1120-06-5Relevant articles and documents
Catalytic enantioselective addition of alkyl grignard reagents to aliphatic aldehydes
Fernandez-Mateos, Emilio,Macia, Beatriz,Yus, Miguel
, p. 1249 - 1254 (2013)
Herein, we report an efficient catalytic system for the enantioselective addition of alkyl Grignard reagents to a broad range of aliphatic aldehydes with good yields and enantioselectivities. Remarkably, the challenging methylmagnesium bromide (MeMgBr) can also be added to a variety of aliphatic aldehydes, providing versatile chiral methyl carbinol units with unprecedented yields and enantioselectivities in a simple one-pot procedure under mild conditions. Copyright
Regio- And stereoselective subterminal hydroxylations of n-decane by fungi in a liquid-liquid interface bioreactor (L-L IBR)
Oda, Shinobu,Isshiki, Kunio,Ohashi, Shinichi
, p. 105 - 109 (2009)
This article may be the first report to describe the excellent regio- and stereoselective subterminal hydroxylations of n-alkane with microorganisms. Approximately 2000 fungal strains were screened for the regioselective hydroxylation of n-decane with a s
Novel Pd/C-catalyzed redox reactions between aliphatic secondary alcohols and ketones under hydrogenation conditions: Application to H-D exchange reaction and the mechanistic study
Esaki, Hiroyoshi,Ohtaki, Rumi,Maegawa, Tomohiro,Monguchi, Yasunari,Sajiki, Hironao
, p. 2143 - 2150 (2007)
A liquid-phase redox system between secondary alcohols and ketones is described. Deuteration of either secondary alcohols or ketones using the Pd/C-H2-D2O system gave a mixture of deuterium-labeled secondary alcohols and ketones. The results indicated that the secondary alcohol was oxidized to the corresponding ketone without oxidants under the hydrogenation conditions and the hydrogenation of the aliphatic ketone to the corresponding secondary alcohol simultaneously proceeded. Detailed mechanistic studies on the redox system as well as the H-D exchange reaction are discussed.
Borane - THF: New solutions with improved thermal properties and stability
Potyen, Mark,Josyula, Kanth V. B.,Schuck, Mike,Lu, Sean,Gao, Peng,Hewitt, Chris
, p. 210 - 214 (2007)
A new generation of borane-THF solutions stabilized with 0.005 M of 1,2,2,6,6-pentamethylpiperidine or N-isopropyl-N-methyl-tert-butylamine have been developed. These BTHF solutions show superior stability and reactivity at ambient temperatures when compared to BTHF complex unstabilized or stabilized with 0.005 M NaBH4.
Highly enantioselective reduction of ketones by chiral diol-modified lithium aluminum hydride reagents
Ren, Yunlai,Tian, Xinzhe,Sun, Kunpeng,Xu, Jian,Xu, Xianlun,Lu, Shijie
, p. 463 - 465 (2006)
Some readily available chiral diols from indene and d-mannitol were investigated as chiral modifiers in lithium aluminum hydride reduction of ketones, and it was discovered that further modification of these reducing reagents by a simple a-amino alcohol resulted in a remarkable increase in optical yield. Among the investigated chiral modifiers, chiral diol 1 gave the highest enantioselectivities.
Towards the development of a selective ruthenium-catalyzed hydroformylation of olefins
Fleischer, Ivana,Wu, Lipeng,Profir, Irina,Jackstell, Ralf,Franke, Robert,Beller, Matthias
, p. 10589 - 10594 (2013)
The ruthenium-catalyzed hydroformylation of 1- and 2-octene to give preferentially the corresponding linear aldehyde is reported. The catalyst system comprising of Ru3(CO)12 and an imidazole- substituted monophosphine ligand allows for high chemo- and regioselectivity. The hydroformylation proceeds with unprecedented rates for a ruthenium-based catalyst. Copyright
Utilising hardly-water soluble substrates as a second phase enables the straightforward synthesis of chiral alcohols
Kohlmann, Christina,Robertz, Nora,Leuchs, Susanne,Greiner, Lasse,Na'Amnieh, Shukralla
, p. 3093 - 3095 (2011)
So far, the alcohol dehydrogenase-catalysed conversion of longer chain aliphatic substrates has been challenging due to their low solubility in aqueous solution. However, by utilising the ketone directly as a second organic phase, the straightforward synthesis of long chain aliphatic chiral alcohols is enabled. The Royal Society of Chemistry.
Acceleration effects of phosphine ligands in the nickel catalyzed methylation of aldehydes using trimethylaluminum
Ichiyanagi, Tsuyoshi,Kuniyama, Satoru,Shimizu, Makoto,Fujisawa, Tamotsu
, p. 1033 - 1034 (1998)
A nickel catalyzed methylation of aldehydes was conducted successfully using trimethylaluminum as an alkylation reagent. In the presence of a phosphine or phosphite ligand, the reaction was considerably accelerated to give the methylation product in good yields.
Benzo[h]quinoline pincer ruthenium and osmium catalysts for hydrogenation of ketones
Baratta, Walter,Fanfoni, Lidia,Magnolia, Santo,Siega, Katia,Rigo, Pierluigi
, p. 1419 - 1423 (2010)
Chiral orthometalated osmium complexes [OsCl(CN′N)(PP)] {PP = (S,R)-Josiphos type diphosphane} based on 2-aminomethylbenzo[h]quinoline ligands (HCN′N) were prepared by reaction of [OsCl2(PPh 3)3] with a Josiphos diphosphane and a HCN′N ligand in the presence of NEt3. Ruthenium and osmium complexes [MX(CN′N)(PP)] {M = Ru, Os; X = Cl, OCH(p-C6H 4F)2; PP = dppb, (S,R)-Josiphos}, in the presence of KOtBu, efficiently catalyze the chemoselective hydrogenation (H2 = 5 atm) of aromatic and aliphatic ketones to secondary alcohols in methanol or methanol/ethanol mixtures, when a S/C ratio of 10000-50000 is used. With use of these chiral phosphanes, alkyl aryl ketones have been reduced with ee values up to 99% and turnover frequencies (TOFs) up to 5.6 × 104 h -1.
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Zeiss,Tsutsui
, p. 897,899 (1953)
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Deep eutectic solvents as H2-sources for Ru(II)-catalyzed transfer hydrogenation of carbonyl compounds under mild conditions
Cavallo, Marzia,Arnodo, Davide,Mannu, Alberto,Blangetti, Marco,Prandi, Cristina,Baratta, Walter,Baldino, Salvatore
supporting information, (2021/02/22)
The employment of easily affordable ruthenium(II)-complexes as pre-catalysts in the transfer hydrogenation of carbonyl compounds in deep eutectic media is described for the first time. The eutectic mixture tetrabutylammonium bromide/formic acid = 1/1 (TBABr/HCOOH = 1/1) acts both as reaction medium and hydrogen source. The addition of a base is required for the process to occur. An extensive optimization of the reaction conditions has been carried out, in terms of catalyst loading, type of complexes, H2-donors, reaction temperature and time. The combination of the dimeric complex [RuCl(p-cymene)-μ-Cl]2 (0.01–0.05 eq.) and the ligand dppf (1,1′-ferrocenediyl-bis(diphenylphosphine)ferrocene) in 1/1 molar ratio has proven to be a suitable catalytic system for the reduction of several and diverse aldehydes and ketones to their corresponding alcohols under mild conditions (40–60 °C) in air, showing from moderate to excellent tolerability towards different functional groups (halogen, cyano, nitro, phenol). The reduction of imine compounds to their corresponding amine derivatives was also studied. In addition, the comparison between the results obtained in TBABr/HCOOH and in organic solvents suggests a non-innocent effect of the DES medium during the process.
Biocatalytic synthesis of non-vicinal aliphatic diols
Ebrecht, Ana C.,Aschenbrenner, Jasmin C.,Smit, Martha S.,Opperman, Diederik J.
supporting information, p. 439 - 445 (2021/01/29)
Biocatalysts are receiving increased attention in the field of selective oxyfunctionalization of C-H bonds, with cytochrome P450 monooxygenases (CYP450s), and the related peroxygenases, leading the field. Here we report on the substrate promiscuity of CYP505A30, previously characterized as a fatty acid hydroxylase. In addition to its regioselective oxyfunctionalization of saturated fatty acids (ω-1-ω-3 hydroxylation), primary fatty alcohols are also accepted with similar regioselectivities. Moreover, alkanes such as n-octane and n-decane are also readily accepted, allowing for the production of non-vicinal diols through sequential oxygenation. This journal is
CYP505E3: A Novel Self-Sufficient ω-7 In-Chain Hydroxylase
Maseme, Mpeyake Jacob,Opperman, Diederik Johannes,Pennec, Alizé,Smit, Martha Sophia,van Marwijk, Jacqueline
supporting information, p. 10359 - 10362 (2020/04/23)
The self-sufficient cytochrome P450 monooxygenase CYP505E3 from Aspergillus terreus catalyzes the regioselective in-chain hydroxylation of alkanes, fatty alcohols, and fatty acids at the ω-7 position. It is the first reported P450 to give regioselective in-chain ω-7 hydroxylation of C10–C16 n-alkanes, thereby enabling the one step biocatalytic synthesis of rare alcohols such as 5-dodecanol and 7-tetradecanol. It shows more than 70 percent regioselectivity for the eighth carbon from one methyl terminus, and displays remarkably high activity towards decane (TTN≈8000) and dodecane (TTN≈2000). CYP505E3 can be used to synthesize the high-value flavour compound δ-dodecalactone via two routes: 1) conversion of dodecanoic acid into 5-hydroxydodecanoic acid (24 percent regioselectivity), which at low pH lactonises to δ-dodecalactone, and 2) conversion of 1-dodecanol into 1,5-dodecanediol (55 percent regioselectivity), which can be converted into δ-dodecalactone by horse liver alcohol dehydrogenase.
