Synthesis of a dialuminum-substituted silicotungstate and the diastereoselective cyclization of citronellal derivatives.
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.
Kikukawa
Yuji
Y
Department of Applied Chemistry, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan.
Yamaguchi
Syuhei
S
Nakagawa
Yoshinao
Y
Uehara
Kazuhiro
K
Uchida
Sayaka
S
Yamaguchi
Kazuya
K
Mizuno
Noritaka
N
D000080462:Acyclic Monoterpenes; D000447:Aldehydes / Q000737:chemistry*; D000535:Aluminum / Q000737:chemistry; D003500:Cyclization; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D015394:Molecular Structure; D039821:Monoterpenes / Q000737:chemistry*; D012825:Silicon / Q000737:chemistry*; D013053:Spectrophotometry; D013237:Stereoisomerism; D017973:Tungsten Compounds / Q000138:chemical synthesis* / Q000737:chemistry
D000080462:Acyclic Monoterpenes; D000447:Aldehydes; D039821:Monoterpenes; D017973:Tungsten Compounds; D000535:Aluminum; C108217:citronellal; D012825:Silicon