10408-15-8Relevant articles and documents
TRANSPOSITION D'OXY-COPE A TEMPERATURE AMBIANTE CATALYSEE PAR LE DICHLORURE DE PALLADIUM-BISBENZONITRILE.
Bluthe, Norbert,Malacria, Max,Gore, Jacques
, p. 1157 - 1160 (1983)
Tertiary hexa-1,5-diene-3-ols substituted on the carbon 5 (1 ; R1, R3 H) are isomerized at room temperature into δ-ethylenic ketones 2 by using 0.1 molar equivalent of the entitled palladium (II) complex.The yield of the transformation is good and the stereoselectivity is higher than 90 percent.
Enantioselective synthesis of the 6,8-dioxabicyclo-[3.2.1]octane skeleton by asymmetric dihydroxylation
Turpin,Weigel
, p. 6563 - 6564 (1992)
Sharpless asymmetric dihydroxylation (AD) of 6-hepten-2-one with AD-mix-α followed by acidification gives (1S,5R)-5-methyl-6,8-dioxabicyclo[3.2.1]octane in moderate ee. This methodology defines a two-pot enantioselective construction of the (-)-frontalin and brevicomin skeleton from the corresponding 2-alkyl-1,3-dithiane and 5-bromo-1-hexene derivatives.
Transformation of presumptive precursors to frontalin and ex-brevicomin by bark beetles and the West Indian sugarcane weevil (Coleoptera)
Perez,Gries,Gries,Oehlschlager
, p. 445 - 450 (1996)
(Z)-6-Nonen-2-one (1) has recently been shown to be the biosynthetic precursor for the aggregation pheromone exo-brevicomin (2) in mountain pine beetle (MPB) males, Dendroctonus ponderosae (Hopkins). We tested the hypotheses that (1) 6-methyl-6-hepten-2-one (3) is the biosynthetic precursor for the aggregation pheromone frontalin (4) in the spruce beetle (SB), Dendroctonus rufipennis (Kirby), and (2) that frontalin and exo-brevicomin are produced from 3 and 1, respectively, only by beetles that utilize them as aggregation pheromones. Exposure of scolytids MPB, SB, pine engraver (PE), Ips pini (Say) and Ips tridens (Mannerheim) and West Indian sugar cane weevil (WISW), Metamasius hemipterus sericeus (Olivier) to deuterio- or protio-3 invariably resulted in the production of deuterio- or protio-4. Similarly, exposure of SB, WISW and I. tridens to 1 resulted in the production of 2. We were unable to demonstrate the presence of 3 in SB volatiles, nor were we able to demonstrate the conversion of 6-methyl-5-hepten-2-one to 3 by SB. Production of enantiomerically enriched frontalin and exo-brevicomin by all the beetles exposed to respective precursors reveals widespread occurrence of nonspecific polysubstrate monooxidases in the Coleoptera.
REACTION DES HEXADIENE-1,5 OLS-3 AVEC LE TRIFLUOROACETATE MERCURIQUE; TRANSPOSITION D'OXY-COPE A TEMPERATURE AMBIANTE.
Bluthe, Norbert,Malacria, Max,Gore, Jacques
, p. 4263 - 4266 (1982)
Tertiary 1,5-hexadien-3-ols 1 are transformed to δ-ethylene ketones 2 in 35-75 percent yield by treatment with one equivalent of mercuric trifluoroacetate and subsequent demercuration using sodium borohydride (Scheme I, Table).
REGIOSELECTIVE SYNTHESIS OF 1-OLEFINS BY PALLADIUM-CATALYZED HYDROGENOLYSIS OF TERMINAL ALLYLIC COMPOUNDS WITH AMMONIUM FORMATE
Tsuji, Jiro,Shimizu, Isao,Minami, Ichiro
, p. 1017 - 1020 (1984)
Various terminal allylic compounds such as allylic esters, phenyl esters, carbonates, chlorides, and vinyl epoxides react with ammonium or sodium formate to give 1-olefins with high regioselectivity by using palladium-tributylphosphine complex as a catalyst.The reaction offers a useful synthetic method for 1-olefins.
Stereoselective synthesis of substituted oxocene cores by Lewis acid promoted cyclization
Ghosh, Arun K.,Tomaine, Anthony J.,Cantwell, Kelsey E.
supporting information, p. 396 - 399 (2016/02/18)
Substituted oxocene derivatives have been synthesized by Lewis acid catalyzed reactions of ε-hydroxyalkene and substituted aromatic aldehydes. The Cu(OTf)2-bis-phosphine catalyzed reaction typically provides substituted dihydropyran derivatives through an olefin migration followed by a Prins cyclization. The corresponding reaction catalyzed by TMSOTf or BF3·OEt2 provided eight-membered cyclic ethers (oxocenes), selectively. This methodology provides convenient access to a variety of 2,4,8-trisubstituted oxocenes in good yields and excellent diastereoselectivities.
A reusable unsupported rhenium nanocrystalline catalyst for acceptorless dehydrogenation of alcohols through γ-C-H activation
Yi, Jing,Miller, Jeffrey T.,Zemlyanov, Dmitry Y.,Zhang, Ruihong,Dietrich, Paul J.,Ribeiro, Fabio H.,Suslov, Sergey,Abu-Omar, Mahdi M.
supporting information, p. 833 - 836 (2014/01/23)
Rhenium nanocrystalline particles (Re NPs), of 2 nm size, were prepared from NH4ReO4 under mild conditions in neat alcohol. The unsupported Re NPs convert secondary and benzylic alcohols to ketones and aldehydes, respectively, through catalytic acceptorless dehydrogenation (AD). The oxidant- and acceptor-free neat dehydrogenation of alcohols to obtain dihydrogen gas is a green and atom-economical process for making carbonyl compounds. Secondary aliphatic alcohols give quantitative conversion and yield. Transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), Re K-edge X-ray absorption near-edge structure (XANES), and X-ray absorption fine structure (EXAFS) data confirmed the characterization of the Re NPs as metallic rhenium with surface oxidation to rhenium(IV) oxide (ReO2). Isotope labeling experiments revealed a novel γ-CH activation mechanism for AD of alcohols. Active particles: A rhenium nanoparticle (Re NP) catalyst is generated from NH4ReO4 under mild solution conditions in neat 3-octanol at 180°C. The resulting Re NPs catalyze acceptorless dehydrogenation of alcohols through a novel C-H activation pathway, and are fully recyclable. Copyright
Ultrasound promoted synthesis of (±)-8-hydroxy-5-isopropyl-8-methyl- 6(E)-nonen-2-one ((±)-solanone hydrate) and 3,7-dimethyl-2(E),7- octadienylpropionate
Singh, Vasundhara,Chaudhary, Sangeeta,Sapehiyia, Varinder,Kaur, Irvinder,Kad, Goverdhan Lal,Singh, Jasvinder
, p. 1950 - 1953 (2007/10/03)
A facile synthesis of the title compounds has been accomplished using Zn-Cu couple catalyzed conjugate addition of allylic halides to α,β- unsaturated ketones initiated by ultrasonic waves under aqueous conditions and Horner-Wittig reaction using ethyl α-dimethylphosphonoacetate and NaH as base in dry THF as the key steps in overall good yields.
Halonium ion-mediated reaction of unsaturated hydroperoxy acetals. Competition between the formation of cyclic peroxides and the migration of the methoxy (or hydroxy) group
Tokuyasu, Takahiro,Masuyama, Araki,Nojima, Masatomo,McCullough, Kevin J.
, p. 1069 - 1075 (2007/10/03)
Monoozonolyses of dienes 2 in methanol gave in each case the corresponding unsaturated α-methoxy hydroperoxides 3. Capture of 2-alkyl- substituted cyclohexanone oxides by methanol was highly diastereoselective, thereby providing exclusively the hydroperoxides derived from attack by methanol from the less hindered face of the carbonyl oxide intermediates. Halonium ion-mediated reactions of the hydroperoxides 3 gave the novel methoxy- or hydroxy-migrated products, together with the expected halogen- substituted 1,2-dioxanes and/or 1,2-dioxepanes, the composition of the product mixture being a function of the halogenating agent utilized and the structure of 3.
Reaction of some alkenols with tetrachloromethane
Bugarcic, Zorica M.,Mojsilovic, Biljana,Marjanovic, Ljiljana,Konstantinovic, Stanimir
, p. 1091 - 1096 (2007/10/03)
The reaction of some alkenols with tetrachloromethane in the presence of a radical initiator was investigated. Regarding the effects of structural features of the starting alkenol (number and position of methyl substituents at the double bond and at the carbinol carbon atom, constitutional relationship between the double bond and the hydroxyl group) there are two possible competing reactions: addition and cyclization. In the case of the simplest alkenols (without substituents and with a more remote double bond) addition occurs; mono-and disubstituted secondary and tertiary Δ4-and Δ5-alkenols cyclize in high yields to give the corresponding cyclic ethers.
