- C-substituted, 1H-azoles for amphoteric, solvent-less proton conductivity
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Disclosed herein are the compounds shown below. Also disclosed are methods of making the compounds. R1=—O—; R2=any alkyl chain; R3=—CH3, —CN, —COOCH3, -tetrazole, -imidazole, or -triazole; R4=—H or —R5; R5=—H, -halogen, —C≡CH, or —C≡C—; n is a positive integer; and m is a positive integer.
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- Site-selective aliphatic C-H bromination using N -bromoamides and visible light
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Transformations that selectively functionalize aliphatic C-H bonds hold significant promise to streamline complex molecule synthesis. Despite the potential for site-selective C-H functionalization, few intermolecular processes of preparative value exist. Herein, we report an approach to unactivated, aliphatic C-H bromination using readily available N-bromoamide reagents and visible light. These halogenations proceed in useful chemical yields, with substrate as the limiting reagent. The site selectivities of these radical-mediated C-H functionalizations are comparable (or superior) to the most selective intermolecular C-H functionalizations known. With the broad utility of alkyl bromides as synthetic intermediates, this convenient approach will find general use in chemical synthesis.
- Schmidt, Valerie A.,Quinn, Ryan K.,Brusoe, Andrew T.,Alexanian, Erik J.
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supporting information
p. 14389 - 14392
(2014/12/10)
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- C-SUBSTITUTED, 1H-AZOLES FOR AMPHOTERIC, SOLVENT-LESS PROTON CONDUCTIVITY
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Disclosed herein are the compounds shown below. Also disclosed are methods of making the compounds. R1=—O—; R2=any alkyl chain; R3=—CH3, —CN, —COOCH3, -tetrazole, -imidazole, or -triazole; R4=—H or —R5; R5=—H, -halogen, —C≡CH, or —C≡C—; n is a positive integer; and m is a positive integer.
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Page/Page column
(2014/02/16)
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- Hydrosilanes are not always reducing agents for carbonyl compounds but can also induce dehydration: A ruthenium-catalyzed conversion of primary amides to nitriles
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A practical procedure for production of nitriles is offered by the triruthenium carbonyl cluster catalyzed dehydration of primary carboxamides with hydrosilanes under neutral conditions. This is the first example that a transition-metal-catalyzed activation of Si-H bonds does not lead to the reduction of carbonyl compounds but to dehydration. Possible mechanisms for the dehydration is discussed on the basis of NMR spectroscopic detection of intermediary species. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.
- Hanada, Shiori,Motoyama, Yukihiro,Nagashima, Hideo
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supporting information; experimental part
p. 4097 - 4100
(2009/04/10)
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- Unsymmetrical Ketone Synthesis via a Three-Component Connection Reaction of Organozincs, Allylating Agents, and Carbon Monoxide
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A wide variety of organozincs (diethylzinc, alkylzinc halides, and organozincs 2, 5, and 9a-e, functionalized with ester and nitrile groups) undergo a three-component connection reaction with carbon monoxide and allylic benzoates or phosphates 1a-h to furnish unsymmetrical ketones, e.g., 3, 6, and 10, in good yields uder 1 atm of carbon monoxide at ambient temperature by the catalysis of tetrakis(triphenylphosphine)palladium in THF/HMPA.The regio- and stereoselectivities of the present carbonylation show marked contrast to those reported for the palladium-catalyzed carbonylation of usymmetrical allylic substrates.For example, the reaction of crotyl benzoate with octylzinc iodide provides all the possible stereo- and regioisomers, i.e., cis- and trans-2-butenyl and 1-methyl-2-propenyl octyl ketones in comparable amounts.The carbonylative coupling of carvyl phosphates, trans- and cis-1h, and γ-zincio ester 5 is stereospecific and proceeds with inversion of configuration at the allylic stereocenters to furnish cis- and trans-6h, respectively, as single diastereomers.In the absence of HMPA, the reaction feature changes dramatically and lactones 12 and 13 (composed of organozincs, carbon monoxide, and allylating agents in the ratios of 1:1:2 and 2:1:1, respectively) and symmetrical keto diesters 14 (composed of 2 mol of organozincs and 1 mol of carbon monoxide) are formed in varying ratios depending on the reaction conditions.Synthetic scope of the unsymmetrical ketones and mechanistic rationale for these unique and unprecedented reaction behaviors are discussed.
- Yasui, Kengo,Fugami, Keigo,Tanaka, Shuji,Tamaru, Yoshinao
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p. 1365 - 1380
(2007/10/02)
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- FUNCTIONAL GROUP-TOLERANT HYDROALKYLATION OF ELECTRON-DEFICIENT OLEFINS THROUGH COPPER(I)-CATALYZED PHOTOADDITION OF ORGANIC HALIDES FOLLOWED BY REDUCTION WITH ZINC
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A method of accomplishing hydroalkylation of electron-deficient olefins which tolerates a variety of functional groups, in which organic halides and electron-deficient olefins are subjected to a photoreaction catalyzed by the CuBr-Bun3P complex followed by treatment with Zn dust in the presence of AcOH, has been developed.
- Mitani, Michiharu,Hirayama, Hiroyuki
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p. 1562 - 1572
(2007/10/02)
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- A PRACTICAL REGIOSELECTIVE SYNTHESIS OF ω-FUNCTIONALIZED, LONG-CHAIN 2,3-DIALKYLINDOLES
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Several routes towards the regioselective synthesis of ω-functionalized 2,3-dialkylindoles (1 and 2) have been compared and discussed.A synthesis based on the appropriately modified indolization reaction according to Leimgruber and Batcho resulted the method of choice, being versatile and of quite general applicability for inoles of this type.
- Arcari, Marinella,Aveta, Raffaele,Brandt, Alberto,Cecchetelli, Loredana,Corsi, Giordano Bruno,Rella, Mario Di
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p. 499 - 504
(2007/10/02)
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- Orthocarbonsaeure-ester mit 2,4,10-Trioxaadamantanstruktur als Carboxylschutzgruppe; Verwendung zur Synthese von substituierten Carbonsaeuren mit Hilfe von Grignard-Reagenzien
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The surprising stability of 2,4,10-trioxa-3-adamantyl derivatives 1 against nucleophilic substitution by organomagnesium compounds is discussed and shown to be caused by unfavourable stereoelectronic and steric factors governing the substitution of these cage compounds (Scheme 2).As a consequence, a number of Grignard reagents 2 containing the carboxyl group masked as 2,4,10-trioxa-3-adamantyl group could be prepared and have been reacted in a second step with various electrophiles (cf.Scheme 4).In the products 7-13 and 15b the carboxyl masking group is removed by mild ac id hydrolysis and saponification (cf.Scheme 3) to yield the corresponding acids 16a-21a, 22, and 23a.Acids 21a and 23a have been further transformed to give the macrocyclic lactones 24 and 26, isolated from Galbanum oleo-gum-resin, and acid 22 to give 12-methyl-13-tridecanolide (25), isolated from Angelica root oil.In addition 1-bromo-ω-(2,4,10-trioxa-3-adamantyl)alkanes 1c and 1b have been used to synthesize (+/-)-methyl recifeiolate (29b) and pure cis-ambrettolic acid ((Z)-32a).
- Voss, Gundula,Gerlach, Hans
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p. 2294 - 2307
(2007/10/02)
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