Unique reactivity of a 1,4-dilithiobutadiene with methyl iodide

Tetrahedron Letters

Volumn 47, Issue 20, 2006, Pages 3427-3430

  Hudrlik, Paul F ^a   Dai, Donghua ^a   Hudrlik, Anne M ^a  

^a HOWARD UNIVERSITY   (United States)

Author keywords

Alkenyllithium; Dilithiobutadiene; Metal halogen exchange; Methyl iodide

Indexed keywords

1,3 BUTADIENE DERIVATIVE; ALKENE DERIVATIVE; HALOGEN; IODINE DERIVATIVE; METAL; METHYL IODIDE;

ARTICLE; CHEMICAL REACTION;

EID: 33646060716     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.tetlet.2006.03.067     Document Type: Article

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11. 20 was prepared by treatment of diiodide 4 in THF with t-BuLi (4 mol per mol of 4) followed by hydrolysis.
12. 1H NMR: 6:10:9 = 76:15:9. No evidence for the monomethyldiene 12 was obtained.
13. 1H NMR; a small peak at the retention time of monoiododiene 9 (3%) was also observed by GC, but negligible amount (<0.2%) at that of the monomethyldiene 12.
14. Small GC peaks corresponding to monoiododiene 9 (3%) and methyl iododiene 6 (5%) were also visible, with no significant peaks (>0.2%) for 10 or 12. In a separate experiment, GC analysis of an aliquot (before addition of MeI) worked up with water showed considerable amounts of monoiododiene 9 as well as diiodide 4, with a smaller amount of diene 10 (GC ratio 9:4:10 = 21:48:15). Excess MeI was added to the reaction mixture, and after workup, GC analysis showed diiodide 4 to be the major product (72% of GC area). Small peaks corresponding in retention time to 9 (4%), methyl iododiene 6 (7.5%) and monomethyldiene 12 (1%) were also visible.
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