Intramolecular heck reactions of unactivated alkyl halides

Journal of the American Chemical Society

Volumn 129, Issue 37, 2007, Pages 11340-11341

  Firmansjah, Luke ^a   Fu, Gregory C ^a  

^a MASSACHUSETTS INSTITUTE OF TECHNOLOGY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKYL GROUP; HALIDE;

ARTICLE; ARYLATION; BIOTRANSFORMATION; CATALYSIS; CYCLIZATION; DIASTEREOISOMER; ELIMINATION REACTION; HECK REACTION; REACTION ANALYSIS; STEREOSPECIFICITY;

ALKYLATION; CATALYSIS; CYCLIZATION; HYDROCARBONS, BROMINATED; HYDROCARBONS, CHLORINATED; MOLECULAR STRUCTURE; PALLADIUM;

EID: 35048894985     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja075245r     Document Type: Article

References (30)

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2. For examples of palladium-catalyzed Heck reactions of activated alkyl halides that lack β hydrogens, see: (a) benzylic electrophiles: Heck, R. F.; Nolley, J. P., Jr. J. Org. Chem. 1972, 37, 2320-2322.
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18. For the sake of simplicity, this discussion is based on irreversible elementary steps.
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25. For entries 2, 3, 7, 8, 9, and 11 of Table 1, unreacted starting material accounts for the majority of the mass balance.
26. Under our standard conditions, the following alkyl-Heck cyclizations were not successful (<30% yield): (1) reaction of a disubstituted olefin; (2) formation of a six-membered ring; and, (3) cyclization of an unactivated secondary alkyl bromide.
27. Under the conditions described for alkyl-Heck cyclizations of alkyl bromides (Table 2), the reaction of an alkyl chloride (entry 1 of Table 3) proceeds in <5% yield.
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30. N2 pathway, see: Netherton, M. R.; Fu, G. C. Angew. Chem., Int. Ed. 2002, 41, 3910-3912.