6064-48-8Relevant articles and documents
New strategy for production of primary alcohols from aliphatic olefins by tandem cross-metathesis/hydrogenation
Jia, Ruilong,Zuo, Zhijun,Li, Xu,Liu, Lei,Dong, Jinxiang
supporting information, p. 1525 - 1529 (2019/11/11)
Primary alcohols are widely used in industry as solvents and precursors of detergents. The classic methods for hydration of terminal alkenes always produce the Markovnikov products. Herein, we reported a reliable approach to produce primary alcohols from terminal alkenes combining with biomass-derived allyl alcohol by tandem cross-metathesis/hydrogenation. A series of primary alcohol with different chain lengths was successfully produced in high yields (ca. 90percent). Computational studies revealed that self-metathesis and hydrogenation of substrates are accessible but much slower than cross-metathesis. This new methodology represents a unique alternative to primary alcohols from terminal alkenes.
Enantiospecific total synthesis of the squalene synthase inhibitors (-)-CJ-13,982 and its enantiomer from a common intermediate
Sturgess, Dayna,Chen, Zongjia,White, Jonathan M.,Rizzacasa, Mark A.
, p. 234 - 239 (2018/03/21)
The total syntheses of both the natural and unnatural enantiomers of the alkyl citrate natural product CJ-13,982 (1) from the common d-ribose-derived acid 6 are described.
Synthesis of 6-Hydroxysphingosine and α-Hydroxy Ceramide Using a Cross-Metathesis Strategy
Wisse, Patrick,De Geus, Mark A. R.,Cross, Gen,Van Den Nieuwendijk, Adrianus M. C. H.,Van Rooden, Eva J.,Van Den Berg, Richard J. B. H. N.,Aerts, Johannes M. F. G.,Van Der Marel, Gijsbert A.,Codée, Jeroen D. C.,Overkleeft, Herman S.
, p. 7258 - 7265 (2015/07/27)
(Chemical Equation Presented) In this paper, a new synthetic route toward 6-hydroxysphingosine and α-hydroxy ceramide is described. The synthesis employs a cross-metathesis to unite a sphingosine head allylic alcohol with a long-chain fatty acid alkene that also bears an allylic alcohol group. To allow for a productive CM coupling, the sphingosine head allylic alcohol was protected with a cyclic carbonate moiety and a reactive CM catalyst system, consisting of Grubbs II catalyst and CuI, was employed.
Extended structural modulation of bio-inspired chiral lipidic alkynylcarbinols as antitumor pharmacophores
Listunov, Dymytrii,Billot, Chelmia,Joly, Etienne,Fabing, Isabelle,Volovenko, Yulian,Génisson, Yves,Maraval, Valérie,Chauvin, Remi
, p. 7920 - 7930 (2015/09/15)
The chiral alkynylcarbinol motif typically found in natural marine products, has been the subject of intense research activity for its pharmacophoric properties, in particular cytotoxicity against tumor cell lines. In a chemical synthesis-driven four-parameter structure-activity relationship (SAR) study from the (S,E)-eicos-4-en-1-yl-3-ol natural reference 1, the (S)-dialkynylcarbinol unit of the non-natural dehydro derivative 2 emerged as an unprecedented anti-tumoral pharmacophore. An extended study of lipidic alkynylcarbinol pharmacophores is presented, addressing additional structural parameters: Z→E isomerization of the alkenyl carbinol substituent of 1, variation of the lipidic chain length of 2 (C3n, n=3, 4, 6), oxidation or substitution of the carbinol unit of 2 (to ketone, tertiary methylcarbinol, or methylether), cyclomethylenation of the double bond of 1. The synthesis of these analogues is described, including the preparation of enantio-enriched chiral alkynylcarbinol derivatives using a modified Carreira procedure for Zn-mediated addition of (trialkylsilyl)acetylene substrates to ynals in the presence of (-)- or (+)-N-methylephedrine. Preliminary cytotoxicity evaluation of 12 new products against the HCT 116 tumor cell line are finally reported and the results compared with those obtained for 1 and 2. These observations support and refine the relevance of the pharmacophoric character of secondary DAC units.
De novo asymmetric syntheses of muricatacin and its analogues via dihydroxylation of dienoates
Ahmed, Md. Moinuddin,Cui, Hu,O'Doherty, George A.
, p. 6686 - 6689 (2007/10/03)
A short and highly efficient route to both enantiomers of muricatacin as well as the C-5-epimer has been developed. The key to the overall transformation is the highly regio- and enantioselective Sharpless asymmetric dihydroxylation of an (E,Z)-dienoate. The highly efficient stereoselective synthesis prepares (-)-muricatacin in seven steps and 66% overall yield.
The first total synthesis of the 6-hydroxy-4E-sphingenines
Yadav,Geetha,Raju, A. Krishnam,Gnaneshwar,Chandrasekhar
, p. 2983 - 2985 (2007/10/03)
Ceramides containing the 6-hydroxy-4E-sphingenines, previously unknown long-chain bases, have recently been found in human skin. A total synthesis of 6-hydroxy-4E-sphingenines has been achieved.
Electrophilic selenocyclization in 2-ene-1,5-diol systems: Unexpected oxetane vs. tetrahydrofuran formation
Van De Weghe, Pierre,Bourg, Stéphane,Eustache, Jacques
, p. 7365 - 7376 (2007/10/03)
Electrophile-induced cyclization of (E)- and (Z)-2-ene-1,5-diols to tetrahydrofurans and oxetanes is described. Significant differences between the present report and previous work have been noted. A tentative model is proposed.
A simple synthetic method for chiral 1,2-epoxides and the total synthesis of a chiral pheromone epoxide
Zhang, Zhi-Bo,Wang, Zhi-Min,Wang, Yu-Xiu,Liu, Huan-Quan,Lei, Gui-Xin,Shi, Min
, p. 53 - 58 (2007/10/03)
Chiral 1,2-epoxyalkan-3-ol tosyl esters 4a-h were successfully synthesized from alkynols or allyl chlorides in three steps using Sharpless AD reaction as a key step in good yields. The chiral insect pheromone epoxide (6Z,9S,10R)-9,10-epoxyhenicos-6-ene 9 was thus smoothly synthesized from the corresponding key intermediate 4g.
A facile synthetic method for chiral 1,2-epoxides and the total synthesis of chiral pheromone epoxides
Zhang, Zhi-Bo,Wang, Zhi-Min,Wang, Yu-Xiu,Liu, Huan-Quan,Lei, Gui-Xin,Shi, Min
, p. 837 - 840 (2007/10/03)
Chiral 1,2-epoxy-3-alkanol tosylates were successfully synthesized from alkynols in three steps using the Sharpless AD reaction as a key step in good yields. Two chiral insect pheromone epoxides were smoothly obtained from the corresponding key intermediate.
Structure determination of an endogenous sleep-inducing lipid, cis-9-octadecenamide (oleamide): A synthetic approach to the chemical analysis of trace quantities of a natural product
Cravatt, Benjamin F.,Lerner, Richard A.,Boger, Dale L.
, p. 580 - 590 (2007/10/03)
The pursuit of endogenous sleep-inducing substances has been the focus of an extensive, complicated body of research. Several compounds, including Δ-sleep-inducing peptide and prostaglandin D2, have been suggested to play a role in sleep induction, and yet, the molecular mechanisms of this physiological process remain largely unknown. In recent efforts, the cerebrospinal fluid of sleep-deprived cats was analyzed in search of compounds that accumulated during sleep deprivation. An agent with the chemical formula C18H35NO was found to cycle with sleep-wake patterns, increasing in concentration with sleep deprivation and decreasing in amount upon recovery sleep. Since the material was generated in minute quantities and only under the special conditions of sleep deprivation, efforts to isolate sufficient material for adequate characterization, structure identification, and subsequent detailed evaluation of its properties proved unrealistic. With the trace amounts of the impure endogenous compound available, extensive MS studies on the agent were completed, revealing key structural features of the molecule including two degrees of unsaturation, a long alkyl chain, and a nitrogen substituent capable of fragmenting as ammonia. Additionally, HPLC traces suggested a weak UV absorbance for the unknown material. With this data in hand and encouraged by the relatively small size of the molecule, MW = 281, a synthetic approach toward the structural identification of the natural compound was initiated. Herein, we report the full details of the synthesis and comparative characterization of candidate structures for this endogenous agent that led to the unambiguous structural correlation with synthetic cis-9-octadecenamide.
