Xi:Irritant;
112-31-2Relevant articles and documents
One-pot conversion of olefins to carbonyl compounds by hydroboration/NMO-TPAP oxidation
Yates, Matthew H.
, p. 2813 - 2816 (1997)
An efficient method to oxidize an olefin to the less substituted carbonyl compound is described. This new methodology utilizes borane dimethyl sulfide followed by tetrapropylammonium perruthenate N-methylmorpholine N-oxide to oxidize the resulting alkylborane.
Formamides undergo in-plane bimolecular nucleophilic vinylic substitutions (S(N)2) by the reaction with (E)-alkenyl(phenyl)iodonium tetrafluoroborates: Stereoselective synthesis of (Z)-vinyl formates
Ochiai, Masahito,Yamamoto, Shinji,Sato, Koichi
, p. 1363 - 1364 (1999)
Reported for the first time is the stereoselective synthesis of (Z)-vinyl formates, which involves in-plane bimolecular nucleophilic vinylic substitutions of (E)-β-alkylvinyl(phenyl)iodonium tetrafluoroborates with formamides.
A useful and catalytic method for protection of carbonyl compounds into the corresponding 1,3-oxathiolanes and deprotection to the parent carbonyl compounds
Mondal, Ejabul,Sahu, Priti Rani,Khan, Abu T.
, p. 463 - 467 (2002)
A wide variety of carbonyl compounds 1 can be easily protected to the corresponding 1,3-oxathiolanes 2 in good yields in the presence of catalytic amount of perchloric acid in dry CH2Cl2 at 0-5 °C. On the other hand, various 1,3-oxathiolanes 2 can be selectively deprotected to the parent carbonyl compounds 1 in very good yields by H2MoO4·H2O-H2O2 catalyzed oxidation of ammonium bromide in the presence of perchloric acid in CH2Cl2-H2O solvent system. Mild reaction condition, high selectivity, efficient and relatively good yields are some of the major advantages of the procedure.
Reversal of regioselectivity in Wacker-Type oxidation of simple terminal alkenes and its paired interacting orbitals (PIO) analysis
Ogura, Toshihiko,Kamimura, Ryuichiro,Shiga, Akinobu,Hosokawa, Takahiro
, p. 1555 - 1557 (2005)
The trend of aldehyde selectivity observed in the oxidation of 1-decene with PdCl2(CH3CN)2/CuCl2 in alcohol (ROH) under O2 can be evaluated by the overlap populations for Pd-C and C-OR bonds in the oxypalladation step with paired interacting orbitals (PIO) analysis. The use of t-BuOH affords decanal in 84% regioselectivity.
An exceptionally simple and convenient method for dethioacetalization
Mehta, Goverdhan,Uma
, p. 1897 - 1898 (1996)
Thioacetals derived from aldehydes and ketones can be unmasked to the corresponding carbonyl compounds in high yield on exposure to a solution of 'oxides of nitrogen' in dichloromethane.
Polymer-supported Chain Homologation
Regen, Steven L.,Kodomari, Mitsuo
, p. 1428 - 1429 (1987)
Addition of hept-1-ene to a suspension of polystyrene-bound forms of hydridocarbonyltris(triphenylphosphine)rhodium(I) and methylenetriphenylphosphorane in tetrahydrofuran, under a hydrogen/carbon monoxide atmosphere (60 deg C; 120 lb in-2), produces 2-methylheptanal (10percent), n-octanal (45percent), n-decanal (12percent), n-dodecanal (2percent), and n-tetradecanal (0.3percent) as major products.
Well-defined alkylpalladium complexes with pyridine-carboxylate ligands as catalysts for the aerobic oxidation of alcohols
Melero, Cristobal,Shishilov, Oleg N.,Alvarez, Eleuterio,Palma, Pilar,Campora, Juan
, p. 14087 - 14100 (2012)
Neophylpalladium complexes of the type [Pd(CH2CMe 2Ph)(N-O)(L)], where N-O is picolinate or a related bidentate, monoanionic ligand (6-methylpyridine-2-carboxylate, quinoline-2-carboxylate, 2-pyridylacetate or pyridine-2-sulfonate) and L is pyridine or a pyridine derivative, efficiently catalyze the oxidation of a range of aliphatic, benzylic and allylic alcohols with oxygen, without requiring any additives. A versatile method is described which allows the synthesis of the above-mentioned complexes with a minimum synthetic effort from readily available materials. Comparison of the rates of oxidation of 1-phenylethanol with different catalysts reveals the influence of the structure of the bidentate N-O chelate and the monodentate ligand L on the catalytic performance of these complexes. The Royal Society of Chemistry 2012.
TiO2-Photocatalyzed Epoxidation of 1-Decene by H2O2 under Visible Light
Ohno, Teruhisa,Masaki, Yuji,Hirayama, Seiko,Matsumura, Michio
, p. 163 - 168 (2001)
1-Decene was converted to 1,2-epoxydecane on UV-irradiated TiO2 powder using molecular oxygen as the oxygen source. Other main products were nonanal and 2-decanone. For anatase-form TiO2 powders, the reaction rate was hardly affected by addition of hydrogen peroxide to the solution. In contrast, for rutile-form TiO2 powders, the rate of epoxide generation was significantly increased by addition of hydrogen peroxide. In this case, the reaction occurred under visible light as well as UV light. The selectivity of the production of 1,2-epoxydecane was higher under visible light than under UV light. The conversion efficiency of an incident photon to 1,2-epoxydecane was about 2 percent when irradiated with visible light in the range 440-480 nm. UV-visible diffuse reflection spectroscopy, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy suggested the generation of a Ti-η2-peroxide on rutile TiO2 surface after treatment with hydrogen peroxide. The initial step of the reaction under visible light was attributed to a photochemical reaction of this peroxide with 1-decene.
Unexpected highly chemoselective deprotection of the acetals from aldehydes and not ketones: TESOTf-2,6-lutidine combination
Fujioka, Hiromichi,Sawama, Yoshinari,Murata, Nobutaka,Okitsu, Takashi,Kubo, Ozora,Matsuda, Satoshi,Kita, Yasuyuki
, p. 11800 - 11801 (2004)
Acetal functions are recognized as good protecting groups of carbonyl groups. Although many deprotecting methods of acetals to carbonyl functions have already been developed, there is no methodology which can deprotect acetals in the presence of ketals because the usual acidic or radical reactions occur more easily via the more stable cationic or radical intermediates from the ketals. On the other hand, this new method can proceed in a reverse manner to that described in previous reports. That is, the method can deprotect aliphatic acetals in the presence of ketals. The reaction condition is common for silylation, i.e., the TESOTf-2,6-lutidine combinations. Although the TMSOTf-2,6-lutidine combination can also deprotect acetals, it lacks chemoselectivity in deprotection of the acetals from aldehydes and ketones. The treatment of acetals with TESOTf and 2,6-lutidine in CH2Cl2 followed by a H2O workup gave the corresponding aldehydes. Of course, the compounds, which have both acetal and hydroxyl functions afforded the compounds obtained by the usual silylation of an alcohol and deprotection of an acetal without any problem. However, deprotection of the ketals from ketones was not observed during the conversion reaction of acetals from aldehydes. This chemoselectivity was confirmed in the reactions of the compounds that have the acetal and ketal in the same molecule. In both cases, the acetal functions were deprotected to give aldehydes with intact ketals. Furthermore, under the conditions described here, many functional groups such as methoxy, acetoxy, allyl alcohol, and silyloxy ether are intact. This method is very mild and available for many compounds. Copyright
C-H functionalization of sp3centers with aluminum: A computational and mechanistic study of the baddeley reaction of decalin
Lyall, Catherine L.,Sato, Makoto,Uosis-Martin, Mario,Asghar, Syeda Farina,Jones, Matthew D.,Williams, Ian H.,Lewis, Simon E.
, p. 13745 - 13753 (2014)
Decalin undergoes reaction with aluminum trichloride and acetyl chloride to form a tricyclic enol ether in good yield, as first reported by Baddeley. This eye-catching transformation, which may be considered to be an aliphatic Friedel-Crafts reaction, has not previously been studied mechanistically. Here we report experimental and computational studies to elucidate the mechanism of this reaction. We give supporting evidence for the proposition that, in the absence of unsaturation, an acylium ion acts as a hydride acceptor, forming a tertiary carbocation. Loss of a proton introduces an alkene, which reacts with a further acylium ion. A concerted 1,2-hydride shift/oxonium formation, followed by elimination, leads to formation of the observed product.
