117919-55-8Relevant articles and documents
Synthesis and properties of disulfide-bond containing eight-membered rings
Ruggles, Erik L.,Hondal, Robert J.
, p. 4281 - 4284 (2006)
The cyclocystine ring structure (CRS, 3), which results from a disulfide-bond between adjacent cysteine residues, is a rare motif in protein structures and is functionally important to those few proteins that posses it. This letter will focus on the const
A new facile preparation of a bifunctionalized C6 homologating agent from 1,4-cyclohexadiene
Michaud, Sabine,Viala, Jacques
, p. 3019 - 3024 (1999)
a new preparation of the bifunctionalized unsaturated C6 homologating agent 2b which is an efficient synthetic tool is described. This method is atom economic, very efficient on grams scale and easy to handle from cheap commercially available 1,4-cyclohexadiene. Synthetic applications by using a mild and selective monohydrolysis of acetal catalyzed by FeCl3 are described.
Hydrogen Bonding-Assisted Enhancement of the Reaction Rate and Selectivity in the Kinetic Resolution of d,l-1,2-Diols with Chiral Nucleophilic Catalysts
Fujii, Kazuki,Mitsudo, Koichi,Mandai, Hiroki,Suga, Seiji
, p. 2778 - 2788 (2017/08/23)
An extremely efficient acylative kinetic resolution of d,l-1,2-diols in the presence of only 0.5 mol% of binaphthyl-based chiral N,N-4-dimethylaminopyridine was developed (selectivity factor of up to 180). Several key experiments revealed that hydrogen bonding between the tert-alcohol unit(s) of the catalyst and the 1,2-diol unit of the substrate is critical for accelerating the rate of monoacylation and achieving high enantioselectivity. This catalytic system can be applied to a wide range of substrates involving racemic acyclic and cyclic 1,2-diols with high selectivity factors. The kinetic resolution of d,l-hydrobenzoin and trans-1,2-cyclohexanediol on a multigram scale (10 g) also proceeded with high selectivity and under moderate reaction conditions: (i) very low catalyst loading (0.1 mol%); (ii) an easily achievable low reaction temperature (0 °C); (iii) high substrate concentration (1.0 M); and (iv) short reaction time (30 min). (Figure presented.).
Synthesis of saturated benzodioxepinone analogues: Insight into the importance of the aromatic ring binding motif for marine odorants
Plummer, Christopher M.,Gericke, Robert,Kraft, Philip,Raynor, Aaron,Froese, Jordan,Hudlick, Tom,Rook, Trevor J.,Jones, Oliver A. H.,Hügel, Helmut M.
, p. 486 - 495 (2015/01/30)
As part of our research exploring the influence of molecular variations of Calone 1951 on marine fragrance performance, we report the synthesis, crystal structures, and olfactory analysis of the first saturated benzodioxepinone analogues. By su
Regioselective cyclopolymerization of 1,7-octadiynes
Naumann, Stefan,Unold, Joerg,Frey, Wolfgang,Buchmeiser, Michael R.
, p. 8380 - 8387 (2012/03/11)
The regioselective cyclopolymerization of two structurally different 1,7-octadiynes, i.e. of 1,4-dihexyloxy-2,3-dipropargylbenzene (M1) and (R,R)/(S,S)-4,5-bis(trimethylsilyloxy)-1,7-octadiyne (M2) has been achieved with the modified Grubbs-Hoveyda-type metathesis initiator Ru(NCO) 2(IMesH2)(=CH-(2-(2-PrO)C6H4)) (I1, IMesH2 = 1,3-dimesitylimidazolidin-2-ylidene) and with a series of Schrock initiators in the presence of quinuclidine, yielding conjugated polymers consisting virtually exclusively of 1,2-cyclohex-1-enylenvinylene units. In contrast to I1, Mo(N-2,6-(2-Pr)2C6H3) (CHCMe2Ph)(OCHMe2)2 (I3) allows for establishing a living polymerization with M2 in the presence of quinuclidine. The structure of the polymers, which represent highly soluble and stable poly(acetylene) analogues, was confirmed by comparing the 13C NMR shifts of model compounds with those of the corresponding polymer. Poly(ene)s that are virtually solely based on six-membered repeat units show a bathochromic shift in UV-absorption compared to poly(ene)s based on six- and seven-membered rings.
Synthesis, redox properties, and conformational analysis of vicinal disulfide ring mimics
Ruggles, Erik L.,Deker, P. Bruce,Hondal, Robert J.
experimental part, p. 1257 - 1267 (2009/05/07)
A vicinal disulfide ring (VDR) results from disulfide-bond formation between two adjacent cysteine residues. This eight-membered ring is a rare motif in protein structures and is functionally important to those few proteins that posses it. This article focuses on the construction of strained and unstrained VDR mimics, discernment of the preferred conformation of these mimics, and the determination of their respective disulfide redox potentials.
Epoxide hydrolase-catalyzed enantioselective synthesis of chiral 1,2-diols via desymmetrization of meso-epoxides
Zhao, Lishan,Han, Bin,Huang, Zilin,Miller, Mark,Huang, Hongjun,Malashock, Dan S.,Zhu, Zuolin,Milan, Aileen,Robertson, Dan E.,Weiner, David P.,Burk, Mark J.
, p. 11156 - 11157 (2007/10/03)
The discovery, from nature, of a diverse set of microbial epoxide hydrolases is reported. The utility of a library of epoxide hydrolases in the synthesis of chiral 1,2-diols via desymmetrization of a wide range of meso-epoxides, including cyclic as well as acyclic alkyl- and aryl-substituted substrates, is demonstrated. The chiral (R,R)-diols were furnished with high ee's and yields. The discovery of the first microbial epoxide hydrolases providing access to complementary (S,S)-diols is also described. Copyright
One-Pot and Stereospecific Synthesis of cis-1,2-Diazides via Mitsunobu Reaction of Epoxides
Goeksu, Sueleyman,Secen, Hasan,Suetbeyaz, Yasar
, p. 2373 - 2378 (2007/10/03)
Mitsunobu reaction of epoxides using hydrazoic acid, diethylazodicarboxylate, and triphenylphosphine as reagents gave the corresponding cis-1,2-diazides in moderate yield. Application of similar reaction conditions to trans-diols furnished the corresponding trans-1,2-diazides.
Hydroxyl-radical-induced Oxidation of Cyclohexa-1,4-diene by O2 in Aqueous Solution. A Pulse Radiolysis and Product Study
Pan, Xian-Ming,Schuchmann, Man Nien,Sonntag, Clemens von
, p. 1021 - 1028 (2007/10/02)
Hydroxyl radicals have been generated radiolytically in N2O/O2 (4 : 1)-saturated aqueous solutions.They react with cyclohexa-1,4-diene by H-abstraction and by addition to a double bond yielding equal amounts of cyclohexadienyl 1 and 6-hydroxycyclohex-3-enyl radicals 2.As shown by pulse radiolysis, 1 and 2 react with O2 with an overall rate constant of k = 1.2 * 109 dm3 mol-1s-1.Radical 1 yields two isomeric peroxyl radicals: 4(cyclohexa-1,3-diene structure) and 5(cyclohexa-1,4-diene structure).Since the C-H ... radical-O-O distance in 4 is only ca. 1.8 Angstroem, it is suggested that 4 is the radical which rapidly eliminates HO2(radical) (k 8 * 105 s-1 as measured by pulse radiolysis) yielding benzene (ca. 60percent of 4 + 5).The peroxyl radical 5 which has a longer C-H ...radical-O-O distance (ca. 3.8 Aongstrem) might not undergo this reaction.Instead it undergoes intramolecular cyclization thereby forming endoperoxidic intermediates which are believed to be the precursors of products which upon reduction with NaBH4 yield trihydroxycyclohexenes.In the presence of superoxide dismutase to remove O2(anion) radicals and at low cyclohexa-1,4-diene concentration (4 * 10-4 mol dm-3), the 6-hydroxycyclohex-3-en-yl-peroxyl radicals 6 and 7 derived from 2 decay bimolecularly yielding equal amounts of 4,5-dihydroxycyclohexene, 6-hydroxycyclohex-3-enone and oxygen (k = 1.3 * 108 dm3 mol-1 s-1).At high cyclohexa-1,4-diene concentration (10-2 mol dm-3) 6 and 7 abstract H-atoms from the substrate (k = 820 dm3 mol-1 s-1) yielding the corresponding 6-hydroxycyclohex-3-enyl hydroperoxides.In competition with these bimolecular reactions, 6 and 7 also undergo intramolecular cyclization similar to radical 5.In subsequent reactions endoperoxidic products are formed which have been identified as tetrahydroxycyclohexanes after reduction with NaBH4.A number of fragment products with one to three carbon atoms have also been found which may result from the degradation of some of the endoperoxidic intermediates derived from the radicals 5, 6 and 7.A material balance is presented which accounts for the oxygen consumed in this system.
Preparation of Optically Active γ-Hydroxyethyl α,β-Unsaturated γ-Lactone Using an Enzymatic Procedure
Suemune, Hiroshi,Hizuka, Michiyo,Kamashita, Tomoko,Sakai, Kiyoshi
, p. 1379 - 1381 (2007/10/02)
γ-Hydroxyethyl α,β-unsaturated γ-lactone (2) is a promising intermediate for the synthesis of eldanolide and cis,cis-1,2,3-trisubstituted cyclopentane, which could be converted to 11-deoxyprostaglandins.In order to prepare optically active 2, enzymatic hy
