3319-03-7Relevant academic research and scientific papers
Synthesis of 1-organyl-1-(trimethylsiloxy)-2-(dimethylamino)ethenes and new hypervalent silicon compounds based thereon
Gostevskii,Albanov,Vashchenko,Smirnov
, p. 1385 - 1389 (2016)
1-Organyl-1-(trimethylsiloxy)-2-(dimethylamino)ethenes were synthesized for the first time, and their reactions with trichloro(methyl)silane and trifluoro(phenyl)silane afforded silicon bis-chelates, methylbis-[2-(dimethylamino)-1-(organyl)ethenolato-N,O]
Modular counter-Fischer?indole synthesis through radical-enolate coupling
Chung, Hyunho,Kim, Jeongyun,Gonzalez-Montiel, Gisela A.,Cheong, Paul Ha-Yeon,Lee, Hong Geun
supporting information, p. 1096 - 1102 (2021/01/26)
A single-electron transfer mediated modular indole formation reaction from a 2-iodoaniline derivative and a ketone has been developed. This transition-metal-free reaction shows a broad substrate scope and unconventional regioselectivity trends. Moreover, important functional groups for further transformation are tolerated under the reaction conditions. Density functional theory studies reveal that the reaction proceeds by metal coordination, which converts a disfavored 5-endo-trig cyclization to an accessible 7-endo-trig process.
Superelectrophilic chemistry of amino-nitriles and related substrates
Raja, Erum K.,Klumpp, Douglas A.
experimental part, p. 4494 - 4497 (2011/07/08)
The superacid-promoted Houben/Hoesch reactions of amino-nitriles and related compounds have been studied. The nitriles form dicationic electrophiles and react with benzene in fair to good yields (12-95%). The intermediate iminium ions may also be reduced to the benzylic amines by NaBH4 or H 2.
Tandem catalytic allylic amination and [2,3]-stevens rearrangement of tertiary amines
Soheili, Arash,Tambar, Uttam K.
supporting information; experimental part, p. 12956 - 12959 (2011/10/08)
We have developed a catalytic allylic amination involving tertiary aminoesters and allylcarbonates, which is the first example of the use of tertiary amines as intermolecular nucleophiles in metal-catalyzed allylic substitution chemistry. This process is
Asymmetric synthesis of β-dialkylamino alcohols by transfer hydrogenation of α-dialkylamino ketones
Kosmalski, Tomasz,Wojtczak, Andrzej,Zaidlewicz, Marek
experimental part, p. 1138 - 1143 (2009/09/27)
Transfer hydrogenation of representative aryl and heteroaryl dialkylaminomethyl ketones with formic acid-triethylamine, catalyzed by RuCl[(R,R)-TsDPEN](η-p-cymene), produces the corresponding β-dialkylamino alcohols, 97-99% ee, in 50-73% yields. Asymmetric synthesis of (R)-macromerine, 98% ee, the cactus Coryphantha macromeris alkaloid, is also described.
Requirements for selective hydrophobic acceleration in the reduction of ketones
Biscoe, Mark R.,Uyeda, Christopher,Breslow, Ronald
, p. 4331 - 4334 (2007/10/03)
(Chemical Equation Presented) Reductions of various quaternized hydrophobic β-keto amines were performed in water and in methanol using borohydride anions carrying hydrophobic groups. The most important requirement of the substrate to permit hydrophobical
Method for preparing chiral diphosphines
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, (2008/06/13)
The invention concerns a method for preparing a compound of formula (1) wherein: A represents naphthyl or phenyl optionally substituted; and Ar1, Ar2independently represent a saturated or aromatic carbocyclic group, optionally substituted.
Hydrophobically Directed Selective Reduction of Ketones
Biscoe, Mark R.,Breslow, Ronald
, p. 12718 - 12719 (2007/10/03)
Three hydrophobic borohydrides carrying phenyl, pentafluorophenyl, and β-naphthyl groups were used to reduce ketones in water and in methanol. With ketones carrying phenyl, naphthyl, or biphenyl substituents, there was preferential reduction in methanol o
Substituent Effects on the Strength of C-C Bonds, 14. - Kinetic and Thermodynamic Stability of 2,3-Bis(dialkylamino)-1,4-diketones - Energy of Stabilization of α-Dialkylamino α-Carbonylalkyl Radicals with Capto-dative Substituents
Welle, Frank,Verevkin, Sergej P.,Keller, Manfred,Beckhaus, Hans-Dieter,Ruechardt, Christoph
, p. 697 - 710 (2007/10/02)
The equilibrium constants and rate constants for the dissociation of the 2,3-bis(dialkylamino)-1,4-diketone diastereomers meso- and DL-7a and 7b were measured over a temperature range of 40 deg C.From the enthalpies of dissociation ΔHDiss and ethalpies of activation ΔH(excit.) and the strain enthalpies of 7 the bond dissociation enthalpies BDE(C-C) of 7 were determined.By comparison with the dissociation enthalpies of Ct-Ct alkanes the change of these BDEs(C-C) by the capto-dative substitution was determined to be 85.4 kJ mol-1 (20.4 kcal mol-1).The heats of formation ΔHf0(g) of a series of amino ketones 8 were determined from their heats of combustion and their heats of evaporation.From the ΔHf0(g) values in combination with MM2 calculations of their strain enthalpies strain-free increments CHn2-n> with n = 0, 1, 2 were derived and geminal interaction enthalpies in the ground states were obtained thereof.The radical stabilization enthalpy RSE of 6 was deduced from the ΔBDE(C-C) values and the ground state effect to be 73.6 kJ mol-1 (17.6 kcal mol-1).From these data and the radical stabilization enthalpies RSE of α-aminoalkyl radicals (4.2 kJ mol-1) and α-carbonyl radicals (28.9 kJ mol-1) a synergetic radical stabilization enthalpy of 40.5 kJ mol-1 (9.7 kcal mol-1) is deduced.This number combines "extra" resonance stabilization and general inductive or anomeric geminal substituent interaction in the radicals.The crystal structure of meso-7a has been determined by X-ray diffraction methods. - Key Words: C-C Bond cleavage, kinetics of / Heats of formation / Radicals, stability of / Capto-dative effect / Geminal substituents, energetic interaction of
