5222-61-7Relevant academic research and scientific papers
Synthesis of 2′-Alkylspiro[2-X-cyclohexan-1,3′-3′H-indole] (X = H; X = CH3) by an Unexpected Reaction between an Organomagnesium Halide and 2′-Methylspiro[2-X-cyclohexan-1,3′-3′H-indole]. X-ray Structure of a Fluorescent Dimeric Compound
Rodriguez, J. Gonzalo,Urrutia, Anahi,De Diego, J. Eugenio,Martinez-Alcazar, M. Paz,Fonseca
, p. 4332 - 4337 (1998)
The reaction of 2′-methylspiro[cyclohexan-1,3′-3′H-indole] (1a) with methylmagnesium iodide gives 2′-ethyl-, 2′-isopropyl-, and 2′-tert-butylspiro[cyclohexan-1,3′-3′H-indole] as the unexpected 2′-methyl insertion products; their presence and ratio are dependent upon the reaction conditions. Influence of a methyl substituent in 2′-methylspiro[2-methylcyclohexan-1,3′-3′H-indole] (1b) on the reaction with methylmagnesium iodide has been analyzed; the 2′-ethyl (2b) and 2′-isopropyl (3b) derivatives were obtained as the insertion products together with a luminescent compound that was identified by X-ray diffraction analysis as meso-(1R,2S),(1S,2R)-α,β-di{(2′-(spiro[2-methylcyclohexan-1, 3′-3′H-indolyl]}ethene (10). The reaction of 1a or 1b with some active organomagnesium halides (allyl or benzyl) afforded the 2′-methyl-2′-alkyl-3′H-indole derivative (allyl, 5a or 5b; benzyl, 6a) as an apparent addition product. The reaction possibly occurs through a mechanism of radical intermediates.
Copper-Catalyzed Conjugate Addition of Trimethylaluminium to α,β-Unsaturated Ketones
Kabbara, Jazid,Flemming, Steffen,Nickisch, Klaus,Neh, Harribert,Westermann, Juergen
, p. 1489 - 1494 (2007/10/02)
The conjugate methylation of α,β-unsaturated ketones with trimethylaluminium occurs smoothly in a very simple procedure under the catalytic CuI salts.Scope and limitations of this process as well as the influence of solvent and catalyst on the kinetics were studied.In addition, the effect of chlorotrimethylsilane as an additive was investigated.Attack on the carbonyl group in 1,2-fashion could not be observed under the reaction conditions.- Key Words: Conjugate alkylation / Trimethylaluminium / Copper catalysis
Lewis Acid Mediated Reactions of Organocopper Reagents. Entrainment in the Conjugate Addition to α,β-Unsaturated Ketones, Esters, and Acids via the RCu*BF3 System
Yamamoto, Yoshinori,Yamamoto, Sinichi,Yatagai, Hidetaka,Ishihara, Yuji,Maruyama, Kazuhiro
, p. 119 - 126 (2007/10/02)
Lewis acid mediated reactions of organocopper reagents with various kinds of α,β-unsaturated carbonyl derivatives are described.RCu*BF3, as well as RCu-other Lewis acid systems, is useful for the conjugate addition to the α,β-unsaturated ketones and esters, whose double bonds are sterically crowded.Certain α,β-unsaturated carboxylic acids also undergo a 1,4-addition through this reagent.Methyl sorbate undergos a 1,4-addition via BuCu*BF3, while undergoing a 1,6-α,δ-addition via Bu2CuLi.BuCu*BF3 reacts more readily with an aldehyde than with a ketone; the degree of chemoselectivity is greater than that of Bu2CuLi, BuLi, or BuMgBr.The R2CuLi-BF3 system is useful for the double alkylation of α,β-unsaturated esters at the β-position and the carbonyl center.Stereochemical aspects of these new copper reagents are also reported.
