Stereoselective Synthesis of Tetrahydrofurans via the Palladium-Catalyzed Reaction of Aryl Bromides with γ-Hydroxy Alkenes: Evidence for an Unusual Intramolecular Olefin Insertion into a Pd(Ar)(OR) Intermediate

Journal of the American Chemical Society

Volumn 126, Issue 6, 2004, Pages 1620-1621

  Wolfe, John P ^a   Rossi, Michael A ^a  

^a UNIVERSITY OF MICHIGAN   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKENE; BROMIDE; PALLADIUM; POLYCYCLIC AROMATIC HYDROCARBON DERIVATIVE; TETRAHYDROFURAN DERIVATIVE;

ARTICLE; CATALYSIS; REACTION ANALYSIS; STEREOCHEMISTRY; SYNTHESIS;

EID: 1242269280     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0394838     Document Type: Article

References (30)

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15. Trost has noted the formation of a tetrahydrofuran side product in the Heck arylation of an enyne bearing a secondary OH group and suggested a mechanism of intermolecular carbopalladation to account for its formation. See: Trost, B. M.; Pfrengle, W.; Urabe, H.; Dumas, J. J. Am. Chem. Soc. 1992, 114, 1923-1924.
16. 3N) did not afford the desired products.
17. DPE-Phos = bis(2-diphenylphosphinophenyl)ether.
18. See Supporting Information for details of optimization studies.
19. Reactions of electron-deficient aryl bromides afforded low yields of desired products; competing O-arylation of the substrate was observed. Reactions of ary1 iodides were slow and gave large amounts of arene and ketone side products; only small amounts of the desired tetrahydrofurans were formed.
20. Stereochemistry of tetrahydrofuran products was established by nOe experiments or by comparison of NMR spectra to related compounds of known configuration. See Supporting Information for complete details.
21. 1H NMR and/or GC analysis of crude reaction mixtures.
22. The stereoselective conversion of 6 to 7 provides further evidence against this mechanism. We thank a reviewer for this suggestion.
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