2.1. Initial Studies. We initially investigated the possibility of our proposal in the asymmetric reactions of amino acid ester 1a with 2-nitro fluorobenzene 2a, allyl chloride 5a, and benzyl chloride 8a. The simple chiral aldehyde CA-1 was chosen as a catalyst, and the base Cs2CO3, or tetramethylguanidine, was added to accelerate the deprotonation process. We found that the arylation reaction of tertbutyl alaninate 1a and 2-nitro fluorobenzene 2a took place smoothly, providing the desired product 3a in 25% yield with > 99% enantioselective excess (ee), although the side product 4a was obtained in 16% yield (Figure ). For the allylation reaction of 1a with cinnamyl chloride 5a, the desired product 7a was obtained in 23% yield with 8% ee. However, no product 9a was observed in the benzylation of 1a with 8a. To suppress the N-functionalization side reaction, the Lewis acid ZnCl2 was added. As expected, the yield of the allylation product 6a was enhanced to 89%, and the benzylation product 9a was obtained in 15% yield (Figure ).