Suzuki cross-couplings of alkyl tosylates that possess β hydrogen atoms: Synthetic and mechanistic studies

Angewandte Chemie - International Edition

Volumn 41, Issue 20, 2002, Pages 3910-3912

  Netherton, Matthew R ^a   Fu, Gregory C ^a  

^a MASSACHUSETTS INSTITUTE OF TECHNOLOGY   (United States)

Author keywords

Alkyl tosylates; C C coupling; Ligand effects; Palladium; Suzuki reaction

Indexed keywords

9 BORABICYCLONONANE; 9-BORABICYCLONONANE; BORON DERIVATIVE; FUSED HETEROCYCLIC RINGS; HALOGENATED HYDROCARBON; PALLADIUM; SULFONIC ACID DERIVATIVE; DEUTERIUM; HYDROGEN; TOLUENESULFONIC ACID DERIVATIVE;

ARTICLE; CATALYSIS; CHEMISTRY; CHEMICAL REACTION; MEASUREMENT; OXIDATION; REACTION ANALYSIS; STRUCTURE ANALYSIS; SYNTHESIS;

BICYCLO COMPOUNDS, HETEROCYCLIC; BORON COMPOUNDS; CATALYSIS; HYDROCARBONS, HALOGENATED; PALLADIUM; SULFONIC ACIDS;

MOLECULAR STRUCTURE; PHOSPHORUS COMPOUNDS;

LIGANDS;

HYDROGEN;

EID: 0037131506     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/1521-3773(20021018)41:20<3910::AID-ANIE3910>3.0.CO;2-W     Document Type: Article

References (30)

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6. Palladium-catalyzed Suzuki couplings: a) Alkyl iodides: T. Ishiyama, S. Abe, N. Miyaura, A. Suzuki, Chem. Lett. 1992, 691-694; b) alkyl bromides: M. R. Netherton, C. Dai, K. Neuschütz, G. C. Fu, J. Am. Chem. Soc. 2001, 123, 10099-10100; c) alkyl chlorides: J. H. Kirchhoff, C. Dai, G. C. Fu, Angew. Chem. 2002, 114, 2025-2027; Angew. Chem. Int. Ed. 2002, 41, 1945-1947.
7. Palladium-catalyzed Suzuki couplings: a) Alkyl iodides: T. Ishiyama, S. Abe, N. Miyaura, A. Suzuki, Chem. Lett. 1992, 691-694; b) alkyl bromides: M. R. Netherton, C. Dai, K. Neuschütz, G. C. Fu, J. Am. Chem. Soc. 2001, 123, 10099-10100; c) alkyl chlorides: J. H. Kirchhoff, C. Dai, G. C. Fu, Angew. Chem. 2002, 114, 2025-2027; Angew. Chem. Int. Ed. 2002, 41, 1945-1947.
8. Palladium-catalyzed Suzuki couplings: a) Alkyl iodides: T. Ishiyama, S. Abe, N. Miyaura, A. Suzuki, Chem. Lett. 1992, 691-694; b) alkyl bromides: M. R. Netherton, C. Dai, K. Neuschütz, G. C. Fu, J. Am. Chem. Soc. 2001, 123, 10099-10100; c) alkyl chlorides: J. H. Kirchhoff, C. Dai, G. C. Fu, Angew. Chem. 2002, 114, 2025-2027; Angew. Chem. Int. Ed. 2002, 41, 1945-1947.
9. Palladium-catalyzed Suzuki couplings: a) Alkyl iodides: T. Ishiyama, S. Abe, N. Miyaura, A. Suzuki, Chem. Lett. 1992, 691-694; b) alkyl bromides: M. R. Netherton, C. Dai, K. Neuschütz, G. C. Fu, J. Am. Chem. Soc. 2001, 123, 10099-10100; c) alkyl chlorides: J. H. Kirchhoff, C. Dai, G. C. Fu, Angew. Chem. 2002, 114, 2025-2027; Angew. Chem. Int. Ed. 2002, 41, 1945-1947.
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14. For the reactions outlined in Scheme 2, we observe an 11-36% yield of 1-dodecene (resulting from β-hydride elimination), with the balance of the material being unreacted tosylate or side products.
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19. 3] was not;
20. 2O, and KOtBu led to decreased yields.
21. 3, no coupling was observed.
22. 2Me-based catalyst system represents significant progress, important challenges remain, including the coupling of more hindered reaction partners, as well as the coupling of boronic acids, neither of which proceed in appreciable yield under the conditions described in Table 1.
23. M. R. Netherton, G. C. Fu, Org. Lett. 2001, 3, 4295-4298.
24. 4 will be commercially available from Strem Chemicals (Dr. Mike Strem. personal communication).
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29. 2H(OTs)].
30. We have confirmed these results by investigating the corresponding reaction of the diastereomer of tosylate 1.