Acylpalladation carbopalladation

Negishi E, Tan Z (2005) Diastereoselective, Enantioselective, and Regioselective Carbo-alumination Reactions Catalyzed by Zirconocene Derivatives. 8 139-176 Negishi E, Wang G, Zhu G (2006) Palladium-Catalyzed Cyclization via Carbopalladation and Acylpalladation. 19 1-48... 

Negishi E, Wang G, Zhu G (2006) Palladium-Catalyzed Cyclization via Carbopalladation and Acylpalladation. 19 1-48... 

Cyclic acylpalladation. Another major subtopic of carbopalladation is acylpalladation. In the mid-1960s, two seemingly independent papers were published by J. Tsuji [24] and P.R. Hughes [25,26]. The former reported a perfectly alternating copolymerization of norbornadiene with CO (Scheme 8), while the latter described two related Pd-catalyzed carbonylation cyclizations shown in Scheme 9. 

In addition to a couple of reviews focused on results obtained in the authors group [38,39], a comprehensive book on organopalladium chemistry for organic synthesis [40] contains two dozens or so chapters on cyclic car-bopalladation and cyclic acylpalladation. Thus, its Part IV (pi 123-1659) on carbopalladation contains reviews of cyclic carbopalladation on the synthe-... 

Table 1 Effect of ring size ont he competition between cyclic carbopalladation and cyclic acylpalladation in the presence of CO...

Ring size Substrate Cyclic carbopalladation Cyclic acylpalladation... 

Double or Multiple Carbopalladative Cyclization Reactions Involving One or More Cyclic Acylpalladation Processes... 

A systematic investigation of cyclic acylpalladation of haloenes, haloynes, and related electrophiles conducted since 1983 [30] has led to the development of three types of cyclic acylpalladation processes (Types I—III Ac-Pd) and Pd-catalyzed carbonylation-induced ketene [2 + 2] cycloaddition (Sect. 3.1). Collectively, these cyclic acylpalladation and related reactions have provided a number of new and attractive routes to cyclic compounds. Significantly, they nicely complement and supplement the non-carbonylative cyclic carbopalladation reactions. Thus, they have become integral and indispensable parts of the carbopalladation-based cyclization methodology. 

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