Palladium-catalyzed negishi cross-coupling reactions of unactivated alkyl iodides, bromides, chlorides, and tosylates

Journal of the American Chemical Society

Volumn 125, Issue 41, 2003, Pages 12527-12530

  Zhou, Jianrong ^a   Fu, Gregory C ^a  

^a MASSACHUSETTS INSTITUTE OF TECHNOLOGY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

FUNCTIONAL GROUPS;

BROMINE COMPOUNDS; CHLORINE COMPOUNDS; IODINE COMPOUNDS; PALLADIUM;

CATALYST ACTIVITY;

BROMINE DERIVATIVE; CHLORINE DERIVATIVE; IODINE DERIVATIVE; PALLADIUM; TOLUENESULFONIC ACID DERIVATIVE;

ARTICLE; CATALYSIS; CHEMICAL ANALYSIS; CHEMICAL REACTION; CHEMICAL STRUCTURE; PARAMETER; REACTION ANALYSIS; TEMPERATURE DEPENDENCE;

CATALYSIS; HYDROCARBONS, HALOGENATED; ORGANOMETALLIC COMPOUNDS; PALLADIUM; TOSYL COMPOUNDS; ZINC;

EID: 0141988949     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0363258     Document Type: Article

References (41)

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3. (c) Handbook of Organopalladium Chemistry for Organic Synthesis; Negishi, E.-i., Ed.; Wiley-Interscience: New York, 2002.
4. For an overview of the difficulty of achieving coupling reactions of alkyl electrophiles, see: Cárdenas, D. J. Angew. Chem., Int. Ed. 2003, 42, 384-387; Cárdenas, D. J. Angew. Chem., Int. Ed. 1999, 38, 3018-3020. See also: Luh, T.-Y.; Leung, M-k; Wong, K.-T. Chem. Rev. 2000, 100, 3187-3204.
5. For an overview of the difficulty of achieving coupling reactions of alkyl electrophiles, see: Cárdenas, D. J. Angew. Chem., Int. Ed. 2003, 42, 384-387; Cárdenas, D. J. Angew. Chem., Int. Ed. 1999, 38, 3018-3020. See also: Luh, T.-Y.; Leung, M-k; Wong, K.-T. Chem. Rev. 2000, 100, 3187-3204.
6. For an overview of the difficulty of achieving coupling reactions of alkyl electrophiles, see: Cárdenas, D. J. Angew. Chem., Int. Ed. 2003, 42, 384-387; Cárdenas, D. J. Angew. Chem., Int. Ed. 1999, 38, 3018-3020. See also: Luh, T.-Y.; Leung, M-k; Wong, K.-T. Chem. Rev. 2000, 100, 3187-3204.
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8. (a) Bromides: Netherton, M. R.; Dai, C.; Neuschütz, K.; Fu, G. C. J. Am. Chem. Soc. 2001, 123, 10099-10100.
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23. For reviews of Negishi cross-couplings of organozinc reagents, see ref 1.
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27. 3-catalyzed Negishi cross-coupling of 1-chlorohexane with PhZnBr that proceeds in 41% yield: Reference 7.
28. (a) For reviews and leading references, see: Rieke, R. D.; Hanson, M. V. In Organozinc Reagents, A Practical Approach; Knochel, P., Jones, P., Eds.; Oxford: New York, 1999; pp 23-36. Rieke, R. D.; Hanson, M. V. Tetrahedron 1997, 53, 1925-1956.
29. (a) For reviews and leading references, see: Rieke, R. D.; Hanson, M. V. In Organozinc Reagents, A Practical Approach; Knochel, P., Jones, P., Eds.; Oxford: New York, 1999; pp 23-36. Rieke, R. D.; Hanson, M. V. Tetrahedron 1997, 53, 1925-1956.
30. (b) For a recent report, see: Hou, S. Org. Lett. 2003, 5, 423-425.
31. For a report of enhanced reactivity of an alkylzinc reagent in the presence of NMI, see: Inoue, S.; Yokoo, Y. J. Organomet. Chem. 1972, 39, 11-16.
32. 3-based catalyst.
33. For the less-effective ligands, the major identifiable side products are the alkyl chloride (organozinc reagents from Aldrich can contain 2-3 wt % chloride) and/or the alkane (from reduction of the alkyl bromide).
34. 2Zn (0.65 or 1.3 equiv) furnishes an ∼68% yield (by GC versus an internal standard) of the desired cross-coupling product.
35. (b) When a secondary alkylzinc reagent is employed as the coupling partner, isomerization is observed (e.g., for the reaction of 1-bromononane with i-PrZnBr, we obtain an ∼60% yield of n-dodecane). Isomerization is common for Negishi cross-couplings of aryl halides with branched alkylzinc reagents, when catalyzed by Pd/monodentate phosphine) complexes. For example, see: Hayashi, T.; Konishi, M.; Kobori, Y.; Kumada, M.: Higuchi, T.; Hirotsu, K. J. Am. Chem. Soc. 1984, 106, 158-163.
36. Notes: (a) Negishi cross-couplings of secondary alkyl halides/tosylates are inefficient under these conditions.
37. (b) Because organozinc reagents (e.g., n-BuZnBr) from Aldrich can contain 2-3 wt % chloride, some transhalogenation (RBr→RC1 occurs under the cross-coupling conditions. As a consequence, selective mono-functionalization of 1-bromo-6-chlorohexane (Table 4, entry 7) cannot be achieved with these reagents.
38. For previous applications of this general strategy, see: (a) Netherton, M. R.; Fu, G. C. Org. Lett. 2001, 3, 4295-4298.
39. (b) References 9 and 10.
40. Gao, Y.; Harada, K.; Hata, T.; Urabe, H.; Sato, F. J. Org. Chem. 1995, 60, 290-291.
41. 3 is effective for coupling reactions of aryl bromides (PhBr + BuZnBr: 85% yield; PhBr + PhZnBr: 70% yield), iodides (PhI + BuZnBr: 87% yield; PhI + PhZnBr: 72% yield), and triflates (PhOTf + BuZnBr: 88% yield; PhOTf + PhZnBr: 76% yield). Aryl chlorides react very slowly.