- Soluble lanthanide salts (LnCl3,·2 LiCl) for the improved addition of organomagnesium reagents to carbonyl compounds
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(Chemical Equation Presented) Easy-to-prepare solutions of LnCl 3·2 LiCl (Ln = La, Ce, Nd) (0.3-0.5 M in THF) are a unique source of soluble lanthanide salts with versatile applications in organic synthesis. These salts can serve as promoters or catalysts for the addition of organometallic compounds to sterically hindered, enolizable or α,β-unsaturated ketones or imines.
- Krasovskiy, Arkady,Kopp, Felix,Knochel, Paul
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- Development of a Scalable Lanthanide Halide/Quaternary Ammonium Salt System for the Nucleophilic Addition of Grignard Reagents to Carbonyl Groups and Application to the Synthesis of a Remdesivir Intermediate
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This manuscript describes the development and implementation of a scalable additive system, consisting of a lanthanide salt and a solubilizing quaternary ammonium salt, to improve the yield and robustness of the addition of an organomagnesium reagent to a
- Brak, Katrien,Bremner, W. Stacy,Brown, Angela M.,Chtchemelinine, Andrei,Heumann, Lars,Kerschen, James A.,Stevens, Andrew C.,Subotkowski, Witold,Vieira, Tiago,Wolfe, Lydia C.,Xu, Boran,Yu, Chia-Yun
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- Solutions of anhydrous lanthanide salts and its preparation
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The present invention relates to anhydrous solutions of MX 3 €￠z LiA in a solvent, wherein M is a lanthanide including lanthanum, or yttrium or indium; z > 0; and X and A are independently or both monovalent anions, preferably Cl, Br or I. The solution is readily prepared by dissolving or suspending MX 3 or its hydrate and z equiv LiA in water or hydrophilic solvents, or mixtures thereof, removing the solvent under vacuum and dissolving the resulting powder in another solvent. The solution of MX 3 €￠z LiA can advantageously be used e.g. in addition reactions of Grignard reagents to ketones and imines. Even the catalytic use of MX 3 €￠z LiA is possible. Also claimed are a method for preparing the anhydrous solutions, the use of such solution in a chemical reaction and chemical compositions MX 3 €￠z LiA, with M, z, X and A as indicated above.
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- Improved addition of phenyllithium to hindered ketones by the use of non-polar media
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The use of a non-polar medium at room temperature is an efficient, cheap and easy way to improve the low reactivity of six hindered ketones towards phenyllithium.
- Lecomte, Vincent,Stéphan, Elie,Jaouen, Gérard
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p. 3463 - 3465
(2007/10/03)
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- SYNTHESIS AND RITTER REACTION OF 1,7,7-TRIMETHYL-2-PHENYLBICYCLOHEPTAN-2-EXO-OL
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1,7,7-Trimethyl-2-phenylbicycloheptan-2-exo-ol is formed stereospecifically in the reaction of camphor with phenyllithium.The corresponding individual 1,7,7-trimethyl-4-phenylbicyclohept-2-yl-exo-acyl-amines were obtained as a result of the nucleophilic addition of acetonitrile, propionitrile, or methoxypropionitrile to this tertiary alcohol, which takes place in the presence of concentrated sulfuric acid.A scheme is proposed for their formation as a result of rearrangements of the intermediately formed 1,7,7-trimethylbicyclohept-2-yl cation.
- Kozlov, N. G.,Popova, L. A.,Vyalimyae, T. K.,Knizhnikov, V. A.,Ol'dekop, Yu. A.
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p. 702 - 705
(2007/10/02)
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