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Chiral tertiary phosphines are versatile Lewis base catalysts capable of promoting a wide range of asymmetric reactions. In particular, recently designed chiral phosphines based on the concept of bifunctionality and multifunctionality have been demonstrated to be effective catalysts for various types of asymmetric reactions such as (aza)-MBH reactions, cycloadditions, nucleophilic additions, etc. This chapter summarises the recent advances in this field and highlights selected significant achievements.

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