183378-26-9

Basic information

• Product Name: 2-Oxepanone,7-(1-methylethyl)-,(R)-(9CI)
• Synonyms: 2-Oxepanone,7-(1-methylethyl)-,(R)-(9CI)
• CAS NO: 183378-26-9
• Molecular Formula: C9H16O2
• Molecular Weight: 0
• Product Categories: ISOPROPYL
• Mol File: 183378-26-9.mol

Chemical Properties

• Appearance: /
• CAS DataBase Reference: 2-Oxepanone,7-(1-methylethyl)-,(R)-(9CI)(CAS DataBase Reference)
• NIST Chemistry Reference: 2-Oxepanone,7-(1-methylethyl)-,(R)-(9CI)(183378-26-9)
• EPA Substance Registry System: 2-Oxepanone,7-(1-methylethyl)-,(R)-(9CI)(183378-26-9)

Safety Data

• Hazardous Substances Data: 183378-26-9(Hazardous Substances Data)

Upstream product

• 1004-77-9 2-isopropylcyclohexanone 

Relevant articles and documents

Continuous Production of Biorenewable, Polymer-Grade Lactone Monomers through Sn-Β-Catalyzed Baeyer–Villiger Oxidation with H2O2

The Baeyer–Villiger oxidation is a key transformation for sustainable chemical synthesis, especially when H2O2 and solid materials are employed as oxidant and catalyst, respectively. 4-substituted cycloketones, which are readily available from renewables, present excellent platforms for Baeyer–Villiger upgrading. Such substrates exhibit substantially higher levels of activity and produce lactones at higher levels of lactone selectivity at all values of substrate conversion, relative to non-substituted cyclohexanone. For 4-isopropyl cyclohexanone, which is readily available from β-pinene, continuous upgrading was evaluated in a plug-flow reactor. Excellent selectivity (85 % at 65 % conversion), stability, and productivity were observed over 56 h, with over 1000 turnovers (mol product per mol Sn) being achieved with no loss of activity. A maximum space–time yield that was almost twice that for non-substituted cyclohexanone was also obtained for this substrate [1173 vs. 607 g(product) kg(catalyst)?1 cm?3 h?1]. The lactone produced is also shown to be of suitable quality for ring opening polymerization. In addition to demonstrating the viability of the Sn-β/H2O2 system to produce renewable lactone monomers suitable for polymer applications, the substituted alkyl cyclohexanones studied also help to elucidate steric, electronic, and thermodynamic elements of this transformation in greater detail than previously achieved.

Induced allostery in the directed evolution of an enantioselective Baeyer-Villiger monooxygenase

The molecular basis of allosteric effects, known to be caused by an effector docking to an enzyme at a site distal from the binding pocket, has been studied recently by applying directed evolution. Here, we utilize laboratory evolution in a different way, namely to induce allostery by introducing appropriate distal mutations that cause domain movements with concomitant reshaping of the binding pocket in the absence of an effector. To test this concept, the thermostable Baeyer-Villiger monooxygenase, phenylacetone monooxygenase (PAMO), was chosen as the enzyme to be employed in asymmetric Baeyer-Villiger reactions of substrates that are not accepted by the wild type. By using the known X-ray structure of PAMO, a decision was made regarding an appropriate site at which saturation mutagenesis is most likely to generate mutants capable of inducing allostery without any effector compound being present. After screening only 400 transformants, a double mutant was discovered that catalyzes the asymmetric oxidative kinetic resolution of a set of structurally different 2-substituted cyclohexanone derivatives as well as the desymmetrization of three different 4-substituted cyclohexanones, all with high enantioselectivity. Molecular dynamics (MD) simulations and covariance maps unveiled the origin of increased substrate scope as being due to allostery. Large domain movements occur that expose and reshape the binding pocket. This type of focused library production, aimed at inducing significant allosteric effects, is a viable alternative to traditional approaches to designed directed evolution that address the binding site directly.

Laboratory evolution of robust and enantioselective Baeyer-Villiger monooxygenases for asymmetric catalysis

The Baeyer-Villiger Monooxygenase, Phenylacetone Monooxygenase (PAMO), recently discovered by Fraaije, Janssen, and co-workers, is unusually thermostable, which makes it a promising candidate for catalyzing enantioselective Baeyer-Villiger reactions in organic chemistry. Unfortunately, however, its substrate scope is very limited, reasonable reaction rates being observed essentially only with phenylacetone and similar linear phenyl-substituted analogs. Previous protein engineering attempts to broaden the range of substrate acceptance and to control enantioselectivity have been met with limited success, including rational design and directed evolution based on saturation mutagenesis with formation of focused mutant libraries, which may have to do with complex domain movements. In the present study, a new approach to laboratory evolution is described which has led to mutants showing unusually high activity and enantioselectivity in the oxidative kinetic resolution of a variety of 2-aryl and 2-alkylcyclohexanones which are not accepted by the wild-type (WT) PAMO and of a structurally very different bicyclic ketone. The new strategy exploits bioinformatics data derived from sequence alignment of eight different Baeyer-Villiger Monooxygenases, which in conjunction with the known X-ray structure of PAMO and induced fit docking suggests potential randomization sites, different from all previous approaches to focused library generation. Sites harboring highly conserved proline in a loop of the WT are targeted. The most active and enantioselective mutants retain the high thermostability of the parent WT PAMO. The success of the "proline" hypothesis in the present system calls for further testing in future laboratory evolution studies.

Recombinant baker's yeast as a whole-cell catalyst for asymmetric Baeyer - Villiger oxidations

Cyclohexanone monooxygenase (E.C. 1.14.13.22) from Acinetobacter sp. NCIB 9871 has been expressed in baker's yeast (Saccharomyces cerevisiae) to create a general reagent for asymmetric Baeyer - Villiger oxidations. This 'designer yeast' approach combines

MMPP (Magnesium Monoperoxyphthalate) in acetonitrile; a new approach to the synthesis of lactones via Baeyer-Villiger oxidation of cyclic ketones

A variety of unsubstituted and mono- or di-substituted cycloalkanones can be oxidised with modest excess of magnesium monoperoxyphthalate hexahydrate in acetonitrile to produce the corresponding lactones in facile, selective, and high yielding manner.