Preparation and reaction of 2-aryl-3-silyl-1,3-butadiene

[reaction: see text] A conjugated pi-electron compound, 2-aryl-3-silyl-1,3-butadiene, was easily prepared from 1-benzyloxy-3-silyl-2-propyne, bis(iodozincio)methane, and an aryl halide in the presence of nickel catalyst. A subsequent cross-coupling reaction of the product with another aryl halide gave an unsymmetrical 2,3-diaryl-1,3-butadiene efficiently.     

Determination of sulfates of androsterone and epiandrosterone in human serum using isotope diluted liquid chromatography-electrospray ionization-mass spectrometry

A promising liquid chromatography-electrospray ionization-mass spectrometry (LC-ESI-MS) for analysis of the sulfates of 5alpha-androgen, androsterone and epiandrosterone (A-S and EpiA-S) in human serum was developed. The method was used to assess one of the markers of 5alpha-reductase activity of males including patients with prostate cancer (PC). After deproteinization with acetonitrile, the androgen sulfates and the internal standard, [7,7,16,16-2H4]dehydroepiandrosterone-S, were extracted from human serum using a solid-phase extraction cartridge and washed with hexane. The extract was reconstituted and applied to the LC/ESI-MS system operated in the selected ion monitoring mode. The method was validated over the range 0.02-5 microg/mL (A-S) and 0.005-1.5 microg/mL (EpiA-S) using 10 microL of human serum. The method was a concise procedure without chemical or enzymatic hydrolysis of the conjugates, purification by high-performance liquid chromatography and/or derivatization, and proved to be satisfactory in its reproducibility and accuracy. The levels of these androgen sulfates tended to decrease during aging, and the A-S levels in the sera obtained from both healthy males and patients with PC were correlated with their EpiA-S levels.     

1,3-Rearrangement of ketene-N,O-acetals

Ketene N,O-acetals were prepared stereoselectively and submitted to a Lewis acid-mediated 1,3-rearrangement to afford C-alkylated products. The reactions proceeded in a stereoselective manner to construct a chiral quaternary carbon in high selectivity. The stereochemistry of the quaternary center was found to be opposite to that obtained by an anionic direct dienolate alkylation.     

Remote asymmetric induction with vinylketene silyl n,o-acetal

A highly regio- and diastereoselective TiCl4-mediated vinylogous Mukaiyama aldol reaction using the chiral vinylketene silyl N,O-acetal has been developed. The present vinylogous Mukaiyama aldol reaction provides a unique and effective means of controlling remote asymmetric induction. The methyl group at the alpha-position is important in achieving a high level of stereoselectivity. From a synthetic point of view, this methodology can provide a one-step construction of delta-hydroxy-alpha,gamma-dimethyl-alpha,beta-unsaturated carbonyl unit that is seen in many natural polyketide products.     

The first total synthesis of lactonamycin, a hexacyclic antitumor antibiotic

The total synthesis of lactonamycin has been achieved. The synthesis includes sequential intramolecular conjugate addition of alcohols to the acetylenic ester, stereoselective glycosylation of the tertiary alcohol, and Michael-Dieckmann type cyclization with the thioester, by which the highly convergent route has been established.     

Preparation of a cycloheptane ring from a 1,2-diketone with high stereoselectivity

Treatment of 1,6-dialkylhexa-1,5-diene-3,4-diones with bis(iodozincio)methane gave zinc alkoxides of cis-5,6-dialkylcyclohepta-3,7-diene-1,3-diol in good yields at room temperature. The reaction proceeded with high stereospecificity. Bis(iodozincio)methane converted the diketone into the cis-divinylcyclopropane-1,2-diol stereoselectively; this diol transformed into the corresponding cycloheptane derivative stereospecifically via Cope rearrangement.     

Resistivity control of sputtered amorphous-silicon by ion-implantation

The resistivity of a hydrogenated sputtered amorphous-silicon is controlled by using room temperature implantation of P⁺. It is found that the defects produced by implantation can be minimized by annealing at 300°C in an H₂ atmosphere, and also found that there is a threshold implanted dose, beyond which the resistivity begins to be controlled by changing the dose.     

A Triphenylamine with Two Phenoxy Radicals Having Unusual Bonding Patterns and a Closed‐Shell Electronic State

Reported herein is the structure and the electronic properties of a novel triphenylamine derivative having two phenoxy radicals appended to the amino nitrogen atom. X‐ray single crystal analysis and the magnetic resonance measurements demonstrates the unexpected closed‐shell electronic structure, even at room temperature, of the molecule and two unusual C? N bonds with multiple‐bond character. The theoretical calculations support the experimentally determined molecular geometry with the closed‐shell electronic structure, and predicted a small HOMO–LUMO gap originating from the nonbonding character of the HOMO. The optical and electrochemical measurements show that the molecule has a remarkably small HOMO–LUMO gap compared with its triphenylamine precursor.     

Asymmetric Synthesis of Spiroketals with Aminothiourea Catalysts

Chiral spiroketal skeletons are found as core structures in a range of bioactive compounds. These natural compounds and their analogues have attracted much attention in the field of drug discovery. However, methods for their enantioselective construction are limited, and easily available optically active spiroketals are rare. We demonstrate a novel catalytic asymmetric synthesis of spiroketal compounds that proceeds through an intramolecular hemiacetalization/oxy‐Michael addition cascade mediated by a bifunctional aminothiourea catalyst. This results in spiroketal structures through the relay formation of contiguous oxacycles, in which multipoint recognition by the catalyst through hydrogen bonding imparts high enantioselectivity. This method offers facile access to spiroketal frameworks bearing an alkyl group at the 2‐position, which are prevalent in insect pheromones. Optically active (2S,5S)‐chalcogran, a pheromone of the six‐spined spruce bark beetle, and an azide derivative could be readily synthesized from the bicyclic reaction product.     

The first total synthesis and structural determination of antibiotics K1115 B1s (alnumycins)

K1115 B₁, isolated from the broth of Streptomyces species, was found to be a mixture of stereoisomers. Authors synthesized all stereoisomers of K1115 B₁ by convergent synthesis coupling a rhamnose derivative, an isobenzofuranone, and a chiral tetraol. Comparison of ¹H NMR spectra and optical rotations made it clear that the absolute structures of K1115 B_1α (the major isomer) and K1115 B_1β (the minor isomer) were (1R, 17S)- and (1R, 17R)-configurations, respectively. The optical rotations of the stereoisomers revealed that alnumycin, reported as the identical structure with K1115 B₁, might be another mixture of stereoisomers.