37172-15-9Relevant academic research and scientific papers
Addition of novel benzylmagnesium “ate” complexes of BnR2MgLi type to 2-(thio)pyridones and related compounds
So?nicki, Jacek G.,Idzik, Tomasz,Borzyszkowska, Aleksandra,Wróblewski, Emil,Maciejewska, Gabriela,Struk, ?ukasz
, p. 481 - 493 (2017/01/13)
Novel benzylation reagents BnR2MgLi were obtained by mixing benzylmagnesium chloride (BnMgCl) and appropriate organolithium compounds (RLi). As BnR2MgLi complexes are more nucleophilic than the parent Grignard compound they enabled regioselective C6-addition to electrophilic N-substituted 2-(thio)-pyridones and C4-addition to poorly reactive NH 2-(thio)pyridones in high and good yields, respectively. Thus, the application of these new reagents in efficient synthesis of 6-benzyl-3,6-dihydro- and 4-benzyl-3,4-dihydropyridin-2(1H)-ones is described. The prospect of wider application of BnR2MgLi in 1,4-addition to other electrophiles, comprising six-membered α,β-unsaturated systems is also presented.
Preparation and reactivity of cyanocuprates containing alkylseleno and alkyltelluro groups as non-transferable ligands
Zinn, Fabiano K.,Ramos, Eduardo C.,Comasseto, Jo?o V.
, p. 2415 - 2417 (2007/10/03)
Alkylseleno and alkyltelluro groups are efficient non-transferable ligands of cyanocuprates in 1,4-addition reactions to enones.
3-Metallated enamines XI. Transmetallation of 3-Stannylated enamines - A new method to generate 1-aminoallyllithium compounds
Ahlbrecht,Weber
, p. 1018 - 1025 (2007/10/02)
The transmetallation of 3-stannylated enamines, 1-morpholino-3-(trialkylstannyl)cycloalk-1-enes and 3-morpholino-5-(tributylstannyl)hex-3-ene, with butyllithium is a new and general way to generate s1-aminoallyllithium compounds. Stabilization by aromatic substituents is not further necessarily as in the case of preparation by deprotonation and even the thermodynamically less stable exoamino derivatives are accessible. Therefore homoenolate-equivalents of cyclic ketones are made available. Thus, the corresponding 3-alkylated or 3-silylated cycloalkanones and alken-3-ones were prepared via the 1-morpholinoallyllithium compounds.
CONJUGATE ADDITION TO α,β-UNSATURATED KETONES WITH MIXED LITHIUM TRIORGANOZINCATES
Watson, Randall A.,Kjonaas, Richard A.
, p. 1437 - 1440 (2007/10/02)
Lithium Triorganozincates of the type RR'2ZnLi, where R'=Me and R=n-Bu or sec-Bu, efficiently transfer the R group in a 1,4 fashion to α,β-unsaturated ketones.
Reactions of Mixed Homocuprates containing Sulphonyl-stabilized Carbanions as Non-transferable Ligands
Johnson, Carl R.,Dhanoa, Daljit S.
, p. 358 - 359 (2007/10/02)
Treatment of α-lithiosulphones with copper(I) iodide in tetrahydrofuran followed by 1 mol. equiv. of an alkyl-lithium or Grignard reagent produces mixed homocuprates - M+ (M = Li or MgX) which are effective reagents for the conjugate addition of R to enones and substitution of chloride in acid chlorides to produce ketones (>90percent yields).
ENZYMATIC "IN VITRO" REDUCTION OF KETONES. VI.(1) Reduction rates and stereochemistry of the HLAD-catalyzed reduction of 3-alkyl- and 4-alkylcyclohexanones.
Osselaer, T. A. Van,Lemiere, G. L.,Lepoivre, J. A.,Alderweireldt, F. C.
, p. 133 - 150 (2007/10/02)
Reaction rate constants for the catalytic step HLAD-NADH + ketone * HLAD-NAD+ + alcohol in the HLAD-catalyzed reduction of 3-alkyl- and 4-alkylcyclohexanones are determined from initial rate measurements in the coenzyme recycling system ketone-ethanol-NAD+-HLAD.By rate measurements at several temperatures, activation parameters were determined and isokinetic relationships tracked down.Two different isokinetic relationships show that the 3-alkylcyclohexanones pass through an other type of transition state than cyclohexanone and the 4-alkylcyclohexanones, which means that they have a different arrangement on the HLAD-NADH complex.The results are rationalized in view of the most recent principles on nucleophilic additions to carbonyl functions.The resulting model for the HLAD-catalyzed reduction adequately explains the observed rate accelerating and decelerating effects and the stereochemistry of the reduction as well.
