Alkali Metal Adducts of an Iron(0) Complex and Their Synergistic FLP-Type Activation of Aliphatic C–X Bonds

The formation of alkali metal adducts of N-benzylidene aniline in several inert solvents is studied by protonolysis of the adducts and analysis of the reaction products, the diastereomeric N,N′,1,2-tetraphenylethylenediamines. With sodium and potassium metal in polar solvents, the product is predominantly the dd,ll diamine. With lithium metal or with solvents of low polarity, the product contains approximately equal quantities of the two diastereomers.It is demonstrated that the initially formed diastereomeric mixture generally contains appreciable amounts of the meso isomer. In polar solvents with sodium, isomerization to the stable dd,ll diastereomer occurs. However, with lithium or with sodium in nonpolar solvents, the isomerization does not occur. The reasons for the preponderance of the dd,ll-disodio compound in the equilibrating systems are discussed.

Download Full-text

MALDI TOF Post-Source Decay Investigation of Alkali Metal Adducts of Apolar Polypentylresorcinol Dendrimers

Macromolecules ◽

10.1021/ma034728m ◽

2003 ◽

Vol 36 (22) ◽

pp. 8297-8303 ◽

Cited By ~ 15

Author(s):

Hendrik Neubert ◽

Kevin A. Knights ◽

Yolanda R. de Miguel ◽

David A. Cowan

Keyword(s):

Alkali Metal ◽

Post Source Decay ◽

Maldi Tof ◽

Metal Adducts

Download Full-text

Phosphorobenzene-Alkali Metal Adducts

The Journal of Organic Chemistry ◽

10.1021/jo01355a009 ◽

1957 ◽

Vol 22 (4) ◽

pp. 385-387 ◽

Cited By ~ 25

Author(s):

J. W. B. REESOR ◽

GEORGE F WRIGHT

Keyword(s):

Alkali Metal ◽

Metal Adducts

Download Full-text

Alkylation of the alkali metal adducts of benzophenone anil

Tetrahedron Letters ◽

10.1016/s0040-4039(01)88128-4 ◽

1969 ◽

Vol 10 (27) ◽

pp. 2227-2230 ◽

Cited By ~ 2

Author(s):

Richard Turle ◽

James G. Smith

Keyword(s):

Alkali Metal ◽

Metal Adducts

Download Full-text

The alkali metal adducts of acetophenone anil

Canadian Journal of Chemistry ◽

10.1139/v67-287 ◽

1967 ◽

Vol 45 (15) ◽

pp. 1785-1794 ◽

Cited By ~ 4

Author(s):

James G. Smith ◽

C. Doreen Veach

Keyword(s):

Nitrogen Atom ◽

Alkali Metal ◽

Alkyl Halide ◽

Chemical Behavior ◽

Methyl Group ◽

Metal Adducts ◽

Hydrolysis Of

Contrary to previous reports, the reaction between acetophenone anil and sodium produces a product containing one atom of sodium per mole of anil. In its chemical behavior, this adduct appears to consist of equal parts of N-sodio-N,1-diphenylethylamine and α-sodioacetophenone anil. Thus, treatment with an alkyl halide results in products derived by alkylation of the nitrogen atom of N,1-diphenylethylamine and alkylation of the methyl group of acetophenone anil.The behavior of acetophenone anil towards lithium is quite different and very solvent dependent. In ether, hydrolysis of the lithium adduct produces a dimer, N,N′,2,3-tetraphenyl-2,3-butanediamine. In tetrahydrofuran with either lithium or potassium, another dimer, N,N′,l,4-tetraphenyl-1,4-butanediamine, is formed by dimerization through the methyl group of acetophenone anil. The structure of this new dimer was established by separation of the diastereomers and cyclization of each to the corresponding 1,2,5-triphenylpyrrolidine.The mechanism by which these products are formed is discussed.

Download Full-text