PDF《5-Pyrimidyl alkanol 2》

1.

Asymmetric autocatalysis initiated with N-myristoyl alanine. The direction of asymmetric induction has been examined employing N-myristoyl alanine[1] as a chiral initiator of asymmetric autocatalysis (Table S1). As a result of asymmetric autocatalysis, N-myristoyl-D-alanine induced the formation of (S)-pyrimidyl alkanol

2 with a high ee value, and N-myristoyl-L-alanine promoted the production of enantiomerically enriched (R)-alkanol 2, respectively. Table S1. Asymmetric autocatalysis initiated with N-myristoyl alanine.[a] 5-Pyrimidyl alkanol

2 Entry Config. of N-myristoyl alanine Yield (%)[b] ee (%)[c] Config.

1 D

87 94 S

2 L

91 93 R

3 D

93 93 S

4 L

86 90 R [a] The aldehyde

1 and diisopropylzinc were added in three separate portions in the presence of N-myristoyl alanine. [b] Isolated yield. [c] The ee was determined using HPLC employing a chiral stationary phase. [S1] Asymmetric autocatalysis induced by chiral amino acids: a) T. Shibata, J. Yamamoto, N. Matsumoto, S. Yonekubo, S. Osanai, K. Soai, J. Am. Chem. Soc. 1998, 120, 12157C12158;

b) I. Sato, Y. Ohgo, H. Igarashi, D. Nishiyama, T. Kawasaki, K. Soai, J. Organomet. Chem. 2007, 692, 1783C1787. 2. Determination of ee of chiral mesoporous silica. The enrichment of the handedness of chiral mesoporous silica (Sample A, B, C, D and E) were determined from the SEM images. Determination of the ee of Sample C was shown in Figure S1. Figure S1. SEM images of right-handed enriched (P)-helical mesoporous silica (Sample C) used as chiral initiators of asymmetric autocatalysis shown in Table 1, Entries

7 and 8. The numbers of (P)- and (M)-helical silica in each images are (a) (P) : (M) =

36 : 21, (b)

44 : 25, (c)

65 : 22, (d)

30 : 18, (e)

47 : 18, (f)

46 : 14. Therefore, the ee of Sample C was calculated to be 39% ee (P) from the total numbers of

268 (P)- and

118 (M)-mesoporous silica.