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Cinchona alkaloids and their derivatives catalyse an astounding variety of synthetically important stereoselective reactions, thus providing access to a huge number of products of high enantiopurity. This chapter covers the use of natural and modified Cinchona alkaloids (quaternised, urea and thiourea derivatives are not included) in carbon–heteroatom bond-forming reactions – specifically: anhydride ring opening, hydrophosphonylation, epoxidations and hydroperoxidations, aziridination, lactone and lactam formation, epoxide and aziridine ring opening, amination, hydroxylation, sulfenylation and halogenation. Asymmetric hetero-Michael (oxa, aza, sulfa) additions catalysed by Cinchona alkaloids are also included.

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