Halides double carbonylation, palladium-catalyzed

For the preparation of a-ketoamides, palladium-catalyzed double carbonylation of aryl halides with carbon monoxide and secondary amines is also a useful reaction Kobayashi, T. Tanaka, M. J. Organomet. Chem. 1982, 233, C64 Ozawa, F. Soyama, H. Yamamoto, T. Yamamoto, A. Tetrahedron Lett. 1982, 23, 3383. 

Palladium-catalyzed double carbonylations of aromatic halides have also been studied (equation 63). ° As might be expected, higher pressure is favorable for both reaction rate and selectivity. Selectivity for the formation of keto esters is also maximized by the use of sterically hindered alcohols and solvents of low polarity. 

B. DOUBLE CARBONYLATION OF ARYL HALIDES TO GIVE a-KETO ACID DERIVATIVES CATALYZED BY PALLADIUM COMPLEXES... 

With the exception of double carbonylation of allylic halides catalyzed by palladium-phosphine complexes as described above, there are few precedents of the catalytic double carbonylation of other kinds of aliphatic substrates. One example is the double carbonylation of 1-perfluoroaIkyl-substituted 2-iodoaIkanes promoted by palladium-phosphine complexes to give corresponding a-keto amides in good yields (Eq. 17). 

---