Aryl derivatives primary arylamines

Methylations. Phenols are converted to their methyl ethers on reaction with CsjCOj and COCOMe). At a relatively high temperature (180°) alkyl aryl sulfones undergo mono-C-methylation. Primary arylamines also give monomethyl derivatives when a zeolite catalyst is present. ... 

A full paper detailing the conversion of primary alkylamines into the corresponding thiocyanates has appeared,and this important contribution to thiocyanate synthesis has now been extended to include aromatic derivatives. Thus, the readily prepared (56) reacts, in refluxing ethanol, with arylamines to give (57), which are smoothly pyrolysed to aryl thiocyanates in preparatively useful yields (Scheme 55). 

This approach has been extended to the conjugate addition of primary dialkylzincs to 2-aryl- and 2-heteroaryl-nitroolefins to obtain enantioenriched 2-arylamines. Dendritic styryl TADDOLs and polymer-bound Ti-TADDOLates have proved to be very practical chiral catalysts for the enantioselective addition of organozinc to aldehydes. Likewise, the immobilization of BfNOL by a cross-linking copolymerization of styryl derivatives has allowed several enantioselective Ti- and Al-Lewis acid-mediated additions to aldehydes. Dialkylzines obtained via an 1/Zn exchange or a B/Zn exchange have also been successfully used for the enantioselective additions to... 

---