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A background of desulfitative cross coupling of thioorganic compounds and boronic acids is well introduced in chapter 1. Desulfitative cross coupling reactions are successfully applied to synthesize organo nitrile, alkyne, heterocycle, amidine. As an efficient and very mild reaction, desulfitative cross coupling is the best way to prepare high enantiopurity alpha-amino ketone and peptidyl ketone. The major part of this book describes how to develop the chemistry of palladium catalyzed N-protected peptidyl thiol ester and boronic acid cross coupling to generate peptidyl ketone with high yield and enantiopurity. Moreover, this methodology has been used as the key reaction to synthesize (-)-D-erythro-sphingosine and relative sphingolipids. In the end, the second generation of peptidyl ketone synthesis by copper catalysis is fully described in chapter 4, which represents the future of desulfitative carbon-carbon cross coupling reaction.