Stochiometric transformations

Moreover, there are already two other oxidative amination processes on the horizon, namely allylic amination of olefins and 1,2-diamination of 1,3-dienes [14]. Could these useful, but stochiometric transformations be rendered catalytic and perhaps also asymmetric some day ... 

Following the Fischer procedure, alkynyl carbyne complexes trans-X(CO)4M=C—CPh 189 have been obtained in 30-60% yields by reaction of (l-alkynyl)carbene complexes la,b (M = Cr, W) with BX3 (X = Cl, Br, I). To date, (l-alkynyl)carbyne compounds have found application as catalysts as well as stochiometric reagents in organic synthesis.205c-206 Among the transformations reported thus far is the formation of a 4-amino-l-metalla-l-yne-3-ene (= enamino carbyne complex) 190 by addition of HNMe2 to compound 189 (Scheme 79).207... 

Applications of stochiometric transition metal complexes in synthesis and transformations of heterocycles 00JCS(P1)109. 

The reaction with a Pd catalyst implies the use of a reoxidant reagent in stochiometric amount to transform Pd(0) (that results from the reaction) into Pd(II) (the reactive specie of the catalyst) usually high pressures of CO and O2 are necessary sometimes, in combination with l2 [26] alternatively, CO, O2 and copper salts can be nsed.[27]... 

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