A novel dialuminum-substituted silicotungstate TBA(3)H[gamma-SiW(10)O(36){Al(
OH(2))}(2)(mu-
OH)(2)] x 4 H(2)O (1, TBA = tetra-n-butylammonium) was synthesized by the reaction of the
potassium salt of [gamma-SiW(10)O(36)](8-) (SiW10) with 2 equiv of Al(NO(3))(3) in an acidic aqueous medium. It was confirmed by the X-ray crystallographic analysis that compound 1 was a monomer of the gamma-Keggin dialuminum-substituted silicotungstate with the {Al(2)(mu-
OH)(2)}
diamond core. The cluster framework of 1 maintained the gamma-Keggin structure in the
solution states. The reaction of 1 with
pyridine yielded TBA(3)[(C(5)H(5)N)H][gamma-SiW(10)O(36){Al(C(5)H(5)N)}(2)(mu-
OH)(2)] x 2 H(2)O (2), and the molecular structure was successfully determined by the X-ray crystallographic analysis. In compound 2, two of three
pyridine molecules coordinated to the axial positions of
aluminum centers and one of them existed as a pyridinium
cation, showing that compound 1 has two
Lewis acid sites and one Brønsted
acid site. Compound 1 showed high catalytic activity for the intramolecular cyclization of
citronellal derivatives such as (+)-
citronellal (3) and 3-methylcitronellal (4) without formation of byproduct resulting from etherification and
dehydration. For the 1-catalyzed cyclization of 3, the diastereoselectivity toward (-)-
isopulegol (3a) reached ca. 90% and the value was the highest level among those with reported systems so far. The reaction rate for the 1-catalyzed cyclization of 3 decreased by the addition of
pyridine, and the cyclization hardly proceeded in the presence of 2 equiv of
pyridine with respect to 1. On the other hand, the reaction rate and diastereoselectivity to 3a in the presence of
2,6-lutidine were almost the same as those in the absence. Therefore, the present cyclization is mainly promoted by the
Lewis acid sites (
aluminum centers) in 1. DFT calculations showed that the formation of the transition state to produce 3a is sterically and electronically more favorable than the other three transition states for the present 1-catalyzed cyclization of 3.