Diazabicyclo octane metal complexes

Phosphite 56 equipped with three zinc porphyrins reacts with l,4-diazabicyclo[2.2.2]octane as the templating agent to give selectively 57 as a bis-phosphite rhodium metal complex. In the absence of the templating diamine, the l b ratio is 2-3 in the rhodium-catalyzed hydroformylation, but after addition of the template, it raised to 15-23, similar to covalently bonded bidentate phosphates with a wide bite angle. 

A lower rim conjugate in which the p-bu -calix[4]arene was covalently linked at 1,3-distal positions to tetraphenylporphyrin through -CH2-CO-NH- at the para position of one of the phenyl rings was metallated using zinc acetate/triethyl amine to form 192. It reacts with the bidentate ligand l,4-diazabicyclo[2.2.2]octane (DABCO) to form a 1 2 complex in which both porphyrin units are ligated separately (2003T2409). 

Excellent results have again been reported for the condensation of allyl bromides or chlorides with l-phenylthio-2-alkenyllithiums. These "soft" nucleophiles are readily generated by the treatment of suitable 2-alkenyl phenyl sulfides with the -butyllithium/DABCO complex (DABCO = l,8-diazabicyclo[2.2.2]octane). The "tail-to-tail" connected products can be desulfurized without double bond shift as demonstrated by the synthesis of a/Z-fE -squalene (123 Scheme 1-88) and a (Z,E,E,E)-isomer thereof as well. Similar allyl-allyl couplings have also been executed using metalated allylic sulfones rather than sulfides. ... 

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