Hf. Chow et Cc. Mak, PREPARATION AND STRUCTURE-CHIROPTICAL RELATIONSHIPS OF TARTARIC ACID-BASED LAYER-BLOCK CHIRAL DENDRIMERS, Journal of the Chemical Society. Perkin transactions. I, (2), 1997, pp. 91-95
Two optically active, diastereoisomeric, first generation layer-block
dendrimers 1 and 2 have been prepared by a convergent synthetic proced
ure. These chiral, layer-block dendrimers utilize 4-tert-butylphenoxy
moieties as the surface groups and phloroglucinol as the branching jun
ctures. Two different chiral units, which are derivatives of (D)- and
(L)-tartaric acid, serve as the chiral linkers between the surface gro
up and the branching juncture, or between two branching junctures. The
first layer-block dendrimer 1 has an outer chiral layer made up of si
x (L)-tartrate derived units and an inner chiral layer of three (D)-ta
rtrate derived units. The second layer-block dendrimer 2 has an outer
shell consisting of three (D)- and three (L)-chiral units and an inner
shell of three (D)-chiral units. The molar rotation of these structur
ally flexible, low generation dendritic compounds is proportional to t
he number of chiral tartrate units in excess, with the chiroptical eff
ect of a (D)-tartrate derived chiral unit cancelling that of an (L)-ta
rtrate derived unit on a 1:1 basis. Circular dichroism studies, howeve
r, reveal that this cancellation effect is more effective when both th
e (D)- and (L)-chirons are situated within the same layer.