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Volumn 129, Issue 13, 2007, Pages 4099-4104

Copper-catalyzed anti-hydrophosphination reaction of 1-alkynylphosphines with diphenylphosphine providing (Z)-1,2-diphosphino-1-alkenes

Author keywords

[No Author keywords available]

Indexed keywords

AROMATIC COMPOUNDS; CATALYSIS; ISOMERIZATION; REACTION KINETICS; SULFIDE MINERALS; SYNTHESIS (CHEMICAL);

EID: 34247138826     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja070048d     Document Type: Article
Times cited : (110)

References (57)
  • 5
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    • de Meijere, A, Diederich, F, Eds, Wiley-VCH
    • (e) Metal-Catalyzed Cross-Coupling Reactions; de Meijere, A., Diederich, F., Eds.; Wiley-VCH, 2004.
    • (2004) Metal-Catalyzed Cross-Coupling Reactions
  • 10
    • 34247164004 scopus 로고    scopus 로고
    • Togni, A, Grützmacher, H, Eds, Wiley-VCH: Weinheim, Germany, Chapter 5
    • (a) Wicht, D. K.; Glueck, D. S. In Catalytic Heterofunctionalization; Togni, A., Grützmacher, H., Eds.; Wiley-VCH: Weinheim, Germany, 2001; Chapter 5.
    • (2001) Catalytic Heterofunctionalization
    • Wicht, D.K.1    Glueck, D.S.2
  • 22
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    • The only exception: Bookham, J. L.; Smithies, D. M. J. Organomet. Chem. 1999, 577, 305-315.
    • The only exception: Bookham, J. L.; Smithies, D. M. J. Organomet. Chem. 1999, 577, 305-315.
  • 25
    • 0032542394 scopus 로고    scopus 로고
    • Examples of the methods for the synthesis of (Z)-1,2-diphosphino- 1-alkenes, which lack generality: (a) Banert, K.; Fendel, W.; Schlott, J. Angew. Chem., Int. Ed. 1998, 37, 3289-3292.
    • Examples of the methods for the synthesis of (Z)-1,2-diphosphino- 1-alkenes, which lack generality: (a) Banert, K.; Fendel, W.; Schlott, J. Angew. Chem., Int. Ed. 1998, 37, 3289-3292.
  • 29
    • 15044353090 scopus 로고    scopus 로고
    • A number of hydrophosphonylations, the additions of pentavalent hydrophosphorous compounds, aiming at the synthesis of bidentate ligands, were reported: (a) Stockland, R. A., Jr.; Taylor, R. I.; Thompson, L. E.; Patel, P. B. Org. Lett. 2005, 7, 851-853 and references therein.
    • A number of hydrophosphonylations, the additions of pentavalent hydrophosphorous compounds, aiming at the synthesis of bidentate ligands, were reported: (a) Stockland, R. A., Jr.; Taylor, R. I.; Thompson, L. E.; Patel, P. B. Org. Lett. 2005, 7, 851-853 and references therein.
  • 31
    • 34247160377 scopus 로고    scopus 로고
    • Ref 4f
    • (c) Ref 4f.
  • 37
    • 29444434713 scopus 로고    scopus 로고
    • We have observed a copper-mediated phosphination reaction of trialkyl(dibromomethyl)silanes: (c) Kondo, J, Someya, H, Kinoshita, H, Shinokubo, H, Yorimitsu, H, Oshima, K. Org. Lett. 2005, 7, 5713-5715
    • We have observed a copper-mediated phosphination reaction of trialkyl(dibromomethyl)silanes: (c) Kondo, J.; Someya, H.; Kinoshita, H.; Shinokubo, H.; Yorimitsu, H.; Oshima, K. Org. Lett. 2005, 7, 5713-5715.
  • 43
    • 34247175296 scopus 로고    scopus 로고
    • 2] would be labile and mat many sorts of copper-phosphide species might be formed upon the addition of cesium carbonate.
    • 2] would be labile and mat many sorts of copper-phosphide species might be formed upon the addition of cesium carbonate.
  • 44
    • 34247156143 scopus 로고    scopus 로고
    • There can be an interaction between the copper and the acetylenic part of 5.
    • There can be an interaction between the copper and the acetylenic part of 5.
  • 45
    • 34247170808 scopus 로고    scopus 로고
    • 31P NMR spectrum of 1a in DMF. The addition of a stoichiometric amount of CuI to the DMF solution furnished a clear homogeneous solution, which exhibited a broad and highly splitting signal at the same chemical shift. The dissolution of CuI indicates the formation of the complex [CuI·1a]. The NMR experiments suggest that the complex would not be robust.
    • 31P NMR spectrum of 1a in DMF. The addition of a stoichiometric amount of CuI to the DMF solution furnished a clear homogeneous solution, which exhibited a broad and highly splitting signal at the same chemical shift. The dissolution of CuI indicates the formation of the complex [CuI·1a]. The NMR experiments suggest that the complex would not be robust.
  • 53
    • 34247167536 scopus 로고    scopus 로고
    • The radical desulfidation of 15 with TTMSS (1.2 equiv to 15) was also successful. However, after several attempts, separation of 15 and silicon-containing residue proved to be problematic in our hands. Small amounts of the corresponding monooxides of 15 were generated during careful chromatographic purification on silica gel for isolation of 15. Purification using a solid phase technique (see the Supporting Information) resulted in unsatisfactory separation of 15 and the silicon-containing residue. We expect that, if the TTMSS-mediated reduction and purification of 15 were performed in a glovebox filled with inert gas, one could isolate 15 in excellent yield
    • The radical desulfidation of 15 with TTMSS (1.2 equiv to 15) was also successful. However, after several attempts, separation of 15 and silicon-containing residue proved to be problematic in our hands. Small amounts of the corresponding monooxides of 15 were generated during careful chromatographic purification on silica gel for isolation of 15. Purification using a solid phase technique (see the Supporting Information) resulted in unsatisfactory separation of 15 and the silicon-containing residue. We expect that, if the TTMSS-mediated reduction and purification of 15 were performed in a glovebox filled with inert gas, one could isolate 15 in excellent yield.


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