Conformationally driven asymmetric induction of a catalytic dendrimer.
Nature's catalysts promote the reactions necessary for life with extremely high specificity by folding into specific shapes capable of communicating remote structural information to an active site. Achieving this objective in synthetic systems has been hampered by the lack of information concerning how dynamic conformational chirality can influence the stereoselectivity of a catalytic process. Herein, we report the first illustration of a catalytic dendrimer that achieves high enantioselectivity by amplifying/propagating local chirality via a dynamically folded structure. Experimental evidence supports a chiral relay mechanism that propagates local terminal chirality of the dendron to the axial chirality of the biphenyl core through the helical secondary structure of the dendron.
Department of Chemistry, The Ohio State University, 100 West 18th Avenue, Columbus, Ohio 43210, USA.
Jianfeng
J
Yu
T V
TV
RajanBabu
Jon R
JR
Parquette
D002384:Catalysis; D050091:Dendrimers / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D015394:Molecular Structure; D013237:Stereoisomerism
D050091:Dendrimers