Asymmetric synthesis carbodiimide

A one-pot protocol for the synthesis of 1-aryl-5-(N-aryl-N-aroylamino)-tetrazoles 247 from symmetrical diaryl carbodiimides 243 with sodium azide under phase transfer conditions in toluene at room temperature was developed by Ding and Weber. The carbodiimide 243 reacts with sodium azide to form a guanyl azide 244 which, after reaction with an aroyl chloride 245, imdergoes electrocycHzation to yield the substituted tetrazole 247 (Scheme 47). The reaction is limited to symmetrical diaryl carbodiimides. Di-aUcyl carbodiimides fail to react imder these conditions while asymmetrical diaryl carbodiimides lead to a mixture of tetrazole isomers [157]. 

Fig. 7.5. Amine addition to an isocyanate as part of the synthesis of an asymmetrical carbodiimide.

Busacca and co-workers have prepared menthol-derived phosphinite boranes 101 and 102, by direct addition of anionic secondary phosphine borane 100 to carbodiimides, yielding the chiral phosphinite boranes under ambient temperature conditions (Scheme 25). These and other derivatives, prepared by hydrophosphination of carbodiimides, were used in the synthesis of enantiomerically enriched phosphaguanidines with potential use as ligands in asymmetric catalysis. 

The synthesis of asymmetric carbodiimides at low temperatures and in high yields is also an important chemical challenge, due to their versatility as polymer precursors and building blocks for natural product synthesis. A range of homogeneous catalysts have been reported for this reaction and in each case a metal-imido complex was implicated as the reactive intermediate. Recently, Holland et utilised in situ EPR... 

---