A Bioinspired Synthesis of (±)‐Rubrobramide, (±)‐Flavipucine,and (±)‐Isoflavipucine

A biomimetic synthesis of naturally occurring lactams rubrobramide, flavipucine, and isoflavipucine is described. The key step is a regioselective Darzens reaction between isobutyl glyoxal and an α‐bromo‐β‐ketoamide. The construction of the core tricyclic ring system of rubrobramide was achieved by a cascade reaction in a single step from an α,β‐epoxy‐γ‐lactam. Furthermore, the absolute configuration of naturally occurring (+)‐rubrobramide was determined by vibrational circular dichroism. (±)‐Flavipucine and (±)‐isoflavipucine were synthesized from an epoxyimide, which was prepared by reaction of isobutyl glyoxal with a protected α‐bromo‐β‐ketoamide. Deprotection of the epoxyimide and formation of the pyridone ring gave (±)‐flavipucine, which was converted into (±)‐isoflavipucine by thermal isomerization.     

Homochiral helices of oligonaphthalenes inducing opposite-handed cholesteric phases

The helical structure of the chiral nematic phases (cholesterics) obtained by doping nematic solvents with chiral non-racemic compounds is a macroscopic proof of the solute chirality. Oligonaphthalene (tetra-, hexa-, octa-) derivatives linked at the 1,4-positions have been used as chiral dopants: When the chirality axes are configurationally homogeneous (that is, all-S), the molecular structures correspond to right-handed helices. Yet, we have found series of derivatives with the surprising property that the handedness of the induced cholesteric phase alternates from positive to negative and to positive again, on passing from tetra- to hexa- and to octanaphthalene. A comparison with oligonapthalene derivatives, which do not exhibit this twisting ability, points to the importance of the substitution pattern. Both the possibility of inducing oppositely-handed cholesteric phases by homochiral helices of different length, and the role played of substituents, are confirmed by calculations performed with the surface chirality model.     

Facile Synthesis of Proton-Type ZSM-5 by Using Quasi-Solid-Phase (QSP) Method

Herein, a simple and green quasi-solid-phase (QSP) method for facile synthesis of proton-type ZSM-5 avoiding use of excessive water, dry gel, Na⁺ cation and fluoride is reported. Crystallization by using the stoichiometric amount of TPAOH (tetrapropylammonium hydroxide) at 180 °C for only 12 h gave well-structured HZSM-5 crystals with high specific surface area of 429 m² g⁻¹ and high thermal stability. 5MRs was observed to closely relate the formation of MFI structure and QSP method exhibits shorter induction period (t₀), higher nucleation rate (V_n), and faster growth rate (V_g). Moreover, HZ-12–180 showed extremely better and rather stable catalytic activity for methanol-to-propylene reaction by comparison with commercial HZSM-5.     

Generation of 2-Carboethoxyethylzinc iodide and 3-carboethoxypropylzinc iodide and their application to the synthesis of γ- and δ-keto esters

2-Carboethoxyethylzinc iodide and 3-carboethoxypropylzinc iodide are generated by the reaction of the corresponding iodoesters with Zn-Cu couple and utilized for the palladium catalyzed coupling reaction with acid chloride to quantitatively provide gamma- and delta- keto esters, respectively.     

Visual enantiomeric recognition of amino acid derivatives in protic solvents

Various types of chiral host molecules 2-7 based on a phenolphthalein skeleton and two crown ethers were prepared for use in visual enantiomeric recognition, and we examined their enantioselective coloration in complexation with chiral amino acid derivatives 9-22 in methanol solution. Methyl-substituted host (S,S,S,S)-3 showed particularly prominent enantiomer selectivity for the alanine amide derivatives 11 and 12. A combination of methyl-substituted host (S,S,S,S)-3 with guest (R)-11 or (R)-12 developed a purple color, whereas no color development was observed with (S)-11 or (S)-12. On the other hand, phenyl-substituted host (S,S,S,S)-6 showed deeper coloration with a wide range of (S)-beta-amino alcohols compared to that seen with host (S,S,S,S)-6 and the corresponding (R)-beta-amino alcohols at 0 degrees C. Furthermore, absorbance inversion temperatures (AIT) were observed within the range of 0-50 degrees C in many cases.     

Development of xanthene dyes containing arylacetylenes: The role of acetylene linker and substituents on the aryl group

Fluorescent dyes possessing a variety of arylacetylenes at the 9-position of a xanthene skeleton were synthesized and their optical properties were investigated. The π system effectively expanded over the xanthene skeleton and the aryl group through the triple bond. Starting from the emission wavelength (λ_em) of 9-methyl xanthene 20 in basic DMSO solution at 536?nm, the emission wavelengths gradually shifted to the red region for methylacetylene 17 (λ_em?=?600?nm), phenylacetylene 5 (λ_em?=?636?nm), and p-CF₃-phenylacetylene 11 (λ_em?=?660?nm). On the basis of these data, we estimated the substituent effects for the red shift on the emission wavelength and rationally explained the results by DFT calculations. Furthermore, potential applicability of these fluorescent dyes to cell staining was exemplified.     

Memory of chirality in intramolecular conjugate addition of enolates: a novel access to nitrogen heterocycles with contiguous quaternary and tertiary stereocenters

Nitrogen heterocycles with contiguous quaternary and tertiary stereocenters have been prepared in high enantiomeric purity by intramolecular conjugate addition of enolates generated from alpha-amino acid derivatives via memory of chirality.     

Multiple-functional capsule catalysts: a tailor-made confined reaction environment for the direct synthesis of middle isoparaffins from syngas

A capsule catalyst for isoparaffin synthesis based on Fischer-Tropsch reaction was designed by coating a H-ZSM-5 membrane onto the surface of the pre-shaped Co/SiO(2) pellet. Morphological and chemical analysis showed that the capsule catalyst had a core-shell structure. A compact, integral shell of H-ZSM-5 crystallized firmly on the Co/SiO(2) substrate without crack. Syngas passed through the zeolite membrane to reach the Co/SiO(2) catalyst to be converted, and all hydrocarbons formed with straight chain structure must enter the zeolite channels to undergo hydrocracking as well as isomerization in this tailor-made confined reaction environment. A narrow, anti-Anderson-Schultz-Flory law product distribution was observed on these capsule catalysts. Contrary to a mechanical mixture of H-ZSM-5 and Co/SiO(2), C(10+) hydrocarbons were suppressed completely on this novel capsule catalyst, and the selectivity of middle isoparaffins was considerably improved. The carbon number distribution of the products depended on the thickness of the zeolite membrane, and it was possible to selectively synthesize specified distillates, such as gasoline-range, or heavier hydrocarbons from syngas directly, by simply adjusting the thickness of the zeolite membrane of the capsule catalyst. This kind of capsule catalysts can be extended to various consecutive reaction systems as the shell and core components are independent catalysts for different reactions. At the same time, shape selectivity and space-confined effects can be expected for the reactant, intermediates and product of the sequential reactions.