Catalytic Asymmetric Iodocyclization of N-Tosyl Alkenamides using Aminoiminophenoxy Copper Carboxylate: A Concise Synthesis of Chiral 8-Oxa-6-Azabicyclo[3.2.1]octanes
Corresponding Author
Prof. Dr. Takayoshi Arai
Molecular Chirality Research Center, Synthetic Organic Chemistry, Department of Chemistry, Graduate School of Science, Chiba University, 1-33 Yayoi, Inage, Chiba 263-8522 (Japan)
Molecular Chirality Research Center, Synthetic Organic Chemistry, Department of Chemistry, Graduate School of Science, Chiba University, 1-33 Yayoi, Inage, Chiba 263-8522 (Japan)Search for more papers by this authorOhji Watanabe
Molecular Chirality Research Center, Synthetic Organic Chemistry, Department of Chemistry, Graduate School of Science, Chiba University, 1-33 Yayoi, Inage, Chiba 263-8522 (Japan)
Search for more papers by this authorShinnosuke Yabe
Department of Chemistry, Rikkyo University, 3-34-1 Nishi-Ikebukuro, Toshima-ku, Tokyo 171-8501 (Japan)
Search for more papers by this authorProf. Dr. Masahiro Yamanaka
Department of Chemistry, Rikkyo University, 3-34-1 Nishi-Ikebukuro, Toshima-ku, Tokyo 171-8501 (Japan)
Search for more papers by this authorCorresponding Author
Prof. Dr. Takayoshi Arai
Molecular Chirality Research Center, Synthetic Organic Chemistry, Department of Chemistry, Graduate School of Science, Chiba University, 1-33 Yayoi, Inage, Chiba 263-8522 (Japan)
Molecular Chirality Research Center, Synthetic Organic Chemistry, Department of Chemistry, Graduate School of Science, Chiba University, 1-33 Yayoi, Inage, Chiba 263-8522 (Japan)Search for more papers by this authorOhji Watanabe
Molecular Chirality Research Center, Synthetic Organic Chemistry, Department of Chemistry, Graduate School of Science, Chiba University, 1-33 Yayoi, Inage, Chiba 263-8522 (Japan)
Search for more papers by this authorShinnosuke Yabe
Department of Chemistry, Rikkyo University, 3-34-1 Nishi-Ikebukuro, Toshima-ku, Tokyo 171-8501 (Japan)
Search for more papers by this authorProf. Dr. Masahiro Yamanaka
Department of Chemistry, Rikkyo University, 3-34-1 Nishi-Ikebukuro, Toshima-ku, Tokyo 171-8501 (Japan)
Search for more papers by this authorAbstract
A newly developed aminoiminophenoxy copper carboxylate (L7-Cu-OAc)-catalyzed asymmetric iodocyclization of N-Tosyl alkenamides gave O-cyclized products in good yields with high enantioselectivity. From the O-cyclized products, a skeletal transformation was succeeded in the synthesis of biologically important chiral 8-oxa-6-azabicyclo[3.2.1]octanes. DFT calculations suggested that the acetoxy anion of the [L7-Cu-OAc] acts as a base to generate the anion of N-Tosyl alkenamide substrates. The exchanged acetic acid reconstructs a new hydrogen-bonding network between the catalyst and the substrates to accomplish the highly efficient asymmetric O-iodocyclization of N-Tosyl alkenamides.
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