38734-05-3Relevant articles and documents
PREPARATION AND SPECTROSCOPIC PROPERTIES OF CYCLODECA-1,6-DIYNE
Gleiter, Rolf,Karcher, Michael,Schaefer, Wolfgang
, p. 1635 - 1638 (1985)
The preparation of cyclodeca-1,6-diyne (1) is reported.The PE results reveal a strong interaction between the in plane ? molecular orbitals of 1.
Sodium Hypochlorite Pentahydrate as a Reagent for the Cleavage of trans-Cyclic Glycols
Kirihara, Masayuki,Osugi, Rie,Saito, Katsuya,Adachi, Kouta,Yamazaki, Kento,Matsushima, Ryoji,Kimura, Yoshikazu
, p. 8330 - 8336 (2019/06/24)
Sodium hypochlorite pentahydrate (NaOCl·5H2O) can be used toward the efficient glycol cleavage of trans-cyclic glycols, which are generally resistant to this transformation. Interestingly, the reaction of cis-cyclic glycols with NaOCl·5H2O is slower than that observed for the corresponding trans-isomer. This trans selectivity is in sharp contrast to traditional oxidants used for glycol cleavage. Acyclic glycols can also react efficiently with NaOCl·5H2O to form their corresponding carbonyl compounds in high yield.
METHOD FOR PRODUCING CYCLIC DIKETONE COMPOUND
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Paragraph 0170-0172; 0175, (2018/01/18)
Provided is a method for producing a compound represented by general formula (I) by oxidative cleavage of a compound of formula (II), which is a bicyclic tetrasubstituted olefin compound, using hydrogen peroxide. The method for producing a compound represented by general formula (I) includes a step of subjecting a compound represented by general formula (II) to oxidative cleavage using hydrogen peroxide in the presence of an acid catalyst or in the presence of a tungstic acid compound to obtain the compound represented by general formula (I): [In the formulae, formula -A1- (where the front bond denotes a bond that bonds with a carbon atom C1 while the back bond denotes a bond that bonds with a carbon atom C2) is an alkylene group having 2 to 6 carbon atoms that may have been substituted and that may further include an ether bond, an ester bond, a secondary amino group, a thioether group, or these, and formula -A2- (where the front bond denotes a bond that bonds with a carbon atom C1 while the back bond denotes a bond that bonds with a carbon atom C2) is an alkylene group having 4 to 10 carbon atoms that may have been substituted and that may further include an ether bond, an ester bond, a secondary amino group, a thioether group, or these.]
Aliphatic C-H activation with aluminium trichloride-acetyl chloride: Expanding the scope of the Baddeley reaction for the functionalisation of saturated hydrocarbons
Lyall, Catherine L.,Uosis-Martin, Mario,Lowe, John P.,Mahon, Mary F.,Panto?, G. Dan,Lewis, Simon E.
, p. 1468 - 1475 (2013/05/21)
The functionalisation of decalin by means of an "aliphatic Friedel-Crafts" reaction was reported over fifty years ago by Baddeley et al. This protocol is of current relevance in the context of C-H activation and here we demonstrate its applicability to a range of other saturated hydrocarbons. Structural elucidation of the products is described and a mechanistic rationale for their formation is presented. The "aliphatic Friedel-Crafts" procedure allows for production of novel oxygenated building blocks from abundant hydrocarbons and as such can be considered to add significant synthetic value in a single step.
Catalytic, asymmetric transannular aldolizations: Total synthesis of (+)-hirsutene
Chandler, Carley L.,List, Benjamin
, p. 6737 - 6739 (2008/12/22)
We report an asymmetric, catalytic transannular aldolization that provides polycyclic products useful for natural product synthesis. We found that a proline-derivative catalyzes the transannular aldol reaction of 1,4-cyclooctanediones to the corresponding cyclic β-hydroxy ketones in good yields and with high enantioselectivities. The utility of our reaction has been demonstrated in a total synthesis of (+)-hirustene. Copyright
Catalytic oxidation of C-H bonds
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Page 7 - 8, (2008/06/13)
The invention provides a catalytic, chemospecific and stereospecific method of oxidizing a wide variety of substrates without unwanted side reactions. Essentially, the method of the instant invention, under relatively mild reaction conditions, catalytically, stereospecifically and chemospecifically inserts oxygen into a hydrocarbon C—H bond. Oxidation (oxygen insertion) at a tertiary C—H bond to form an alcohol (and in some cases a hemiacetal) at the tertiary carbon is favored. The stereochemistry of an oxidized tertiary carbon is preserved. Ketones are formed by oxidizing a secondary C—H bond and ring-cleaved diones are formed by oxidizing cis tertiary CH bonds.
Chemospecific chromium[VI] catalyzed oxidation of C-H bonds at -40 °C
Lee, Seongmin,Fuchs
, p. 13978 - 13979 (2007/10/03)
H5IO6 in the presence of catalytic chromoyl diacetate is a powerful method for oxidation of C-H bonds. Tertiary and oxygen activated C-H bonds are oxidized to tertiary alcohols or ketones at temperatures as low as -40 °C. The putative reagent is neutral dioxoperoxy chromium[VI] which undergoes C-H oxidation with retention of stereochemistry. This reagent appears to be the first reagent capable of oxidation of a C-H bond in the presence of an olefin without concomitant epoxidation. Copyright
Methods of acylating adamantane, tricyclo[5.2.1.02,6], and decalin compounds
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, (2008/06/13)
An acylating agent of the invention includes (A) a 1,2-dicarbonyl compound or its hydroxy reductant, (B) oxygen, and (C) at least one compound selected from (c1) a metallic compound and (C2) N-hydroxyphthalimide or another imide compound. As the 1,2-dicarbonyl compound or its hydroxy reductant (A), biacetyl, 2,3-butanediolor the like canbeused. As the metallic compound (c1), cobalt acetate, or another cobalt compound, for example, can be employed. By reacting an adamantane derivative or another compound having a methine carbon atom with the acylating agent, an acyl group can be introduced to the methine carbon atom with efficiency.
Intercalation of multiple carbon atoms between the carbonyls of α-diketones
Balskus,Mendez-Andino,Arbit,Paquette
, p. 6695 - 6704 (2007/10/03)
The reaction of open-chain or cyclic α-diketones with specific ω-alkenyl organometallics leads readily under the proper conditions to 1,2-diols bonded to terminal olefinic chains. With 1-phenyl-1,2-propanedione, biacetyl, and cyclohexane-1,2-dione, allylindation in aqueous THF proceeds readily at both adjacent carbonyls. For cyclododecane-1,2-dione, recourse must be made to allylmagnesium bromide for completing the second-stage condensation. Grignard reagents have also served well as reactants for biacetyl monoadducts. In contrast, monoallylated camphorquinone is reluctant to couple to Grignard reagents and reacts only when Barbier-type alkyllithium reactions are applied. The ring closing metatheses of these products have been examined. Where six-membered ring formation operates, cyclization can be performed directly on diols. When larger rings are involved, the diols will react only if structural preorganization capable of facilitating mutual approach of the two double bonds is at play. For this purpose, the prior conversion to a cyclic carbonate holds considerable utility. In the latter setting, saponification must precede the diol cleavage step which has been performed with lead tetraacetate. The latter reagent also exhibits the very beneficial effect of facilitating removal of ruthenium and phosphorus byproducts generated during the metathesis step. This chemistry conveniently lends itself to the controlled intercalation of multiple methylene groups between the carbonyl carbons of readily available α-diketones to deliver linear or cyclic products.
Tandem deployment of indium-, ruthenium-, and lead-promoted reactions. Four-carbon intercalation between the carbonyl groups of open-chain and cyclic α-diketones
Mendez-Andino, Jose,Paquette, Leo A.
, p. 1263 - 1265 (2007/10/03)
(equation presented) An efficient strategy for the conversion of 1,2-diketones into saturated 1,6-diketones and Δ2,3/Δ3,4-unsaturated congeners thereof is reported.
