- Renewable high-density spiro-fuels from lignocellulose-derived cyclic ketones
-
Renewable high-density spiro-fuels are synthesized from lignocellulose-derived cyclic ketones for the first time, which show higher density, higher neat heat of combustion and lower freezing point compared with other biofuels synthesized from the same feedstock, and thus represent a new type of renewable high-density fuel attractive for practical applications.
- Xie, Junjian,Zhang, Xiangwen,Pan, Lun,Nie, Genkuo,Xiu-Tian-Feng,Liu, Qing,Wang, Peng,Li, Yafei,Zou, Ji-Jun
-
supporting information
p. 10303 - 10305
(2017/09/23)
-
- MeOH or H2O as efficient additive to switch the reactivity of allylSmBr towards carbonyl compounds
-
A variety of carbonyl compounds were treated by allylSmBr (allylSmBr) with MeOH as the cosolvent to have further insights on the previously reported reductive coupling of aryl ketones mediated by Sm/alkyl halide/MeOH. The results demonstrate that the real reducing species in Sm/alkyl halide/MeOH system should be allylSmBr, and MeOH has elegantly switched the reactivity of allylSmBr from being nucleophilic to being good reductive coupling reagent. Besides, H2O was also found to be a useful additive to realize the pinacol coupling of aliphatic aldehydes and ketones promoted by allylSmBr.
- Li, Jianyong,Niu, Qingsheng,Li, Shanchan,Sun, Yuehao,Zhou, Qian,Lv, Xin,Wang, Xiaoxia
-
supporting information
p. 1250 - 1253
(2017/03/10)
-
- Use of electrochemistry to provide efficient SmI2 catalytic system for coupling reactions.
-
Samarium metal has been used for the first time as electrode material to perform as an efficient and versatile SmI2 catalytic system assisted by electrochemistry. The established electrocatalytic procedure that excludes any metal additives was successfully applied in various transformations mediated by this useful reagent.
- Sun, Linhao,Sahloul, Kamar,Mellah, Mohamed
-
p. 2568 - 2573
(2013/11/19)
-
- Samarium/N-bromosuccinimide-induced reductive dimerization of carbonyl compounds
-
Stereoselective reductive coupling of carbonyl compounds has been achieved using samarium/N-bromosuccinimide in methanol. The combination of these agents has proved a powerful addition to the arsenal of samarium-based reductants currently utilized.
- Banik, Bimal K.,Banik, Indrani,Samajdar, Susanta,Cuellar, Rogelio
-
p. 2319 - 2322
(2007/10/03)
-
- Study of I-strain relief in the intermediate when forming spiro ketones from unsymmetrical cycloalkylidenecycloalkanes, their dibromides, and their pinacols
-
Three unsymmetrical intercyclic olefins, their dibromides, and their pinacols were prepared, each so the two carbons involved at the functional group were part of a different sized ring. The pinacols were reacted with 25% sulfuric acid and with boron trif
- Sands
-
p. 468 - 471
(2007/10/02)
-
- Dichloromethane as a source of the CH22-synthon: A combination of an arene-catalysed lithiation and a barbier-type reaction
-
The reaction of dichloromethane 1 with an excess of lithium powder (1:7 molar ratio) and catalytic amount of 4,4'-di-tert-butylbiphenyl (5 mol %) in the presence of a carbonyl compound 2 (1:2 molar ratio) in tetrahydrofuran at -40°C yields, after hydrolysis, the corresponding 1,3-diols 3 in moderate yields. The process can be also applied to more complicated gem-dichloro derivatives such as 7,7-dichlorobicyclo[4.1.0]heptane 6 or methyl dichloromethyl ether 9.
- Guijarro, Albert,Vus, Miguel
-
p. 253 - 256
(2007/10/02)
-
- Preparation of Monosilyl Ethers of Vicinal Diols
-
Monosilyl-protected vicinal diols can be prepared by lithiation of silyl derivatives of α-hydroxyalkylstannanes and subsequent addition to carbonyl compounds.Concurrent reaction of the lithium species initially formed is a reverse Brook rearrangement to yield α-hydroxyalkylsilanes.Alternatively, the monosilyl protected diols were prepared by a samarium(II) iodide mediated Barbier type reaction between α-haloalkoxysilanes and carbonyl compounds.
- Antonsen, Oyvind,Benneche, Tore,Undheim, Kjell
-
p. 757 - 760
(2007/10/02)
-
- Samarium diiodide promoted spirolactonization of cycloalkanones
-
Reaction of cycloalkanones with methyl 3-bromopropionate and SmI2 afforded formation of spiroanellated γ-lactones, pinacols and unprecedented 3-(1-hydroxycycloalkyl)-1-oxaspiro[n,m]alkan-2-ones.
- Csuk,Hu,Abdou,Kratky
-
p. 7037 - 7044
(2007/10/02)
-
- TiCl4/Mg/BrCH2CH2Br Reagent System: A 1,2-Diorganometallic Equivalent
-
1,2-Diorganometallic species generated utilizing the TiCl4/Mg/BrCH2CH2/Br reagent system reacts with ketones to give the corresponding 1,4-diols and/or 1,2-diols in moderate yields.
- Rao, S. Achyutha,Periasamy, M.
-
p. 1583 - 1586
(2007/10/02)
-
- ORGANOCERIUM REAGENTS FROM IODINE ACTIVATED CERIUM METAL AND ORGANIC IODIDES: THEIR REACTIONS WITH CARBONYL COMPOUNDS
-
Cerium metal activated by a trace of iodine reacted smoothly with alkyl, allyl, and aryl iodides to give the corresponding organocerium reagents.The reaction of the organocerium reagents thus prepared in situ with carbonyl compounds gave not only Grignard-type adducts but also reduction and reductive coupling products.
- Fukuzawa, Shin-ichi,Fujinami, Tatsuo,Sakai, Shizuyoshi
-
p. 179 - 186
(2007/10/02)
-
- Reaction of Lithium with Alkylidene Halides and Carbonyl Compounds
-
While benzylidene bromide reacts with aromatic aldehydes and lithium to give stilbenes, the reaction with aliphatic carbonyl compounds as well as that of alkylidene halides with carbonyl compounds and lithium are complicated by several competing side reactions.
- Pasha, M. A.,Ravindranath, B.
-
p. 781 - 782
(2007/10/02)
-
- Studies on the Pinacol Coupling Reaction
-
The mixed pinacol coupling reaction has been carefully analyzed.Although a trend toward statistical distribution of products can be found, it is observed that true statistical distributions are rarely observed.Ring-size and alkyl substituent effects are examined.A through-space heteroatom influence on coupling is noted.By use of (R)-(+)-3-methylcyclohexanone, a very specific effect of coupling conditions on product stereochemistry is observed.
- Mundy, Bradford P.,Srinivasa, Ramanujan,Kim, Youseung,Dolph, Thomas,Warnet, Ronald J.
-
p. 1657 - 1661
(2007/10/02)
-
- Reactions of Cyclohexanone with Metal Vapors
-
Metal atom vapors of several d and f transition elements were cocondensed with cyclohexanone at -196 deg C.Radical reduction of cyclohexanone to -1,1'-diol, a pinacol, was observed for elements which are both highly electropositive and form strong metal-oxygen bonds, for example, the early transition, lanthanide, and actinide elements.High yields of aldol condensation products were produced along with a small amount of bicyclohexylidene.Metal atoms of the latter transition elements were much less reactive with cyclohexanone and did not yield a pinacol product.Titanium clusters were prepared by codepositing titanium atoms with a large excess of solvent.Titanium clusters were less reactive than titanium atoms toward cyclohexanone radical reduction reactions.High surface area titanium powders produced by solution techniques yield pinacols when cyclohexanone reacts in excess and further deoxygenate pinacolic dianions to olefins under conditions of limited stoichiometry.
- Miller, Jeffrey T.,DeKock, Carroll W.
-
p. 516 - 520
(2007/10/02)
-
- Deoxygenation and Desulfurization of Organic Compounds via Transition Metal Atom Cocondensation
-
Reactions resulting from the cocondensation of transition metal atoms with a variety of oxygen- and sulfur-containing organic compounds are surveyed.Alkenes are the major or exclusive volatile products when epoxides are reacted with Ti, V, Cr, Co, and Ni atoms. 2,6-Dimethylpyridine-N-oxide and dimethyl sulfoxide undergo deoxygenation upon cocondensation with chromium, but diisopropyl ether and decyl methyl ether do not.Dibenzyl ether yields bis(η6-dibenzyl ether)chromium(0) with Cr atoms, but dibenzyl sulfide undergoes desulfurization.Cyclohexanone and cycloheptanone afford low yields of reductive coupling and aldol products when cocondensed with Cr, Co, and Ni atoms.Nitro- and nitrosoarenes are deoxygenated to coupled azo and azoxy products with Cr atoms.Carbazole (3) is obtained from 2-nitrosobiphenyl, implicating nitrene or nitrenoid intermediates.Whereas isocyanides are not formed from isocyanates and metal atoms, they are produced when isothiocyanates are cocondensed with Cr and V atoms.
- Togashi, Shigeo,Fulcher, John G.,Cho, Bong Rae,Hasegawa, Minoru,Gladysz, J.A.
-
p. 3044 - 3053
(2007/10/02)
-