Arenes, nucleophilic addition onto

Alkyl and 2-Alkenyl Halides or Sulfonates Ring Opening of Cyclic Amines and Ethers Addition onto Carbon-Carbon Multiple Bonds Addition onto Heteroconjugated Multiple Bonds Nucleophilic Substitution of 1-Alkenyl Halides Nucleophilic Addition onto Arenes and Hetarenes Substitution of Halo-, Alkoxy-, and Metalloarenes or -hetarenes Addition onto Nonaromatic Carbon-Nitrogen Multiple Bonds Addition onto Carbonyl Compounds... 

The factors that control the site of attack of nucleophiles on arene complexes are complex, and the position of attack is controlled by the electronic properties of the substituents. These properties dictate whether attack will occur meta or para to the substituent. Steric effects discourage attack ortho to the substituent. In many cases, the attack of nucleophiles on coordinated arenes is reversible. Thus, the final productive reaction may result from addition at a site of the arene that is not the kinetic site for attack. For example, nucleophilic attack onto the ortho, meta, or para positions of the phenyl chloride coordinated to Cr(CO)j in Equation 11.53 is reversible, and it is only attack at the ipso position that leads to productive substitution chemistry. - ... 

The preparation of enantiopure or enriched complexes possessing planar chirality has been accomplished either by resolution of racemic mixtures or by asymmetric syntheses. Reported methods for the resolution of planar chirality include both chemical and kinetic resolution procedures, whilst reported asymmetric syntheses of enantiomerically pure or enriched benchrotrenic complexes include enantioselective ort/io-deprotonations with chiral lithium amide bases, and the transfer of side chain chirality onto the arene ring mediated by diastereoselective orf/io-nucleophilic additions and o/tfeo-metalations. 

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