Studies toward the total synthesis of gambieric acids, potent antifungal polycyclic ethers: convergent synthesis of the CDEFG-ring system

[reaction: see text] A convergent synthetic route to the CDEFG-ring system of gambieric acids, potent antifungal polycyclic ether marine natural products, has been developed. The present synthesis features convergent union of the CD- and G-rings through esterification, formation of the E-ring as a lactone form, stereoselective allylation to set the C26 stereocenter, and ring-closing metathesis reaction to construct the nine-membered F-ring.     

Dissociation study of tellurium cluster ions, Te(n)(+) (n = 25-85) using secondary ion mass spectrometry

Dissociation pathways of tellurium clusters, Te(n)(+) (n = 25-85), were investigated by secondary ion mass spectrometry. Positively charged ions were generated from a tellurium sheet by bombardment with 10 keV xenon ion beam. Mass analyses of cluster ions were performed using a grand-scale sector mass spectrometer. In the first field-free region, Te(n)(+) (n = 25-80) had a large dissociation probability with five- and six-atom emission and Te(n)(+) (n = 50-85) had a slightly large dissociation probability with 10- and 11-atom emission. Five- and six-atom dissociation in the second field-free region could be also observed. These results were most likely due to the cluster emission processes for Te(n)(+), although sequential atom emission and cluster emission could not be distinguished by this type of experiments.     

Sequence distribution of 1,4 and 3,4 units in polyisoprenes

The ¹³C-NMR spectra of hydrogenated polyisoprenes were investigated. Polyisoprenes containing various ratios of 1,4 and 3,4 units were prepared with n-BuLi/Et₂O and were hydrogenated by using p-toluenesulfonylhydrazide. ¹³C-NMR signals of the hydrogenated polymers were assigned for the triad sequences arising respectively from the 1, 4 and 3, 4 units of polyisoprenes. On the basis of these assignments it was confirmed that 1,4 and 3,4 units were randomly distributed in the polyisoprenes prepared with n-BuLi and that these polymers did not contain appreciable amounts of head-to-head or tail-to-tail 1,4 linkages.     

Infrared lattice bands of some pearls

From analysis of anisotropical lattice bands properties of 50 reflection spectra both of the CO stretching and bending bands measured from some pearl (Ca⁺⁺CO ₃ ^–– or Ca⁺⁺HCO ₃ ^–– layer) we discussed following subjects.i) Quantized properties present both in reflectivity and in energy. ii) classifications of the Optical Activity. iii) Polar distributions of the CO₃ oscillators in Ca⁺⁺CO ₃ ^–– surface mono-layer. iv) Force constants of these oscillators. v) Step variation of the dipolemoment and their influences to the degree of Optical Activity. vi) Two types of hysteresis loops of the values of Y_N (M_2Jbend ()/M_1Jstret. ()) derived from the oscillators which are at innert-state, at weak active-state and at active-state.     

Relationship between the configurations of 2-phenyltetrahydrothiophenium 1-methylides and their rearrangement products

trans-2-Phenyltetrahydrothiophenium 1-methylide (trans-3), which is generated by fluoride ion-induced desilylation of trans-2-phenyl-1-[(trimethylsilyl)methyl]tetrahydrothiophenium salt (trans-2), gave a mixture of 1,4,5,10a-tetrahydro-3H-2-benzothiocine (4) ([2,3]sigmatropic rearrangement product) and 4-methylsulfanyl-1-phenyl-1-butene (5) (Hofmann elimination product). Ylide trans-3 cannot undergo [2,3]sigmatropic rearrangement because the ylide-carbon is too far from the phenyl group, and trans-3 would instead isomerize to cis-3. In this paper, we discuss the mechanism of the isomerization of trans-3 to cis-3.     

13CNMR-Untersuchung der Taktizität von Poly-(RS)tert-butyloxiran,das durch Polymerisation mit tert-C4H9OK erhalten wurde

Ohne Zusammenfassung     

Site-selective mono-titanation of conjugated diynes with a Ti(II) alkoxide reagent. Concise preparation of stereo-defined enynes and dienynes

Conjugated diynes underwent selective mono-titanation with a Ti(II) reagent to give 1:1 diyne-titanium alkoxide complexes, which reacted with proton, aldehyde, and another acetylene to give stereo-defined enynes, enynols, and dienynes.