Total syntheses of naturally occurring diacetylenic spiroacetal enol ethers

A highly stereoselective method for constructing a (2E)-methoxymethylidene-1,6-dioxaspiro[4.5]decane skeleton has been developed on the basis of the palladium(II)-catalyzed ring-closing reaction of the 3,4-dioxygenated-9-hydroxy-1-nonyn-5-one derivatives as a crucial step. The newly developed procedures could be successfully applied to the first total synthesis of five diacetylenic spiroacetal enol ether natural products starting from commercially available (R,R)- or (S,S)-diethyl tartrate.     

Nucleoside analogs. I. A synthesis of 1,3-dihydroxy-2-(6-substituted-9-purinyl)cyclohexane

Biologically active 1,3-dihydroxy-2-(6-substituted-9-purinyl)cyclohexanes (VI-X) were prepared by a reaction between trans-2-amino-1,3-cyclohexanediol (I) and 4,6-dichloro-5-amino-pyrimidine (II), followed by cyclization and nucleophilic substitution. Compounds VI and VII showed a weak inhibitory effect against Xanthomonas oryzae, a pathogenic bacteria of leaf blight of rice plant.     

Metal-centered ferrocene clusters from 5-ferrocenylpyrimidine and ferrocenylpyrazine

A series of metal-centered ferrocene compounds has been designed by using 5-ferrocenylpyrimidine (L1) and ferrocenylpyrazine (L2). These ligands, when combined with transition metal salts, produce mixed-metal polynuclear complexes with structural diversity. Reaction of L1 with M(SCN)(2) (M = Ni, Co) produces the pinwheel-like 4:1 complexes (L1)(4).M(SCN)(2), while reactions of L1 and L2 with Cu(NO(3))(2) give the 3:1 complex (L1)(3).Cu(NO(3))(2) and the 2:1 complex (L2)(2).Cu(NO(3))(2), respectively. Reactions of L1 and L2 with M(hfac)(2) (hfac = 1,1,1,5,5,5-hexafluoroacetylacetonate, M = Mn, Ni, Cu, Zn) produce 2:1 complexes (L)(2).M(hfac)(2) with cis and trans configurations, respectively. Crystal structures as well as solid-state electrochemical properties of these redox active complexes were investigated.     

Rh(I)-catalyzed ring-closing reaction of allenynes: selective construction of cycloheptene, bicyclo[5.3.0]decadienone, and bicyclo[5.2.0]nonene frameworks

Highly selective formation of cycloheptene, bicyclo[5.3.0]decadienone, and bicyclo[5.2.0]nonene skeletons from tri- and tetrasubstituted allenynes has been achieved via a Rh(I)-catalyzed ring-closing reaction and proper choice of substrate and/or reaction conditions.     

High levels of cholesteryl esters, progesterone and estradiol in the testis of aging male Fischer 344 rats: feminizing Leydig cell tumors

The levels and fatty acid composition of cholesteryl esters (CEs), and the levels of steroid hormones in the testis of aging Fischer 344 (F344) rats were studied in comparison with those of 6-month-old rats without Leydig cell tumors (controls). The total lipid content in the testis increased as Leydig cell tumors developed: in 23-month-old rats, the content increased to five times higher than that of the controls. The CE level reached about 300 times higher than that of the controls and comprised 57.5% of the total lipid of the testis. The fatty acid composition of the CEs in the tumor compared to the normal tissue from the controls was characterized by a marked increase in 22:4 (n-6) and a decrease in 22:5 (n-6), a characteristic acid in rat testis lipids. Testicular progesterone levels considerably increased with the development of tumors (23-month-old rats, 2870 ng/wet wt; controls, 7 ng/g wet wt). Also, levels of estradiol showed striking increments (23-month-old rats, 2205 pg/g wet wt; controls, 153 pg/g wet wt). On the other hand, testosterone levels decreased (23-month-old rats, 13 ng/g wet wt; controls, 50 ng/g wet wt). These results suggest that Leydig cell tumors in aging F344 rats resemble the ovary tissue of rats in the levels and fatty acid composition of the CEs, and in the levels of steroid hormones. This is supported by the observation that the two kinds of cells found in the tumor tissue resemble cells of the corpus luteum and granulosa cells of the follicles, respectively, in the ovary of rats. In conclusion, the study shows that Leydig cell tumors in aging male F344 rats have a tendency towards feminization.     

First total synthesis of (+)-indicanone

The first total synthesis of the guaiane-type sesquiterpene, (+)-indicanone (1), isolated from the root of Wikstroemia indica, was accomplished based on the rhodium(I)-catalyzed Pauson-Khand-type reaction of the allenyne derivative, which was derived from (+)-limonene. This total synthesis unambiguously confirmed the complete structure of (+)-indicanone involving its absolute stereochemistry.