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Volumn 74, Issue 1, 2009, Pages 135-143

Studies on the 1,2-migrations in Pd-catalyzed negishi couplings with JosiPhos ligands

Author keywords

[No Author keywords available]

Indexed keywords

ALKENYL; CATALYTIC ACTIVITIES; CHEMICAL EQUATIONS; COUPLING REACTIONS; CROSS COUPLINGS; FERROCENYL; NEGISHI COUPLINGS; NUCLEOPHILICITY; ORGANOMETALLIC REAGENTS; PALLADIUM CATALYSTS; PALLADIUM COMPLEXES; STRUCTURAL FEATURES; TRANSMETALATION; VINYL TOSYLATES;

EID: 58149299823     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo801824e     Document Type: Article
Times cited : (46)

References (76)
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    • and references cited therein. For examples on the 1,3- to the 1,6-migrations, see
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    • For a recent review on 1,4-migrations, see
    • For a recent review on 1,4-migrations, see: Ma, S.; Gu, Z. Angew. Chem., Int. Ed. 2005, 44, 7512.
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    • For some recent examples, see: a
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    • For some recent reviews on the Kumada-Corriu coupling, see: a
    • For some recent reviews on the Kumada-Corriu coupling, see: (a) Corbet, J.-P.; Mignani, G. Chem. Rev. 2006, 106, 2651.
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    • For some recent reviews on the Mizoroki-Heck reaction, see: a
    • For some recent reviews on the Mizoroki-Heck reaction, see: (a) Heck, R. F. Synlett 2006, 2855.
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    • Brase, S.; de Meijere, A. In Metal-Catalyzed Cross-Coupling Reactions; DiederichF., Stang, P. J., Eds.; Wiley-VCH: New York, 1998; Chapter 3.
    • (f) Brase, S.; de Meijere, A. In Metal-Catalyzed Cross-Coupling Reactions; DiederichF., Stang, P. J., Eds.; Wiley-VCH: New York, 1998; Chapter 3.
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    • Link, J. T.; Overman, L. E. In Metal-Catalyzed Cross-Coupling Reactions; DiederichF., Stang, P. J., Eds.; Wiley-VCH: New York, 1998; Chapter 6.
    • (g) Link, J. T.; Overman, L. E. In Metal-Catalyzed Cross-Coupling Reactions; DiederichF., Stang, P. J., Eds.; Wiley-VCH: New York, 1998; Chapter 6.
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    • For the use of this ligand in coupling reactions, see: a
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    • For reviews and general literature on the Negishi reaction, see: a, Knochel, P, Jones, P, Eds, Oxford: New York
    • For reviews and general literature on the Negishi reaction, see: (a) Organozinc Reagents, A Practical Approach; Knochel, P., Jones, P., Eds.; Oxford: New York, 1999.
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    • Efforts were made to couple either p-tolyl or p-methoxyphenyl trimethylstannane with 1-cyclohexyl vinyl tosylate, with the presence of lithium chloride, with the expectation that cross-coupling with less reactive organotin compounds would lead to higher preferences for the 1,2-disubstituted alkene compared to that observed for the corresponding zinc reagents. Nevertheless, the reaction conditions employed for the described Negishi couplings were not effective for promoting cross-couplings with the aryltin compounds. Further work is ongoing to identify suitable conditions which may promote migrations in the Kosugi-Migita-Stille couplings.
    • Efforts were made to couple either p-tolyl or p-methoxyphenyl trimethylstannane with 1-cyclohexyl vinyl tosylate, with the presence of lithium chloride, with the expectation that cross-coupling with less reactive organotin compounds would lead to higher preferences for the 1,2-disubstituted alkene compared to that observed for the corresponding zinc reagents. Nevertheless, the reaction conditions employed for the described Negishi couplings were not effective for promoting cross-couplings with the aryltin compounds. Further work is ongoing to identify suitable conditions which may promote migrations in the Kosugi-Migita-Stille couplings.
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    • For some applications of JosiPhos ligands in Pd-catalyzed C-heteroatom bond forming reactions, see: a
    • For some applications of JosiPhos ligands in Pd-catalyzed C-heteroatom bond forming reactions, see: (a) Shen, Q.; Ogata, T.; Hartwig, J. F. J. Am. Chem. Soc. 2008, 130, 6586.
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    • It should be noted that DPPF has also been reported to be a ligand with a capacity to bind Pd(II) either with one phosphorus atom or with two phosphorus atoms as demonstrated for example by Cabri et al. Cabri, W, Candiani, I, DeBernardinis, S, Francalanci, F, Penco, S, Santo, R. J. Org. Chem. 1991, 56, 5796. Nevertheless, DPPF does not promote the 1,2-migration in these Negishi reactions, suggesting that certain JosiPhos ligands may possess a greater tendency for monodentate character than DPPF
    • It should be noted that DPPF has also been reported to be a ligand with a capacity to bind Pd(II) either with one phosphorus atom or with two phosphorus atoms as demonstrated for example by Cabri et al. Cabri, W.; Candiani, I.; DeBernardinis, S.; Francalanci, F.; Penco, S.; Santo, R. J. Org. Chem. 1991, 56, 5796. Nevertheless, DPPF does not promote the 1,2-migration in these Negishi reactions, suggesting that certain JosiPhos ligands may possess a greater tendency for monodentate character than DPPF.
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    • For a few papers on the topic of the Mizoroki-Heck reaction with electron-rich alkenes, see: a
    • For a few papers on the topic of the Mizoroki-Heck reaction with electron-rich alkenes, see: (a) Ozawa, F.; Kubo, A.; Hayashi, T. J. Am. Chem. Soc. 1991, 113, 1417.
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    • There is additionally another possible mechanism involving base-promoted elimination of the alkenyl tosylate or phosphate that could also be invoked followed by addition of the organometallic reagent. However, in this scenario, it would be expected that greater levels of the 1,2-disubstituted alkene would be formed employing the more nucleophilic and most likely also more basic organometallic reagents. Yet, the opposite trend is observed in many of these coupling reactions
    • There is additionally another possible mechanism involving base-promoted elimination of the alkenyl tosylate or phosphate that could also be invoked followed by addition of the organometallic reagent. However, in this scenario, it would be expected that greater levels of the 1,2-disubstituted alkene would be formed employing the more nucleophilic and most likely also more basic organometallic reagents. Yet, the opposite trend is observed in many of these coupling reactions.
  • 76
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    • We thank the reviewers for helpful comments and suggestions to this work
    • We thank the reviewers for helpful comments and suggestions to this work.


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