Acyclic stereoselection. 35. Effect of cation on diastereofacial selectivity in aldol reactions of a chiral α-silyloxy ketone.

By an appropriate choice of cation, three of the four possible aldols from the reactions of the chiral α-silyloxy ketone 1 with aldehydes may be obtained. The $\text{Z}$, lithium enolate provides 6, the $\text{Z}$, boron enolate gives 7, and the $\text{E}$ magnesium enolate affords 8.     

Experimental and theoretical study of the V → T,R relaxation of CD4 between 300 and 100 K

Rate constants for the vibrational deactivation of CD₄ by the collision partners CD₄, He, Ne, Ar, Kr, D₂ and O₂ have been measured using a laser-fluorescence technique. The results are compared with those for the deactivation of CH₄ by the same collision partners and with a modified SSH type theoretical treatment.     

Total Syntheses of (-)-Papuamine and (-)-Haliclonadiamine

The pentacyclic marine alkaloids (-)-papuamine (1) and (-)-haliclonadiamine (2) have been prepared by total synthesis. The synthesis began with (-)-8, which was converted into diester 20 by way of bis-mesylate 17, dinitrile 18, and diacid 19. Dieckmann cyclization of 20 provided keto ester 21, which was transformed into acetal 22. After hydrolysis of the acetal, ketone 25 was subjected to reductive amination with 1,3-propanediamine and sodium triacetoxyborohydride to obtain diamines 26 and 27 as a 71:29 mixture of diastereomers, favoring the symmetrical isomer having the papuamine relative configuration. After transformation of the diamines to their t-Boc derivatives, the benzyl ethers were cleaved and the resulting diol was oxidized to dialdehyde 30. Application of the Seyferth procedure for conversion of aldehydes to alkynes gave a mixture of diynes 31 and 32. After removal of the t-Boc protecting groups from 31, diamino diyne 15 was treated with tributylstannane and azoisobutyronitrile to obtain the bis-vinylstannane 34. Treatment of this compound with Pd(II) and Cu(I) in the presence of air produced (-)-papuamine (1). (-)-Haliclonadiamine (2) was obtained from the unsymmetrical isomer, 32. The NMR spectra of the synthetic alkaloids were identical to those of authentic samples of the natural alkaloids.     

Diffractive production of charmed strange mesons by neutrinos and antineutrinos

The diffractive production of charmed strangeD _s ^* and possiblyD _s mesons by neutrinos and antineutrinos on nucleons in hydrogen, deuterium and neon targets is observed. The slope parameter of thet distribution is 3.3±0.8 (GeV)^?2. The production rate per charged current neutrino interaction with an isoscalar target times the D _s ⁺ →φτ⁺ branching fraction is (1.03±0.27)×10^?4.     

A comparison of two methods for the preparation of 3-Deazapurine ribonucleosides

The reaction of the trimethylsilyl derivative of 4,6-dichloroimidazo[4,5-c]pyridine with 2,3,5-tri-O-benzoyl- D -ribofuranosyl bromide gave four nucleosides-the α- and β-anomers of the 1-isomer and the α- and β-anomers of the 3-isomer (3.9:2.7:1.5:1). In contrast, the fusion reaction of 4,6-dichloroimidazo[4,5-c ]pyridine with 1,2,3,5-tetra-O-acetyl-β- D -ribofuranose gave a high yield of the 1-β-isomer, which was converted to the known 3-deazaadenosine (4-amino-l-β- D -ribofuranosylimidazo[4,5-c]pyridine).     

The Electronic Structure of Vinyl Ethers and Sulfides with Interrupted Conjugation Examined by Photoelectron Spectroscopy

Photoelectron spectroscopy has been used to examine the consequences of steric inhibition of conjugation in a distorted vinyl sulfide and vinyl ether. Based upon the degree of interaction a deviation from coplanarity of 70°–75° is calculated for 9-oxabicyclo[3.3.1]non-1-ene ( 3 ) and approximately 75°–80° for the sulfur analog 6 .