Assembly state of catalytic modules as chiral switches in asymmetric Strecker amino acid synthesis.
Self-assembled chiral polymetallic complexes often demonstrate novel properties as asymmetric catalysts. We report the three-dimensional structures of two such asymmetric catalysts (crystals A and B) for Strecker alpha,alpha-disubstituted amino acid synthesis. These complexes are constructed via assembly of the same chiral modules derived from d-glucose, but their assembly modes differ. The enantioselectivity in the Strecker reaction was dramatically switched, depending on which assembly mode was used: the catalyst generated in situ whose structure is represented by crystal B, or by crystal A. These findings provide insight into the functional importance of higher-order structures of an artificial catalyst.
Kato
Nobuki
N
Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo Bunkyo-ku, Tokyo 113-0033, Japan.
Mita
Tsuyoshi
T
Kanai
Motomu
M
Therrien
Bruno
B
Kawano
Masaki
M
Yamaguchi
Kentaro
K
Danjo
Hiroshi
H
Sei
Yoshihisa
Y
Sato
Akihiro
A
Furusho
Sanae
S
Shibasaki
Masakatsu
M
D000596:Amino Acids / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D002625:Chemistry, Organic / Q000379:methods*; D003460:Crystallization; D015394:Molecular Structure; D021241:Spectrometry, Mass, Electrospray Ionization; D013237:Stereoisomerism; D014961:X-Ray Diffraction
D000596:Amino Acids