- Reactions between lithiated 1,3-dithiane oxides and trialkylboranes
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Various 2-substituted-1,3-dithiane oxides (1-oxide and 1,3-dioxide) have been metalated and reacted for the first time with a trialkylborane (trioctylborane). The 2-chloro-1,3-dioxide results in migration of an octyl group from boron to carbon with the displacement of chloride and gives nonanoic acid after oxidation, but there is no evidence for a second migration involving displacement of a sulfenate group. The reaction involving lithiation of the 2-methoxy-1-oxide results in two migrations, with the displacement of both the methoxy group and the thiolate unit of the dithiane ring, giving dioctyl ketone after oxidation, but the yield is low, primarily because thiophilic addition of the lithiating agent predominates over lithiation. Again, there is no evidence for the displacement of the sulfenate unit. However, the intermediate prior to oxidation can be treated with trifluoroacetic anhydride to induce a Pummerer rearrangement, and the presumed trifluoroacetoxyalkylthiolate group then acts as a novel leaving group and is displaced, resulting in trioctylmethanol on oxidation, but the yield is again very low.
- El-Hiti, Gamal A.,Elliott, Mark C.,Saleh, Basil A.,Smith, Keith
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p. 591 - 603
(2021/09/22)
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- IONIZABLE AMINE LIPIDS AND LIPID NANOPARTICLES
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The disclosure provides ionizable amine lipids and salts thereof (e.g., pharmaceutically acceptable salts thereof) useful for the delivery of biologically active agents, for example delivering biologically active agents to cells to prepare engineered cells. The ionizable amine lipids disclosed herein are useful as ionizable lipids in the formulation of lipid nanoparticle-based compositions.
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- Long-Range Self-Assembly of an Electron-Deficient Hexaazatrinaphthylene with Out-of-Plane Substituents
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The unprecedented time-dependent long-range supramol-ecular assembly of electron-deficient hexaazatrinaphthylene (HATN) core based on peripheral crowding with three out-of-plane cyclic ketals is reported. The single-crystal X-ray structure of the diethyl derivative provided detailed information as to how four molecules in a repeating unit were packed in order to avoid steric crowding of the out-of-plane cyclic ketal side chain, providing locking and fastening for stabilizing the self-assembled structure. The polarizing optical microscopy (POM) and differential scanning calorimetry (DSC) did not instantaneously show any phase transition upon the cooling process. To our surprise, POM images showed a nucleation of spherulite up to 100 μm after 24 hour later. X-ray diffraction data further confirmed that these soft crystal formed a hexagonal-like crystal. The long-range self-assembly of the new material showed a slight red shift in the UV-vis absorption spectra and further substantiated by computational method.
- Chen, Yi-Ru,Zhang, Yong-Yun,Yeh, Ming-Che,Luo, Ying-Ting,Ong, Chi Wi
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p. 613 - 618
(2019/12/24)
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- From Alkyl Halides to Ketones: Nickel-Catalyzed Reductive Carbonylation Utilizing Ethyl Chloroformate as the Carbonyl Source
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Ketones are an important class of molecules in synthetic and medicinal chemistry. Rapid and modular synthesis of ketones remains in high demand. Described here is a nickel-catalyzed three-component reductive carbonylation method for the synthesis of dialkyl ketones. A wide range of both symmetric and asymmetric dialkyl ketones can be accessed from alkyl halides and a safe CO source, ethyl chloroformate. The approach offers complementary substrate scope to existing carbonylation methods while avoiding the use of either toxic CO or metal carbonyl reagents.
- Shi, Renyi,Hu, Xile
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supporting information
p. 7454 - 7458
(2019/04/30)
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- IONIZABLE CATIONIC LIPID FOR RNA DELIVERY
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What is described is a compound of formula I consisting of a compound in which R1 is a branched chain alkyl consisting of 10 to 31 carbons; R2 is a linear alkyl, alkenyl, or alkynyl consisting of 2 to 20 carbons; L1 and L2 are the same or different, each a linear alkylene of 1 to 20 carbons or a linear alkenylene of 2 to 20 carbons; X1 is S or O; R3 is a linear or branched alkylene consisting of 1 to 6 carbons; and R4 and R5 are the same or different, each a hydrogen or a linear or branched alkyl consisting of 1 to 6 carbons; or a pharmaceutically acceptable salt thereof.
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- IONIZABLE CATIONIC LIPID FOR RNA DELIVERY
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What is described is a compound of formula I consisting of a compound in which R1 is a branched chain alkyl consisting of 10 to 31 carbons;R2 is a linear alkyl, alkenyl, or alkynyl consisting of 2 to 20 carbons, or a branched chain alkyl consisting of 10 to 31 carbons;L1 and L2 are the same or different, each a linear alkane of 1 to 20 carbons or a linear alkene of 2 to 20 carbons;X1 is S or O;R3 is a linear or branched alkylene consisting of 1 to 6 carbons; andR4 and R5 are the same or different, each a hydrogen or a linear or branched alkyl consisting of 1 to 6 carbons; or a pharmaceutically acceptable salt thereof.
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-
Paragraph 0389; 0390; 0391
(2018/07/05)
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- Reactions of organoboranes with carbanions bearing three potential leaving groups: unusual processes, products and mechanisms
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Known reagents that transfer three alkyl groups of a trialkylborane intramolecularly to a single carbon atom lack features to influence stereochemistry. We have investigated four reagents of type LiCCl2X, where X might be amenable to variation. All behaved differently. With X=OR (R=cyclohexyl, menthyl), the reagent decomposed, leading to only low yields of triple migration products. With X=S(O)Ph, a single migration occurred, followed by isomerisation to boron enolate-like species that hydrolysed to α-chloroalkyl phenyl sulfoxides or reacted with aldehydes to aldol-like products. With X=SO2Ph, the major product was the corresponding α,α-dichloroalkyl phenyl sulfone, apparently formed through a redox reaction. With X=S(O)(NMe)Ph, products of three intramolecular alkyl migrations were obtained with unhindered trialkylboranes. Attempts have been made to gain understanding of the sulfoxide process by investigating proportions of aldol-like products, using X-ray crystallography and ab initio calculations.
- Saleh, Basil A.,Smith, Keith,Elliott, Mark C.,Jones, D. Heulyn,Kariuki, Benson M.,El Hiti, Gamal A.
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p. 6914 - 6928
(2016/10/14)
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- Factors affecting reactions of trialkylcyanoborates with imidoyl chlorides/trifluoroacetic anhydride
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Abstract Methods for generating tert-alkyl organoboron species are in high demand as they are invaluable intermediates for the synthesis of quaternary carbon centres. Herein we report investigations into generation of tert-alkyl organoboron species using imidoyl chlorides as reagents in the organoboron cyanidation reaction. Although alkenyl side-products predominate in particularly hindered cases, tert-alkyl organoboron species can be successfully generated for less hindered examples.
- Jones, Dyfyr Heulyn,Smith, Keith,Elliott, Mark C.,El-Hiti, Gamal A.
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p. 6285 - 6289
(2015/08/03)
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- Stoichiometric reactions of acylnickel(II) complexes with electrophiles and the catalytic synthesis of ketones
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Acylnickel(II) complexes feature prominently in cross-electrophile coupling (XEC) reactions that form ketones, yet their reactivity has not been systematically investigated. We present here our studies on the reactivity of acylnickel(II) complexes with a series of carbon electrophiles. Bromobenzene, α-chloroethylbenzene, bromooctane, and iodooctane were reacted with (dtbbpy)NiII(C(O)C5H11)(Br) (1b) and (dtbbpy)NiII(C(O)tolyl)(Br) (1c) to form a variety of organic products. While reactions with bromobenzene formed complex mixtures of ketones, reactions with α-chloroethylbenzene were highly selective for the cross-ketone product. Reactions with iodooctane and bromooctane also produced the cross-ketone product, but in intermediate yield and selectivity. In most cases the presence or absence of a chemical reductant (zinc) had only a small effect on the selectivity of the reaction. The coupling of 1c with iodooctane (60% yield) was translated into a catalytic reaction, the carbonylative coupling of bromoarenes with primary bromoalkanes (six examples, 60% average yield).
- Wotal, Alexander C.,Ribson, Ryan D.,Weix, Daniel J.
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supporting information
p. 5874 - 5881
(2015/01/09)
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- Continuous flow synthesis of ketones from carbon dioxide and organolithium or grignard reagents
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We describe an efficient continuous flow synthesis of ketones from CO 2 and organolithium or Grignard reagents that exhibits significant advantages over conventional batch conditions in suppressing undesired symmetric ketone and tertiary alcohol byproducts. We observed an unprecedented solvent-dependence of the organolithium reactivity, the key factor in governing selectivity during the flow process. A facile, telescoped three-step-one-flow process for the preparation of ketones in a modular fashion through the in-line generation of organometallic reagents is also established.
- Wu, Jie,Yang, Xiaoqing,He, Zhi,Mao, Xianwen,Hatton, T. Alan,Jamison, Timothy F.
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supporting information
p. 8416 - 8420
(2014/08/18)
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- 4, 4' disubstituted 4H-cyclopentadithiophene and new methods for synthesising the same
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The present invention relates to a method for the synthesis of a compound having the following general formula: the method comprising the step of reacting, in presence of a diprotic acid having a negative pKa, a compound having the general formula: wherein R1 and R2 are organic groups and wherein X and Y are independently selected from the group consisting of hydrogen, chloro, bromo, iodo, boronic acid, boronate esters, borane, pseudohalogen and organotin. It further relates to compounds so obtained and to compounds resulting from the ring closure of compound (II).
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Page/Page column 45-46
(2012/01/06)
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- Synthesis of symmetrical ketones from Grignard reagents and 1,1′-carbonyldiimidazole
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Coupling reactions of 1,1′-carbonyldiimidazole with Grignard reagents provide a rapid and straightforward method for the synthesis of symmetrical ketones. Georg Thieme Verlag Stuttgart.
- Bottalico, Daniela,Fiandanese, Vito,Marchese, Giuseppe,Punzi, Angela
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experimental part
p. 2316 - 2318
(2010/02/28)
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- Polyfluorenes without monoalkylfluorene defects
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A synthetic route to 9,9-dioctyl-9H-fluorene (free of monoalkyl-substituted fluorene defects) by alkylative cyclization of 9-biphen-2-ylheptadecan-9-ol is described. Polyfluorenes prepared by Yamamoto and Suzuki polymerization of the defect-free monomers, when incorporated in light-emitting devices, exhibited minimal green emission attributable to fluorenone formation. By contrast, devices fabricated with polyfluorene arising from conventionally synthesized 9,9-dioctyl-9H-fluorene showed significant emission at 533 nm, even at the turn-on voltage. Incorporation of as little as 0.06 mol % of 9-octyl-9H-fluorene comonomer in polyfluorene led to evolution of green fluorescence in the photoluminescence (PL) and electroluminescence (EL) emission spectra. Copyright
- Sung, Yong Cho,Grimsdale, Andrew C.,Jones, David J.,Watkins, Scott E.,Holmes, Andrew B.
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p. 11910 - 11911
(2008/03/27)
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- Catalytic ketonisation over oxide catalysts. Part VII. Ketonisation and cross-ketonisation of aliphatic esters over CeO2 and ZrO2 supported on alumina
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Catalysts of general formula xwt% MO2/Al2O 3, where x = 10, 20 or 30 and M = Ce or Zr have been studied in the ketonisation and cross-ketonisation of aliphatic esters under flow conditions between 548-723 K. Ketonisation of ethyl pentanoate, heptanoate and nonanoate has led to nonan-5-one, tridecan-7-one and heptadecan-9-one, respectively. The conversion of esters increased with temperature and at 698 K a quantitative conversion was observed, irrespective of the type of ester used. A maximum yield of ketone (46% for nonan-5-one, 60% for tridecan-7-one and 50% for heptadecan-9-one) was observed at 673 K. As a result of the cross-ketonisation of a mixture of ethyl pentanoate and ethyl nonanoate (3:1 molar ratio), three ketones were formed: nonan-5-one, tridecan-5-one and heptadecan-9-one. At 698 K, maximum yields of ketones were noted (37, 46 and 8%, respectively) together with a 90% conversion of esters. The catalysts were characterized by XRD, TPR and surface area measurements.
- Glinski,Szymanski,Lomot
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p. 1033 - 1038
(2007/10/03)
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- Application of Rh(l)-Catalyzed C - H Bond Activation to the Ring Opening of 2-Cycloalkenones in the Presence of Amines
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(matrix presented) Herein described is the application of the Rh(l)-catalyzed C-H bond activation to the ring-opening of 2-cycloalkenones in the presence of cyclohexylamine. This reaction includes the C-C double bond cleavage of 2-cycloalkenones through the conjugate addition of cyclohexylamine followed by the retro-Mannich-type fragmentation. The resulting ring-opened intermediates subsequently underwent either chelation-assisted hydroacylation to afford a ring-opened dicarbonyl compound or β-alkylation via a ring contraction.
- Jun, Chul-Ho,Moon, Choong Woon,Lim, Sung-Gon,Lee, Hyuk
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p. 1595 - 1597
(2007/10/03)
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- C-H and C-C bond activation of primary amines through dehydrogenation and transimination
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Matrix presented Dehydrogenation and subsequent transimination of primary amines offer a new pathway for C-H bond activation, ortho-alkylation, and C-C bond activation to afford a variety of ketones in the reaction of 1-alkene by a cocatalyt system of Rh(I) and 2-amino-3-picoline.
- Jun, Chul-Ho,Chung, Kwan-Yong,Hong, Jun-Bae
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p. 785 - 787
(2007/10/03)
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- New coupling reactions of some acyl chlorides with samarium diiodide in the presence of samarium: Carbinols from three acyl units
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A mixture of samarium(II) iodide and samarium can induce a coupling reaction of three molecules of alkanoyl halide to give trialkylcarbinols of 2-hydroxy-1,3-diones. When aliphatic, unbranched alkanoyl chlorides are used, this new coupling reaction provides trimeric products as the main reaction products. Tetrahydropyran (THP) proved superior as the solvent because no ring-opening and subsequent reaction with the alkanoyl halides was observed under the reaction conditions, unlike when THF was used. Wiley-VCH Verlag GmbH, 2000.
- Clausen, Christian,Weidner, Ingo,Butenschoen, Holger
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p. 3799 - 3806
(2007/10/03)
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- Catalytic activation of C-H and C-C bonds of allylamines via olefin isomerization by transition metal complexes
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(matrix presented) The metal-catalyzed reaction of olefins with allylamines bearing coordination sites (2-pyridyl groups) was studied. With Ru3(CO)12 as catalyst, activation of C-H bonds led to the formation of ketimines that were hydrolyzed to give asymmetric ketones. With [(C8H14)2RhCl]2, both C-H and C-C bonds were activated and symmetric ketones were formed on hydrolysis. The reaction involves double bond migration of the allylamine to form an aldimine.
- Jun, Chul-Ho,Lee, Hyuk,Park, Jae-Bum,Lee, Dae-Yon
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p. 2161 - 2164
(2008/02/11)
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- The CoCl2/Ph(Et)2N:BH3/CO system: Reactions of the borane and cobalt carbonyl species
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The CoCl2/Ph(Et)2N:BH3/CO system is useful for the hydroboration and carbonylation of alkenes to obtain the corresponding dialkyl ketones. The cobalt carbonyl species formed in situ in this way is also useful for hydroacylation-cyclisation of norbornene and for the Pauson-Khand reaction.
- Rao, M. Lakshmi Narayana,Periasamy, Mariappan
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- Nickel catalyzed electrosynthesis of ketones from organic halides and metal carbonyls
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Ketones can be easily obtained by electroreduction in an undivided cell of an organic halide-metal carbonyl mixture using a Ni-bpy catalytic system in DMF (bpy = 2,2'-bipyridine). The process is especially well convenient for primary benzyl and alkyl halides.
- Dolhem,Ocafrain,Nedelec,Troupel
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p. 17089 - 17096
(2007/10/03)
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- Process for the preparation of diamine intermediates useful in the synthesis of HIV protease inhibitors
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The present invention provides a process for the preparation of compounds of formula (V) below, and analogs thereof, which are useful as intermediates for the synthesis of HIV protease inhibitors, including cyclic ureas. STR1
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- Cathodic carbonylation. Synthesis of aliphatic aldehydes using an electroreductively generated iron-carbonyl anion
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Alkyl halides are electroreductively coupled with pentacarbonyliron to generate the acyliron complexes. After hydrolytic work-up, these anionic acyl compounds produce aldehydes in good yields. The best results were obtained with the bromide as starting halide. The first step in the formation of acyliron complexes is the direct cathodic reduction of [Fe(CO)5] to the anionic species. Synthetic and mechanistic aspects of the reaction are discussed.
- Yoshida, Kunihisa,Kuwata, Hideki
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p. 1873 - 1877
(2007/10/03)
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- Convenient Synthesis of Functionalized Dialkyl Ketones and Alkanoylsilanes: 1-(Benzotriazol-1-yl)-1-phenoxyalkanes as Alkanoyl Anion Equivalents
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(Benzotriazol-1-yl)-1-phenoxyalkanes 10, prepared by two-step transformations of the corresponding aldehydes, are readily deprotonated at the methine group by BuLi.Subsequent reactions with alkyl halides, aldehydes, ketones, and imines yield the corresponding substituted derivatives that undergo hydrolysis under acidic conditions to afford the expected functionalized ketones 13, 15, 17, 19, 21, 24 and 25.Two successive lithiations of (benzotriazolyl)phenoxymethane, each followed by reaction with a trialkylsilyl chloride, alkyl halide, aldehyde, or ketone, generate similar intermediates 27, 39, 31, 33, and 36.Subsequent hydrolyses of 27, 29, 31, 33, and 36 yield the functionalized ketones 28, 30, and 32 and the alkanoylsilanes 34 and 37 in good yields.
- Katritzky, Alan R.,Lang, Hengyuan,Wang, Zuoquan,Lie, Zhu
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p. 7551 - 7557
(2007/10/03)
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- Synthesis of deuterium-labelled polyoctylalkanes
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The synthesis of specifically labelled 9-d-9-octylheptadecane (1) and 9-d-9,10-dioctyloctadecane (2) has been achieved using selective and specific deuterium labelling methods. The precursor to the latter compound, tetraoctyl ethene, has been achieved by a variant of the McMurry reaction which improves upon recently published methods.
- Bolton,Luff,Sutcliffe
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p. 1205 - 1213
(2007/10/03)
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- Synthesis of Dialkyl Ketones from Alkenes Using Ph(Et)2N:BH3/CoCl2/CO Reagent System
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Reaction of alkenes with Ph(Et)2N:BH3/CoCl2/Co in THF followed by oxidation gives the corresponding dialkyl ketones.
- Rao, Maddali L. N.,Periasamy, Mariappan
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p. 9069 - 9070
(2007/10/02)
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- Preparation of polyfunctional ketones by a cobalt(II) mediated carbonylation of organozinc reagents
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Functionalized organozinc halides can be efficiently carbonylated under atmospheric pressure in the presence of cobalt(II) bromide in THF:NMP leading to polyfunctional symmetrical ketones in 56-80% yield.
- Devasagayaraj,Knochel
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p. 8411 - 8414
(2007/10/02)
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- New Electrochemical Synthesis of Ketones from Organic Halides and Carbon Monoxide
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The dissolution of a stainless steel anode provides catalytic nickel species which enable the efficient synthesis of ketones by electrolysis of organic halides in DMF in the presence of bipyridine and carbon monoxide.
- Ocafrain, Maitena,Devaud, Marguerite,Troupel, Michel,Perichon, Jacques
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p. 2331 - 2332
(2007/10/02)
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- Hindered Organoboron Groups in Organic Chemistry. Part 22. Some Interesting Properties of 2,4,6-Triisopropylphenylborane (Tripylborane, TripBH2, A New Useful Monoarylborane
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2,4,6-Triisopropylphenylborane (tripylborane, TripBH2) is a solid, stable, hydroborating agent that hydroborates monosubstituted alkenes to give either TripBHR1 or TripBR12.TripBHR1 can be converted into mixed boranes TripBR1R2 (R1,R2 = primary alkyl, Rp) and TripBRpRs and TripBRs2 are also readily available.Oxidation of these products gives the corresponding alcohols in excellent yields, with a high selectivity for alkan-1-ols in the cases of groups derived from alk-1-enes.Cyanidation of TripBR2 proceeds to give ketones without migration of the aryl group.This establishes the low migratory aptitude of the aryl group and also that no scrambling of alkyl groups occurs.The tripyl group of TripBRp2 can be selectively removed.
- Smith, Keith,Pelter, Andrew,Jin, Zhao
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p. 395 - 396
(2007/10/02)
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- Fluoride-induced Activation of Molybdenum Hexacarbonyl: Formation of Esters and Lactones from Alkyl Iodides
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In the presence of fluoride ion, alkyl iodides RI are carbonylated by molybdenum hexacarbonyl to esters RCO2R, and diiodides lead to good yields of the corresponding lactones.
- Imbeaux, Michele,Mestdagh, Helene,Moughamir, Khadija,Rolando, Christian
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p. 1678 - 1679
(2007/10/02)
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- Carbonylation of R2BI in the presence of NaCo(CO)4 and Na2Fe(CO)4: A simple synthesis of dialkyl ketones
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Reaction of NaCo(CO)4 with R2BI under carbon monoxide at atmospheric pressure at room temperature readily gives the dialkyl ketones in good yields (61-85 percent) after H2O2/OH- oxidation.
- Devasagayaraj, A.,Rao, Narayana M. Lakshmi,Periasamy, M.
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p. 147 - 150
(2007/10/02)
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- Lithiation of Alkoxyalkyl Phenyl Sulfones. New Approach to Acyl Anion Synthesis
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(1-Ethoxyethoxy)methyl and (1-ethoxyethoxy)ethyl phenyl sulfones undergo metalation with LDA in THF in the presence of HMPA.The resulting lithium salts were easily alkylated with various alkyl halides and hydrolyzed under mild conditions to give the corresponding carbonyl compounds.The new synthetic method for the preparation of aldehydes and ketones employing these carbanions has been developed.
- Tanaka, Kazuhiko,Matsui, Syuichi,Kaji, Aritsune
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p. 3619 - 3622
(2007/10/02)
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