Process for the production of tetraaminobiphenol macrocyclic ligands; and novel tetraaminobiphenol macrocyclic ligands

A compound of structure (le)

• wherein R1 and R2 are independently selected from hydrogen, halide, a nitro group, a nitrile group, an imine group, —NCR13R14, an amine, an ether group —OR15 or —R16OR17, an ester group —OC(O)R10 or —C(O)OR10, an amido group —NR9C(O)R9 or —C(O)—NR9(R9), —COOH, —C(O)R15, —OP(O)(OR18)(OR19), —P(O)R20R21, a silyl group, a silyl ether group, a sulfoxide group, a sulfonyl group, a sulfinate group or an acetylide group or an optionally substituted alkyl, alkenyl, alkynyl, haloalkyl, aryl, heteroaryl, alkoxy, aryloxy, alkylthio, arylthio, alicyclic or heteroalicyclic group;
• R3 is independently selected from optionally substituted alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, heteroalkynylene, arylene, heteroarylene or cycloalkylene, wherein alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene and heteroalkynylene, in each case optionally interrupted by aryl, heteroaryl, alicyclic or heteroalicyclic;
• R4 is independently selected from hydrogen, or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylheteroaryl or alkylaryl;
• and E is independently selected from NR5 and NR6,
• wherein R5 is independently selected from optionally substituted aliphatic, heteroaliphatic, alicyclic, alkanoate, arylate, carboxyl, heteroalicyclic, aryl, heteroaryl, alkylheteroaryl or alkylaryl;
• or two R5 species may together be selected from optionally substituted alkylene, alkenylene or alkynylene, bonded to two different N groups of the compound of structure (Ie);
• wherein R6 is independently selected from optionally substituted aliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, ether, polyether, or optionally substituted alkylaryl or alkylheteroaryl;
• with the first proviso that at least one of the species E conforms to the definition given for NR6;
• and with the second proviso that the groups R5 and R6 are not all identical with each other;
• wherein R9, R10, R13, R14, R18, R19, R20 and R21 are independently selected from hydrogen or an optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group and R15, R16 and R17 are independently selected from an optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group.