55373-58-5Relevant articles and documents
Soft Enolization of 3-Substituted Cycloalkanones Exhibits Significantly Improved Regiocontrol vs Hard Enolization Conditions
Dwulet, Natalie C.,Ramella, Vincenzo,Vanderwal, Christopher D.
supporting information, p. 9616 - 9619 (2021/12/17)
Soft enolization conditions are revealed to be markedly better than the typically applied hard enolization protocols for regioselective enoxysilane formation from unsymmetrical 3-substituted cycloalkanones. Five-, six-, and seven-membered cycloalkanones each with 3-methyl, 3-isopropyl, or 3-phenyl substituents were investigated, and in all but one case, regioselectivities were ≥11:1 for enolization away from the substituent. These results are complementary to the regiospecific enoxysilane formation derived from cycloalkenone conjugate addition/enolate silylation.
Development of enantioselective synthetic routes to (-)-Kinamycin F and (-)-lomaiviticin aglycon
Woo, Christina M.,Gholap, Shivajirao L.,Lu, Liang,Kaneko, Miho,Li, Zhenwu,Ravikumar, P. C.,Herzon, Seth B.
, p. 17262 - 17273,12 (2020/09/02)
The development of enantioselective synthetic routes to (-)-kinamycin F (9) and (-)-lomaiviticin aglycon (6) are described. The diazotetrahydrobenzo[b] fluorene (diazofluorene) functional group of the targets was prepared by fluoride-mediated coupling of
GUANIDINE DERIVATIVES AND USE THEREOF AS NEUROPEPTIDE FF RECEPTOR ANTAGONISTS
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Page 54, (2010/02/08)
The invention relates to guanidine derivatives of formula (I) where: A = a chain of 3-c6 carbon atoms, one of which can be replaced by -N(R')- or -O- and R' = H or a substituent, where the ring skeleton only contains both double bonds of the thiazole component, the pharmaceutically-acceptable acid addition salts of basic compounds of formula (I), the pharmaceutically-acceptable salts of compounds of formula (I),, comprising acid groups, with bases, the pharmaceutically-acceptable esters of hydroxy or carboxyl group containing compounds of formula (I) and the solvates or hydrates thereof, which are partly known and partly novel and exhibit a neuropeptide FF receptor antagonist effect. The above are suitable for the treatment of pain and hyperalgesia, withdrawal symptoms in alcohol, psychotropic and nicotine dependencies, for improvement or cure of said dependencies, for regulation of insulin excretion, food intake, memory functions, blood pressure, electrolyte and energy management and for treatment of urinary incontinence. The above can be produced using generally used methods and processed to give medicaments.
New copper chemistry, part 29: Re-evaluation of organocuprate reactivity: Logarithmic reactivity profiles for iodo- versus cyano-Gilman reagents in the reactions of organocuprates with 2-cyclohexenone and iodocyclohexane
Bertz, Steven H.,Chopra, Anu,Eriksson, Magnus,Ogle, Craig A.,Seagle, Paul
, p. 2680 - 2691 (2007/10/03)
Iodo-Gilman reagents Me2-CuLi·LiI, Bu2CuLi·LiI, and BuThCu-Li·LiI and cyano-Gilman reagents (nee "higher order cyanocuprates" Me2Cu-Li·LiCN, Bu2CuLi·LiCN, and BuTh-CuLi·LiCN react with 2-cyclohexenone at various rates, which depend upon the R groups (Me, Bu, Th=thienyl), Li salt (LiI vs. LiCN), solvent (ether vs. THF), and amount of trimethylsilyl chloride (TMSCl) additive. The effect of the Li salt (CuI vs. CuCN precursor) is less than that of solvent or TMSCl. The butylcuprate-iodocyclohexane reaction has also been examined as a function of Li salt, solvent, and TMSCl additive, and similar effects are observed. The reactivity matrix R with elements ri,j is a convenient way to store and present a large amount of relative reactivity data. Entry ri,j is the ratio of the rate with reagent i to the rate with reagent j, which we approximate by using yields measured after a short time (4 s). The logarithmic reactivity profile (LRP) provides an efficient means for determining yields under conditions where such comparisons are valid. The results of a large number of 4-point LRPs and related reactions are tabulated and analyzed to provide a clearer picture of organocuprate reactivity.
Regio- and enantio-selective enolisations of cyclic ketones using chiral lithium amide bases
Bambridge, Kimberley,Clark, Barry P.,Simpkins, Nigel S.
, p. 2535 - 2542 (2007/10/02)
Enolisations of 3-methylcyclohexanone 16, and of a trans-fused perhydroisoquinolone derivative 8, using several chiral lithium amide bases have been examined.In reactions involving a single enantiomer of the ketone 8, the use of a chiral base can result in enhancement or reversal of the normal regioselectivity of enolisation to give the enol silane derivatives 9 and 10, depending on the configuration of the base used.Similar matched and mismatched results are observed when (R)-3-methylcyclohexanone, (R)-16, is treated with either enantiomer of the chiral base 3.A new type of kinetic resolution, termed regiodivergent resolution, is observed when enolisation of the racemic ketones 8 or 16 is carried out using the chiral base 3.
The Kharasch reaction revisited: CuX3Li2-catalyzed conjugate addition reactions of Grignard reagents
Reetz, Manfred T.,Kindler, Alois
, p. C5 - C7 (2007/10/02)
The conjugate addition of Grignard reagents RMgX to α,β-unsaturated ketones and esters is effectively catalyzed by soluble copper ate-complexes of the type CuX3Li2, e.g.CuI*2LiCl.In the presence of Me3SiCl the corresponding ketone enolsilanes are formed in high yield and selectivity.Diastereoselectivity in the case of chiral ketones is similar to that observed by using stoichiometric amounts of cuprates R2CuLi.Thus CuX3Li2-catalyzed 1,4-additions of Grignard reagents may be an industrially viable process.Keywords: Copper; Magnesium; Lithium; Silicon; Ketone; Enolsilanes
Iodotrimethylsilane-Promoted Additions of Monoorganocopper Compounds to α,β-Unsaturated Ketones, Esters, and Lactones
Bergdahl, Mikael,Eriksson, Magnus,Nilsson, Martin,Olsson, Thomas
, p. 7238 - 7244 (2007/10/02)
Conjugate additions with the efficient monoorganocopper-iodotrimethylsilane combination, exemplified mainly with methylcopper, butylcopper, and tert-butylcopper, proceed cleanly, smoothly, and rapidly to a variety of α,β-unsaturated carbonyl compounds; cy
An alternative procedure for the O-trimethylsilylation of enolates generated by copper-catalyzed 1,4-additions
Andringa,Oosterveld,Brandsma
, p. 1393 - 1396 (2007/10/02)
Anhydrous lithium bromide has been successfully used as an additive instead of hexamethylphosphoric triamide in the O-trimethylsilation of enolates generated by copper halide-catalyzed reaction of Grignard reagents with a number of α,β-unsaturated carbony
Trimethylsilyl Chloride/Tetramethylethylenediamine Facilitated Additions of Organocopper Reagents (RCu) to Enones
Johnson, Carl R.,Marren, Thomas J.
, p. 27 - 30 (2007/10/02)
Alkylcoppers (RCu) add readily in a conjugate fashion to enones in the presence of TMSCl and TMEDA to give high yields of trimethylsilyl enol ethers.
