Additions of Organoaluminum Reagents

For alkylation reagents, trialkylaluminum compounds are more interesting than other organometallic reagents because they are economically obtained on an industrial scale from aluminum hydride and alkenes. Despite this 

Enantioselective Nickel-Catalysed Transformations By Helene Pellissier Helene Pellissier, 2016 

the reactivity of air-unstable AlMCj in catalytic synthesis is modified by the presence of oxo-containing by-products attained through 

Methylations of aldehydes with AlMej and (AlMe3)2-DABCO in the presence of an in situ generated nickel catalyst from a D-glucosamine-derived phosphite-oxazoline ligand. 

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The conjugate addition of organoaluminum reagents to quinols is directed by the hydroxy group at C-4. ... 

The nucleophilic addition of organoaluminum reagent 60 to the magnesium salt 57 provided the homopropargylic cyclopropanol 61 in 50% yield. ... 

Stereoselective conjugate addition of organoaluminum reagents has been performed by employing a, (3-unsaturated carbonyl compounds having chiral auxiliary. Kunz et al. have demonstrated the asymmetric 1,4-addition of a,(3-unsaturated... 

Carreno MC, Gonzalez MP, Ribagorda M (1998) Studies of diastereoselectivity in conjugate addition of organoaluminum reagents to (/f)-[(p-Tolylsulfinyl)methyl]quinols and derivatives. J Org Chem 63 3687-3693... 

Asymmetric induction of chirality is also observed for the diastereoselective addition of organoaluminum reagents and allylstannanes to aldehyde groups at the side chain of Ti -allyl(tricarbonyl)iron lactone complexes. Ketones in the side chain of Ti -allyl(tricarbonyl)iron lactone complexes can be transformed into tertiary alcohols in a diastereoselective fashion by addition of organoaluminum reagents (Scheme... 

Scheme 4-96. Addition of organoaluminum reagents to Tj -allyliron-substituted carbonyl groups.

Small quantities of organoaluminum distillation residues and waste solutions may be destroyed by slow addition of a 25% isopropanol solution in a hydrocarbon solvent. Safety procedures for handhug large volumes of organoaluminum reagents can be obtained from commercial vendors. 

Addition of Grignard reagents to ketones to form alcohols is a class of the most fundamental reactions in organic synthesis. Much data on selectivities of this reaction are available. Yamamoto et al. utilized a highly bulky organoaluminum compounds as a... 

Alkynylation of enones. The nickel catalyst obtained from Ni(acac)2 and DIBAH catalyzes the conjugate addition of organoaluminum acetylides even to transoid enones. The acetylenic aluminum reagent is prepared according to Fried s procedure (4, 144) from a lithium acetylide and dimethylaluminum chloride. In all cases only 1,4-addition is observed. -Examples ... 

Kwan and Battiste have employed the Peterson protocol to synthesize vinylsilanes 39/40 in a one-pot process. The procedure involved the addition of trimethylsilylmethyl lithium to non-enolizable aromatic ketones followed by addition of diethylaluminium chloride, then water. The tabulated examples illustrate the rare use of organoaluminum reagents to promote elimination. Good chemo- and stereoselectivity was observed. 

Nitrones also works as precursors of amines via nucleophilic addition of organoaluminum species. Desvergnes and Py et al. described the effective addition of dimethylalkynylaluminum reagents to carbohydrate-derived chiral nitrones 32 (Scheme 29) [51]. This strategy enables diastereoselective access to optically active N-hydroxy pyridine derivatives 33 having four stereogenic centers. 

Guo L-N, Gao H, Mayer P, Knochel P (2010) Preparation of organoaluminum reagents from propargylic bromides and aluminum activated by PbCl2 and their regio- and dlastereoselective addition to carbonyl derivatives. Chem Eur J 16 9829-9834... 

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