From Osmium Hydrido Vinylidene to Osmacycles: The Key Role of Osmabutadiene Intermediates

Authors

  • Qianyi Zhao,

    1. State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005 (P. R. China), Fax: (+86) 592-2186628
    Search for more papers by this author
  • Dr. Xiao-Yu Cao,

    Corresponding author
    1. State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005 (P. R. China), Fax: (+86) 592-2186628
    • State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005 (P. R. China), Fax: (+86) 592-2186628

    Search for more papers by this author
  • Prof. Dr. Ting Bin Wen,

    1. State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005 (P. R. China), Fax: (+86) 592-2186628
    Search for more papers by this author
  • Prof. Dr. Haiping Xia

    Corresponding author
    1. State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005 (P. R. China), Fax: (+86) 592-2186628
    • State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005 (P. R. China), Fax: (+86) 592-2186628

    Search for more papers by this author

Abstract

Osmium hydrido vinylidene 1 shows diverse cyclization reactivity with activated terminal alkynes. Treatment of 1 with HC[TRIPLE BOND]CCOR′ (R′=OEt and Me) gave osmafurans 3 a and 3 b via osmium alkenyl/vinylidenes 2 a and 2 b. In addition, 1 reacted with HC[TRIPLE BOND]CCH(OH)C[TRIPLE BOND]CH to yield osmabenzene 4, in which the alkynol acted as a C5 fragment to cyclize with 1. Mechanistic analysis indicates that these reactions and the previous formal [3+3] cycloadditions between 1 and HC[TRIPLE BOND]CCH(OH)R (R=Ph, Et, and vinyl) or HC[TRIPLE BOND]CCH(OEt)2 all go through similar osmabutadiene intermediates. Subsequently, the intermediates either took a “coordination and cyclization” process or a “carbon–carbon coupling” path to cyclization, depending on the coordination ability of substituents on the terminal alkenyl carbon atom.

Abstract

Thumbnail image of

Ancillary