Total synthesis of antimalarial diterpenoid (+)-kalihinol A

Total synthesis of antimalarial diterpenoid (+)-kalihinol A, isolated from marine sponge Acanthella sp., is achieved. This total synthesis involves regioselective alkylation of an epoxide, construction of a tetrahydropyran ring by iodo-etherification, construction of a cis-decalin ring by intramolecular Diels-Alder reaction, isomerization of cis-decalin to trans-decalin, and subsequent functionalization of the trans-decalin ring.     

Copper-catalyzed coupling reaction of unactivated secondary alkyl iodides with alkyl Grignard reagents in the presence of 1,3-butadiene as an effective additive

Cu-catalyzed cross-coupling of unactivated secondary alkyl iodides with alkyl Grignard reagents in the presence of 1,3-butadiene as a ligand precursor was developed. The use of 1,3-butadiene resulted in improved yields of alkyl-alkyl products with improved selectivities.     

Influence of water on molecular forms of rhodamine B in dip-coated thin films

Dip-coated thin films including rhodamine B have been prepared using the sol-gel reaction of tetraethyl orthosilicate under relative humidity of 30% and 60%. They have been aged under relative humidity of 20%, 60%, and 95% for 5 days. According to the absorption spectra, just after the preparation of the films and under higher humidity, a larger amount of the dimers (H-and J-types) were formed in the films. Five days after the preparation of the films and aged under higher humidity, the H-dimer increased. On the other hand, the J-dimer increased, regardless of humidity under which the films were aged.     

Synthesis and Stereochemical Revision of the C31–C67 Fragment of Amphidinol 3

Amphidinol 3 (AM3) is a marine natural product produced by the dinoflagellate Amphidinium klebsii. Although the absolute configuration of AM3 was determined in 1999 by extensive NMR analysis and degradation of the natural product, it was a daunting task because of the presence of numerous stereogenic centers on the acyclic carbon chain and the limited availability from natural sources. Thereafter, revisions of the absolute configurations at C2 and C51 were reported in 2008 and 2013, respectively. Reported herein is the revised absolute configuration of AM3: 32S, 33R, 34S, 35S, 36S, and 38S based on the chemical synthesis of partial structures corresponding to the C31–C67 fragment of AM3 in combination with degradation of the natural product. The revised structure is unique in that both antipodal tetrahydropyran counterparts exist on a single carbon chain. The structural revision of AM3 may affect proposed structures of congeners related to the amphidinols.     

Constructing one-parameter transformations on white noise functions in terms of equicontinuous generators

Let be a barreled locally convex space. A continuous operator on is called anequicontinuous generator if { ⁿ /n!;n=0,1,2,...} is an equicontinuous family of operators. For each equicontinuous generator a one-parameter group of operators is constructed by means of power series. There is a one-to-one correspondence between the equicontinuous generators and the locally equicontinuous holomorphic one-parameter groups of operators. If two equicontinuous generators ₁, ₂ satisfy [₁,₂]=₂ for some thena₁+b₂ is also an equicontinuous generator for anya, b. These general results are applied to a study of operators on white noise functions. In particular, a linear combination of the number operator and the Gross Laplacian, which are natural infinite dimensional analogues of a finite dimensional Laplacian, is always an equicontinuous generator. This result contributes to the Cauchy problems in white noise (Gaussian) space.Work supported by Alexander von Humboldt-Stiftung and Japan Society for Promotion of Sciences     

Stereoselective synthesis of methyl (Z)-(4,4-difluoro-2,3,4,5-tetrahydro-1H-1-benzazepin-5-ylidene)acetate using a dianion Horner-Wadsworth-Emmons reagent

Stereoselective synthesis of methyl (Z)-(4,4-difluoro-2,3,4,5-tetrahydro-1H-1-benzazepin-5-ylidene)acetate (1a) is described. Z-selectivity of the Horner-Wadsworth-Emmons (HWE) reaction was obtained based on an investigation of the reaction conditions for introduction of a methylidene group onto the 5-position of benzazepine.     

Palladium-catalyzed dimerization disilylation of 1,3-butadiene with chlorosilanes

[reaction: see text] 1,3-Butadiene reacted with chlorosilanes and Grignard reagents at 20 degrees C in the presence of a catalytic amount of Pd(acac)(2) to give disilylated dimers 2 regioselectively, which have two silyl groups (R(3)Si) at the 3- and 8-positions of a 1,6-octadiene skeleton. When phenyl- or allyl-substituted chlorosilanes were used, coupling product was obtained stereo- as well as regioselectively, giving rise to only (E)-olefins. It is proposed that Pd-ate complexes play important roles in both C-Si bond-forming processes.     

Reaction between rare earth elements and HFNO2 solution

Rare earth elements react with HFNO₂ solution to produce nitrosylium fluorometallates (NO)_xLnF_x+3. The value of x is 1.0 or 1.5 for light rare earth elements and 0.5 or 1.0 for heavy rare earths. Nitrosylium fluorometallates of rare earth elements can be decomposed into the simple fluoride and nitrosyl fluoride at low temperatures (46–68°C).     

Carbonylation of lithium enolates with carbon monoxide mediated by selenium

[reaction: see text] Lithium enolates of ketones and aldehydes undergo carbonylation with carbon monoxide with the aid of selenium under mild conditions to yield beta-keto and beta-formyl selenol esters after trapping with alkyl iodides. This reaction proceeds via a unique carbonylation mechanism comprised of O-carbonylation and subsequent migration of the SeCO moiety to the alpha-carbon.