Pd(0)‐Catalyzed Deacylative Allylations (DaA) Strategy and Application in the Total Synthesis of Alkaloids

Abstract

Natural product synthesis has been the prime focus for the development of new carbon-carbon bond forming transformations. In particular, the construction of molecules with all-carbon quaternary centers remain one of the most facinating targets. In this regard, transitionmetal catalyzed processes have gained imporatnce owing to their mild nature. Towards this, Pd(0)-catalyzed decarboxylative allylations (DcA) is worth mentioning and has emerged as a convenient method for synthesis of molecules even in their enantioenriched form. However, in order to have a flexible approach that facilitate rapid production of derivatives by utilizing commercially available allyl alcohols, the concept of Pd(0)-catalyzed deacylative allylations (DaA) methodology gains popularity. In these reactions, the transfer of an acyl group has a functional role in activating the allylic alcohol (proelectrophile) toward reaction with Pd(0)-catalysts. We present here an Account on newly conceptualized deacylative allylations (DaA) methodology and its applications in the synthesis of various intermediates and building blocks. Further, its potential in the total synthesis of naturally occurring alkaloids have been summarized in this personal account.