41601-84-7

Upstream product

• 109-72-8 n-butyllithium 
• 78-59-1 3,5,5-Trimethylcyclohex-2-en-1-one 
• 693-04-9 butyl magnesium bromide 
• 109-65-9 1-bromo-butane 
• 109-69-3 n-Butyl chloride 
• 88626-90-8 BuMnCl 

Relevant academic research and scientific papers

Effects of additives on cuprate 1,4-additions: Gilman reagents in the presence of Me3SiCN

Chemical and spectroscopic studies on Gilman cuprates R2CuLi·LiI in the presence of TMS-CN reveal the lack of independence of these species in THF solutions. A potential role for this additive in enhancing rates and yields of 1,4-, as well as 1,2-additions, is suggested.

Preparation and reactivity of cyanocuprates containing alkylseleno and alkyltelluro groups as non-transferable ligands

Alkylseleno and alkyltelluro groups are efficient non-transferable ligands of cyanocuprates in 1,4-addition reactions to enones.

The copper mediated Barbier reactions of α,β-unsaturated ketones: Regioselective conjugate and 1,2-addition

The one-pot reaction of isophorone and other α,β-unsaturated ketones with alkyl and aryl halides in the presence of magnesium and a copper salt ('Barbier' conditions) leads to the regiospecific formation of 1,4-addition products; the use of lithium leads to regioselective 1,2-addition.

Novel tridentate diamino organomanganese(II) complexes as homogeneous catalysts in manganese(II)/copper(I) catalyzed carbon-carbon bond forming reactions

The new, paramagnetic arylmanganese(II) complex Li[MnCl2(NCN)] (2, NCN [C6H3(CH2NMe2)2-2,6] -) has been obtained in high yield from the reaction of MnCl2 and [Li(NCN)]2 in a 2:1 molar ratio. In THF solution, 2 is likely an ionic species [Li(THF)n] [MnCl2(NCN)] (molecular weight determination and conductivity measurements), while magnetic measurements indicate that a high spin d5 manganese(II) center is present. Subsequent reaction of 2 with RLi afforded [MnR(NCN)] (R=Me (3a), n-Bu (3b)). Complex 2, using CuCl as a co-catalyst, is an effective catalyst system for cross-coupling of Grignard reagents with alkyl bromides and the 1,4-addition of organomagnesium halides to α,β-unsaturated ketones. No further additives or co-solvents are necessary. For both reactions a dramatic decrease in reaction times is observed when compared to standard manganese/copper systems. Alkyl bromides with unsaturated or heteroatom functionalities can be cross-coupled. Also, excellent reactivity towards normally unreactive β,β-disubstituted ketones has been observed in the 1,4-addition reaction.

Some Observations on the Mechanism of Diorganocuprate 1,4-Addition Reactions with α,β-Unsaturated Ketones: Effects of Diethyl Ether in Reactions of Butylcoppers in Toluene

Mixtures of butyllithium and copper iodide prepared in toluene react with α,β-unsaturated ketones predominantly in a 1,2-fashion. Addition of 2 equiv of diethyl ether to the system results in a dramatic preference for the 1,4-product, as found normally with diorganocuprates in ethereal solvents. These results are in accordance with the theoretical predictions that a suitable ligand is required to facilitate the stabilization of a formally copper(III) reaction intermediate on the 1,4-addition mechanistic pathway.

The Role of BF3*Et2O in Reactions of Lower Order (Gilman) Organocuprates

The effects of BF3*Et2O on lower order organocuprate reactions in THF have been investigated so as to determine what factors are responsible for the oftentimes dramatic reaction-rate enhancements observed.From spectroscopic experiments on the reagents alone, supported further by chemical studies, it was found that an orginally formed cuprate (R2CuLi or RR'CuLi) is altered significantly upon exposure to this Lewis acid.The copper-containing species thereby generated, together with BF3, form a more reactive combination and appear to be at least in part responsible forthe accelerated chemistry.

ORGANOMANGANESE (II) REAGENTS XVI: COPPER-CATALYZED 1,4-ADDITION OF ORGANOMANGANESE CHLORIDES TO CONJUGATED ENONES

Copper-catalyzed conjugate addition of organomanganese chlorides to conjugated enones in THF, at 0 deg C, leads to the 1,4-addition products in high yields.The scope of the reaction is very large and the results are generally better than those obtained from organomagnesium compounds in the presence of a copper salts as well as from organocopper or cuprate reagents.Furthermore organomanganese chlorides are indisputably cheaper and more stable than the latter.

Organocuprates Containing Dimethyl Sulfoxide Anion as a Nontransferable Ligand

Mixed homocuprates and in which the anion of dimethyl sulfoxide acts as a nontransferable ligand are readily prepared from MeSOCH2Li, alkyl- or aryllithium reagents, and Cu(I) salts.These novel cuprates are useful in the conversions of acid chlorides to ketones, conjugate additions to α,β-unsaturated ketones, SN2' reactions with allylic or propargylic acetates and epoxides, and coupling reactions with primary iodides and tosylates.All of these reactions proceed with selective transfer of the ligand R.From the points of view of cost, availability, and lack of interference with product isolation, the Me2SO anion is an ideal nontransferable ligand.