TADDOL Mannich reaction

Scheme 11.16 Conjugate addition/Mannich reaction using TADDOL-based ligand 67 [26].

Most notably, the Antilla laboratory has employed VANOL and VAPOL phosphoric acid derivatives in several novel asymmetric transformations. In addition, TADDOL and phosphordiamide phosphoric acid derivatives have been applied in several Mannich-type reactions. 

Akiyama T, Morita H, Itoh J, Fuchibe K (2005a) Chiral Brpnsted acid catalyzed enantioselective hydrophosphonylation of imines asymmetric synthesis of alpha-amino phosphonates. Qrg Lett 7 2583-2585 Akiyama T, Saitoh Y, Morita H, Fuchibe K (2005b) Enantioselective Mannich-type reaction catalyzed by a chiral Bronsted acid derived from TADDOL. Adv Synth Catal 347 1523-1526... 

We have synthesized a TADDOL-based phosphoric acid diester (47), which catalyzed the Mannich-type reaction of ketene silyl acetal with aldimines to give p-amino esters with high enantioselectivity. (Scheme 2.104) [180]. 

Chiral phosphoric acids are not restricted to those originating from BINOL. TADDOL-based phosphoric acid 8 was developed by AMyama et al. and applied to the Mannich-type reaction (Scheme 11.3) [9). Interestingly, the aryl substituents... 

Scheme 11,3 Enantioselective Mannich-type reaction catalyzed by TADDOL-based phosphoric...

---