexane-1,2-dione 
• 286-20-4 cyclohexene oxide 
• 1460-57-7 trans-1,2-cyclohexandiol 
• 98-88-4 benzoyl chloride 
• 133-89-1 UDP-glucose 
• 108-94-1 cyclohexanone 
• 944060-93-9 C₁₆H₂₀O₅ 

Downstream Products

• 113712-84-8 trans-1,2-dipicryloxycyclohexane 
• 98966-21-3 trans-2-picryloxy-1-cyclohexanole 
• 145222-66-8 ((1S,5S,6S)-3-Methyl-bicyclo[3.2.1]oct-3-en-6-yl)-acetic acid (1S,2S)-2-hydroxy-cyclohexyl ester 
• 145222-66-8 ((1R,5R,6R)-3-Methyl-bicyclo[3.2.1]oct-3-en-6-yl)-acetic acid (1S,2S)-2-hydroxy-cyclohexyl ester 
• 145222-68-0 ((1R,5R,6R)-3-Butyl-bicyclo[3.2.1]oct-3-en-6-yl)-acetic acid (1S,2S)-2-hydroxy-cyclohexyl ester 
• 145222-68-0 ((1S,5S,6S)-3-Butyl-bicyclo[3.2.1]oct-3-en-6-yl)-acetic acid (1S,2S)-2-hydroxy-cyclohexyl ester 
• 145264-93-3 2-((1S,5S,6S)-3-Phenyl-bicyclo[3.2.1]oct-3-en-6-yl)-ethanol 
• 145222-77-1 2-((1R,5R,6R)-3-Phenyl-bicyclo[3.2.1]oct-3-en-6-yl)-ethanol 
• 145222-72-6 ((1S,5S,6S)-3-Phenyl-bicyclo[3.2.1]oct-3-en-6-yl)-acetic acid (1S,2S)-2-hydroxy-cyclohexyl ester 
• 145222-72-6 ((1R,5R,6R)-3-Phenyl-bicyclo[3.2.1]oct-3-en-6-yl)-acetic acid (1S,2S)-2-hydroxy-cyclohexyl ester 
• 145511-67-7 2-((1S,5S,6S)-3-Cyclohexyl-bicyclo[3.2.1]oct-3-en-6-yl)-ethanol 
• 145222-76-0 2-((1R,5R,6R)-3-Cyclohexyl-bicyclo[3.2.1]oct-3-en-6-yl)-ethanol 
• 145222-70-4 ((1S,5S,6S)-3-Cyclohexyl-bicyclo[3.2.1]oct-3-en-6-yl)-acetic acid (1S,2S)-2-hydroxy-cyclohexyl ester 
• 145222-70-4 ((1R,5R,6R)-3-Cyclohexyl-bicyclo[3.2.1]oct-3-en-6-yl)-acetic acid (1S,2S)-2-hydroxy-cyclohexyl ester 

Relevant academic research and scientific papers

Enantiotopic Discrimination by Coordination-Desymmetrized meso-Ligands

The first examples of enantiopure catalysts that are chiral merely due to coordination of different metal ions at enantiotopic positions of an achiral meso-ligand are reported. These catalysts exhibit a pseudo-Cs symmetry and are able to catalyze reactions demanding simultaneous involvement of two catalytic sites. The latter was demonstrated by application in the asymmetric ring-opening of meso-epoxides.

SYNTHESIS AND APPLICATION OF CHIRAL SUBSTITUTED POLYVINYLPYRROLIDINONES

Chiral polyvinylpyrrolidinone (CSPVP), complexes of CSPVP with a core species, such as a metallic nanocluster catalyst, and enantioselective oxidation reactions utilizing such complexes are disclosed. The CSPVP complexes can be used in asymmetric oxidation of diols, enantioselective oxidation of alkenes, and carbon-carbon bond forming reactions, for example. The CSPVP can also be complexed with biomolecules such as proteins, DNA, and RNA, and used as nanocarriers for siRNA or dsRNA delivery.

Olefin reaction in the catalyst and the olefin production

PROBLEM TO BE SOLVED: To provide a catalyst for obtaining an olefin in high selectivity with a vicinal diol as a raw material.SOLUTION: A catalyst for olefination reaction for use in a reaction to produce an olefin by a reaction of a polyol, having two adjacent carbon atoms each having a hydroxy group, with hydrogen comprises: a carrier; at least one oxide selected from the group consisting of oxides of the group 6 elements and oxides of the group 7 elements supported on the carrier; and at least one metal selected from the group consisting of silver, iridium, and gold supported on the carrier.SELECTED DRAWING: None

Aromatic Donor-Acceptor Interaction-Based Co(III)-salen Self-Assemblies and Their Applications in Asymmetric Ring Opening of Epoxides

Aromatic donor-acceptor interaction as the driving force to assemble cooperative catalysts is described. Pyrene/naphthalenediimide functionalized Co(III)-salen complexes self-assembled into bimetallic catalysts through aromatic donor-acceptor interactions and showed high catalytic activity and selectivity in the asymmetric ring opening of various epoxides. Control experiments, nuclear magnetic resonance (NMR) spectroscopy titrations, mass spectrometry measurement, and X-ray crystal structure analysis confirmed that the catalysts assembled based on the aromatic donor-acceptor interaction, which can be a valuable noncovalent interaction in supramolecular catalyst development.

Epoxidation of cyclohexene with H2O2 over efficient water-tolerant heterogeneous catalysts composed of mono-substituted phosphotungstic acid on co-functionalized SBA-15

A series of Keggin-type heteropolyacid-based heterogeneous catalysts (Co-/Fe-/Cu-POM-octyl-NH3-SBA-15) were synthesized via immobilized transition metal mono- substituted phosphotungstic acids (Co-/Fe-/Cu-POM) on octyl-amino-co-functionalized mesoporous silica SBA-15 (octyl-NH2-SBA-15). Characterization results indicated that Co-/Fe-/Cu-POM units were highly dispersed in mesochannels of SBA-15, and both types of Br?nsted and Lewis acid sites existed in Co-/Fe-/Cu-POM-octyl-NH3-SBA-15 catalysts. Co-POM-octyl-NH3-SBA-15 catalyst showed excellent catalytic performance in H2O2-mediated cyclohexene epoxidation with 83.8% of cyclohexene conversion, 92.8% of cyclohexene oxide selectivity, and 98/2 of epoxidation/allylic oxidation selectivity. The order of catalytic activity was Co-POM-octyl-NH3-SBA-15?>?Fe-POM-octyl-NH3-SBA-15?>?Cu-POM-octyl-NH3-SBA-15. In order to obtain insights into the role of -octyl moieties during catalysis, an octyl-free catalyst (Co-POM-NH3-SBA-15) was also synthesized. In comparison with Co-POM-NH3-SBA-15, Co-POM-octyl-NH3-SBA-15 showed enhanced catalytic properties (viz. activity and selectivity) in cyclohexene epoxidation. Strong chemical bonding between -NH3 + anchored on the surface of SBA-15 and heteropolyanions resulted in excellent stability of Co-POM-octyl-NH3-SBA-15 catalyst, and it could be reused six times without considerable loss of activity.

Well-confined polyoxometalate-ionic liquid in silicic framework for environmentally friendly asymmetric di-hydroxylation of olefins

Chiral 1,2-diols with a high yield could be directly prepared from asymmetric di-hydroxylation of olefins via an eco-friendly and enduring catalyst, in which abundant "chiral pools" of polyoxometalate-ionic liquid were target-designed into the silicic framework (POM-ILS) and well stabilized in aqueous media.

Organic salts and merrifield resin supported [PM12O40]3? (M = Mo or W) as catalysts for adipic acid synthesis

Adipic acid (AA) was obtained by catalyzed oxidation of cyclohexene, epoxycyclohexane, or cyclohexanediol under organic solvent-free conditions using aqueous hydrogen peroxide (30%) as an oxidizing agent and molybdenum- or tungsten-based Keggin polyoxometalates (POMs) surrounded by organic cations or ionically supported on functionalized Merrifield resins. Operating under these environmentally friendly, greener conditions and with low catalyst loading (0.025% for the molecular salts and 0.001–0.007% for the supported POMs), AA could be produced in interesting yields.

Calix[8]arene as New Platform for Cobalt-Salen Complexes Immobilization and Use in Hydrolytic Kinetic Resolution of Epoxides

Eight cobalt-salen complexes have been covalently attached to a calix[8]arene platform through a flexible linker by a procedure employing Click chemistry. The corresponding well-defined catalyst proved its efficiency in the hydrolytic kinetic resolution (HKR) of various epoxides through an operative bimetallic cooperative activation, demonstrating highly enhanced activity when compared to its monomeric analogue. As an insoluble complex, this multisite cobalt-salen catalyst could be easily recovered and reused in successive catalytic runs. Products were isolated by a simple filtration with virtually no cobalt traces and without requiring a prior purification by flash chromatography.

Structural and Computational Insight into the Catalytic Mechanism of Limonene Epoxide Hydrolase Mutants in Stereoselective Transformations

Directed evolution of limonene epoxide hydrolase (LEH), which catalyzes the hydrolytic desymmetrization reactions of cyclopentene oxide and cyclohexene oxide, results in (R,R)- and (S,S)-selective mutants. Their crystal structures combined with extensive theoretical computations shed light on the mechanistic intricacies of this widely used enzyme. From the computed activation energies of various pathways, we discover the underlying stereochemistry for favorable reactions. Surprisingly, some of the most enantioselective mutants that rapidly convert cyclohexene oxide do not catalyze the analogous transformation of the structurally similar cyclopentene oxide, as shown by additional X-ray structures of the variants harboring this slightly smaller substrate. We explain this puzzling observation on the basis of computational calculations which reveal a disrupted alignment between nucleophilic water and cyclopentene oxide due to the pronounced flexibility of the binding pocket. In contrast, in the stereoselective reactions of cyclohexene oxide, reactive conformations are easily reached. The unique combination of structural and computational data allows insight into mechanistic details of this epoxide hydrolase and provides guidance for future protein engineering in reactions of structurally different substrates.

One-Pot Enzymatic Synthesis of Cyclic Vicinal Diols from Aliphatic Dialdehydes via Intramolecular C?C Bond Formation and Carbonyl Reduction Using Pyruvate Decarboxylases and Alcohol Dehydrogenases

An enzymatic cascade reaction was developed for one-pot enantioselective conversion of aliphatic dialdehydes to chiral vicinal diols using pyruvate decarboxylases (PDCs) and alcohol dehydrogenases (ADHs). The PDCs showed promiscuity in catalysing the cyclization of aliphatic dialdehydes through intramolecular stereoselective carbon-carbon bond formation. Consequently, 1,2-cyclopentanediols in three different stereoisomeric forms and 1,2-cyclohexanediols in two different stereoisomeric forms could be prepared with high conversion and stereoisomeric ratio from the respective initial substrates, glutaraldehyde and adipaldehyde. These cascade reactions represent a promising approach to the biocatalytic synthesis of important chiral vicinal diols. (Figure presented.).