Hydride abstraction of tricarbonylln'vl-tphenylthio)-t ,3-cycIobexadiene]iron(O) complex 2 with Ph 3C+PF6 -regiospecifically provided the title compound 3 in excellent yield. Cationic complex 3 could react with a variety of nucleophiles in good yield. Hard nucleophiles prefer to attack at the C-I position, whereas soft and hindered nucleophiles favor attack at the C-S position. Some synthetic applications were also studied, S-dienylium complex 3 in excellent yield (Eq. 0, which was characterized by 'n and BC NMR spectroscopy and analytical methods.The reactions of 3 with a rangeof nucleophiles (Eq, 2) are shown in Table 1. It can be seen that heteroatom nucleophiles (entries 1-3) reacted smoothly with 3 at C-S to give the T)4-iron complexes 4. The cyanide anion (entry 4), however, gave a mixture of C-5 and C-1 addition products 4d and 5d, respectively. The regiochemistry of 4d and 5d have been assigned based on the III NMR and DEPT experiments. Compound 4d has two protons at 0 6.13 (d, J =4.2 Hz, H-2) and 0 5.43 (dd, J =4.2, 6.4 Hz, H-3), and one quarternary carbon at 0 72.8 (C-l), whereas compound 5d has two protons at 05.50 (dd, J = 4.8, 6.3 Hz, H-3) and 05.40 (dd, J = 4.5, 4.8 Hz, H-4) and a quarternary carbon at 0 43.4
Hydride abstraction of tricarbonyl[η4‐1‐(phenylsulfonyl)‐1,3‐cyclohexadiene]iron(0) complex 2 with Ph3C+PF6− regiospecifically provided the title compound 3 in excellent yield. Cationic complex 3 could react with a variety of nucleophiles in good yields. Soft nucleophiles prefer to attack at the C‐5 position, whereas hard nucleophiles such as methyllithium and the enolate of ethyl acetate gave the C‐5 as well as the C‐2 addition products. Some synthetic applications of the addition products were also studied.
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