Amines halogen-bond basicity

Generally, isolated olefinic bonds will not escape attack by these reagents. However, in certain cases where the rate of hydroxyl oxidation is relatively fast, as with allylic alcohols, an isolated double bond will survive. Thepresence of other nucleophilic centers in the molecule, such as primary and secondary amines, sulfides, enol ethers and activated aromatic systems, will generate undesirable side reactions, but aldehydes, esters, ethers, ketals and acetals are generally stable under neutral or basic conditions. Halogenation of the product ketone can become but is not always a problem when base is not included in the reaction mixture. The generated acid can promote formation of an enol which in turn may compete favorably with the alcohol for the oxidant. 

Accounts of presentations at a symposium have described daunorubicin and doxorubicin amdogues fluorinated at C-2, and other anthracyclines with reduced basicity and increased stability of the glycosidic bond, again by introduction of halogens at C-2 The 4 -morpholino-9-methylanthracycline 21 has been synthesized, and the 3 -amino-function of carminomydn has been incorporated into a morpholine ring which also carries a hypoxanthine unit, by reductive amination with 2, 3 -seco-inosine. ... 

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