Organocatalysis using N-heterocyclic carbene (NHCs) has been widely utilized for the polarity reversal of aldehydes (umpolung).1 Although NHC catalysis is well demonstrated for the enantioselective synthesis of target molecules, related application to the synthesis of axially chiral molecules is limited (especially the heteroatomcontaining axis). We have recently reported the NHC-catalyzed atroposelective synthesis of N-aryl succinimides having an axially chiral C-N bond via the desymmetrization of N-aryl maleimides.2 Moreover, using the acid activation strategy in NHC catalysis, we have demonstrated the atroposelective synthesis of C-N axially chiral phthalimides and maleimides.3 In addition, NHC-catalyzed selective amidation and (3+3) annulation reactions resulted in the atroposelective synthesis of N-N axially chiral 3-amino quinazolinones, indoles and pyrroles.4,5 Further, we have uncovered the NHC-catalyzed synthesis of C-O axially chiral diaryl ethers via atroposelective esterification of dialdehyde-containing diaryl ethers via a desymmetrization strategy.6 The details of these works will be presented.