- A General Approach to Intermolecular Olefin Hydroacylation through Light-Induced HAT Initiation: An Efficient Synthesis of Long-Chain Aliphatic Ketones and Functionalized Fatty Acids
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Herein, an operationally simple, environmentally benign and effective method for intermolecular radical hydroacylation of unactivated substrates by employing photo-induced hydrogen atom transfer (HAT) initiation is described. The use of commercially available and inexpensive photoinitiators (Ph2CO and NHPI) makes the process attractive. The olefin hydroacylation protocol applies to a wide array of substrates bearing numerous functional groups and many complex structural units. The reaction proves to be scalable (up to 5 g). Different functionalized fatty acids, petrochemicals and naturally occurring alkanes can be synthesized with this protocol. A radical chain mechanism is implicated in the process.
- Guin, Joyram,Paul, Subhasis
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supporting information
p. 4412 - 4419
(2021/02/05)
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- Catalytic ketonisation over oxide catalysts. Part IX. Single step synthesis of aliphatic saturated and unsaturated C11 - C 13 ketones from carboxylic acids
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Metameric undecan-x-ones (x = 2-6), dodecan-y-ones (y = 2-5), tridecan-z-ones (z = 4-7) and two unsaturated aliphatic ketones were prepared by vapor phase ketonisation of the appropriate monocarboxylic acids in the presence of 20 wt% MnO2/Al2O3 catalyst under flow conditions. The ketones were obtained in yields between 48 and 89% in a multigram scale (80-250 g). Their physical and spectral data have been determined.
- Glinski,Gibka
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p. 299 - 302
(2007/10/03)
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- Reaction of unstabilized iodonium ylides with organoboranes
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Exposure of monocarbonyl iodonium ylides, generated by the ester exchange of (Z)-(2-acetoxyvinyl)-λ3-iodanes with EtOLi, to organoboranes results in a 1,2-shift of a carbon ligand from boron to the ylide carbons, which probably generates hitherto uncharacterized α-boryl ketones.
- Ochiai, Masahito,Tuchimoto, Yoshimi,Higashiura, Nobuyuki
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p. 1505 - 1508
(2007/10/03)
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- Synthesis of aliphatic ketones from allylic alcohols through consecutive isomerization and chelation-assisted hydroacylation by a rhodium catalyst
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Abstract: An allylic alcohol, utilized as a precursor for an aliphatic aldehyde, reacted with olefins to afford aliphatic ketones in the presence of RhCl(PPh3)3, 2-amino-4-picoline, aniline, and benzoic acid through a tandem reaction of an isomerization and a chelation-assisted hydroacylation.
- Lee, Dae-Yon,Moon, Choong Woon,Jun, Chul-Ho
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p. 3945 - 3948
(2007/10/03)
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- Triethylborane Induced Selective 1,4-Reduction of α,β-Unsaturated Carbonyl Compounds with Triphenyltin Hydride or Tributyltin Hydride
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Reduction of α,β-unsaturated ketones and esters with triphenyltin hydride or tributyltin hydride in the presence of triethylborane has been studied.Whereas the reaction of α,β-unsaturated ketones (R1CH=CHCOR2) with triphenyltin hydride provided the corresponding saturated ketones (R1CH2COR2), treatment of α,β-unsaturated ester (PhCH=CHCOOMe or CH3CH=CHCOO-n-C6H13) afforded an adduct (PhCH2CH(SnPh3)COOMe or CH3CH(SnPh3)CH2COO-n-C6H13).
- Nozaki, Kyoko,Oshima, Koichiro,Utimoto, Kiitiro
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p. 2585 - 2587
(2007/10/02)
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- STUDY OF THE TELOMERIZATION OF ETHYLENE AND 1-HEXENE BY BUTANAL THROUGH COMPARATIVE KINETICS
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The reaction of ethylene and 1-hexene with butanal was studied using tertiary butyl peroxide initiation at 140 deg C and a hydrostatic pressure in the range of 250-450 kg/cm2.Based on calculated values of the rate constant ratios for the addition reaction of the n-C3H7CO radical to ethylene (k0e) and 1-hexene (k0h), we obtained k0e/l0h = 3.7 as the rate constant of the decarbonylation reaction of this radical (kd).The partial chain transfer constants were calculated for the ethylene-butanal system as Cn: C1 = 1.0 +/- 0.16; C2 = 1.0 +/- 0.14; C3 = 0.9 +/- 0.23.The results obtained indicate the nucleophilic character of the n-C3H7CO radical in these reactions.
- Orlova, S. V.,Ikonnikov, N. S.,Terent'ev, A. B.
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p. 1222 - 1225
(2007/10/02)
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- Reductive couplings of acid chlorides mediated by SmI2
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Reductive couplings of acid chlorides and of acid chlorides with aldehydes or ketones in presence of an excess of SmI2 produce ketones in moderate to good yields.
- Collin,Dallemer,Namy,Kagan
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p. 7407 - 7410
(2007/10/02)
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- Cr(III) or Ce(IV) Impregnated Perfluorinated Resin-Sulfonic Acid Catalyst for the Oxidation of Alcohols
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Sereval polymer supported catalysts are prepared by treatment of Nafion 551 (abbreviated NAFK below) with metal salts.Cr/NAFK and Ce/NAFK found to be effective catalysts for the dehydrogenative oxidation of alcohols to the corresponding ketones by means of t-butyl hydroperoxide.Selective oxidation of secondary alcohols in the presence of primary ones was performed using a Ce/NAFK-NaBrO3 system.
- Kanemoto, Shigekazu,Saimoto, Hiroyuki,Oshima, Koichiro,Utimoto, Kiitiro,Nozaki, Hitosi
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p. 519 - 523
(2007/10/02)
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- Chromium(VI) or Ruthenium(II) Complex Catalysis in Oxidation of Alcohols to Aldehydes and Ketones by Means of Bis(trimethylsilyl) Peroxide
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Bis(trimethylsilyl) peroxide (BTSP) serves as an effective oxidant of alcohols in the presence of chromium(VI) or ruthenium(II) complexes as catalysts in dichloromethane.Selective oxidation of primary alcohols in preference to secondary ones using RuCl2(PPh3)3 as a catalyst is also described.
- Kanemoto, Shigekazu,Matsubara, Seijiro,Takai, Kazuhiko,Oshimara, Koichiro,Utimoto, Kiitiro,Nozaki, Hitosi
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p. 3607 - 3612
(2007/10/02)
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- Cerium or Ruthenium Catalyzed Oxidation of Alcohols to Carbonyl Compounds by Means of Sodium Bromate
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Sodium bromate has been found to be effective oxidant for oxidation of alcohols in the presence of cerium or ruthenium compounds in biphase reaction.Selective oxidation of secondary alcohols was performed in the presence of primary ones using cerium(IV) ammonium nitrate (CAN) or cerium(IV) sulfate (CS) as catalyst.For instance, treatment of 1,10-undecanediol with CS/NaBrO3 provided 11-hydroxy-2-undecanone in 82percent yield.Ruthenium catalyzed biphase oxidation of alcohols with sodium bromate provided the corresponding aldehydes or ketones in good to excellent yields.
- Kanemoto, Shigekazu,Tomioka, Hiroki,Oshima, Koichiro,Nozaki, Hitosi
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p. 105 - 108
(2007/10/02)
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- Pyridinium Fluorochromate or benzyltrimethylammonium Chlorochromate for selective Oxidation of Alcohols.
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Selective oxidation of secondary alcohols in the presence of primary ones has been achieved by the following sequences, (1) selective protection of primary alcohols with t-BuMe2SiCl, (2) oxidation of secondary alcohols with title reagents, and (3) deprotection of primary hydroxyls.
- Nonaka, Tsuyoshi,Kanemoto, Shigekazu,Oshima, Koichiro,Nozaki, Hitosi
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p. 2019 - 2020
(2007/10/02)
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- Cr(III) OR Ce(IV) IMPREGNATED PERFLUORINATED RESIN-SULFONIC ACID CATALYSTS FOR THE OXIDATION OF ALCOHOLS
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Several polymer supported catalysts are prepared by treatment of NafionR 511 (abbreviated as NAFK below) with metal salts and found to be effective in promoting the dehydrogenative oxidation of alcohols with tBuOOH.
- Kanemoto, Sigekazu,Saimoto, Hiroyuki,Oshima, Koichiro,Nozaki, Hitosi
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p. 3317 - 3320
(2007/10/02)
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- Novel Acylation of Aliphatic Olefins Promoted by Active Zinc Compounds
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It was found that acylation of a variety of aliphatic olefins with acid chlorides is efficiently promoted by active zinc compounds, which were prepared from a Zn/Cu couple and alkyl iodides.The crude product mixtures were subsequently treated with 1 M KOH in methanol or were subjected to catalytic hydrogenation to afford the corresponding α,β-unsaturated or saturated ketones in good to moderate yields.It was also shown that the reaction fully follows the Markovnikov rule.
- Shono, Tatsuya,Nishiguchi, Ikuzo,Sasaki, Manji,Ikeda, Haruhiko,Kurita, Makoto
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p. 2503 - 2505
(2007/10/02)
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- TRANSITION-METAL CATALYZED OXIDATION OF ALCOHOLS TO ALDEHYDES AND KETONES BY MEANS OF Me3SiOOSiMe3
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Pyridinium dichromate-Me3SiOOSiMe3 system has been found to be effective for the oxidation of alcohols to the corresponding carbonyl compounds.Selective oxidation of primary alcohols in the presence of secondary ones with RuCl2(PPh3)3-Me3SiOOMe3 is also described.
- Kanemoto, Shigekazu,Oshima, Koichiro,Matsubara, Seijiro,Takai, Kazuhiko,Nozaki, Hitosi
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p. 2185 - 2188
(2007/10/02)
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- HIGHLY SELECTIVE OXIDATION OF SECONDARY HYDROXYL FUNCTIONS USING THE VO(acac)2-t-BuOOH SYSTEM
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The VO(acac)2-t-BuOOH system shows high oxidation reactivity for secondary alkohols to give ketones.
- Kaneda, Kiyotomi,Kawanishi, Yasuyuki,Jitsukawa, Koichiro,Teranishi, Shiichiro
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p. 5009 - 5010
(2007/10/02)
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- CERIUM CATALYZED SELECTIVE OXIDATION OF SECONDARY ALCOHOLS IN THE PRESENCE OF PRIMARY ONES
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The combination of (NH4)2Ce(NO3)6-NaBrO3 or Ce(SO4)2.2H2SO4-NaBrO3 has been found to be effective for the title selective oxidation.
- Tomioka, Hiroki,Oshima, Koichiro,Nozaki, Hitosi
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p. 539 - 542
(2007/10/02)
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- Reactions of organoboranes and 2-lithio-2-alkyl-1,3-benzodithioles. A new, improved synthesis of ketones
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Reactions of trialkylboranes with 2-lithio-2-alkyl-1,3-benzodithioles followed by oxidation give ketones in good yields. This method is far less subject to steric hindrance than the analogous reactions using anions derived from bis(phenylthio)alkanes.
- Ncube, Smollie,Pelter, Andrew,Smith, Keith
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p. 1893 - 1894
(2007/10/09)
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