Journal of Synthetic Organic Chemistry, Japan
Online ISSN : 1883-6526
Print ISSN : 0037-9980
ISSN-L : 0037-9980
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Volume 72, Issue 4
Displaying 1-13 of 13 articles from this issue
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Preface
Reviews and Accounts
  • Synthesis of Photoreactive Aromatic α-Amino Acids and Effective Hydrogen-Deuterium Exchange for Aromatic α-Amino Acids
    Makoto Hashimoto, Yuta Murai
    2014 Volume 72 Issue 4 Pages 360-369
    Published: April 01, 2014
    Released on J-STAGE: May 16, 2014
    DOIhttps://doi.org/10.5059/yukigoseikyokaishi.72.360
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    Photoaffinity labeling is one of the favorite methods for chemical biology. The first step in this method is the construction of photophores and their modification to the associated high affinity target ligand. α-Amino acids have biological activities themselves and are fundamental component of peptides and protein. The photoreactive aromatic α-amino acids are useful for investigation of biological phenomenon. Although synthesis of photoreactive phenylalanine analogues has already been reported, there have been few reports of the synthesis of photoreactive tryptophan and side-chain elongated phenylalanine. We report here the effective photoreactive tryptophan and side-chain elongated phenylalanine derivatives. Furthermore, we report the mild and controllable hydrogen-deuterium exchange for aromatic hydrogen with trifluoromethanesulfonic acid-d during the course of the synthesis of side-chain elongated phenylalanine. These hydrogen-deuterium exchange properties for these aromatic α-amino acids are identical to those of the peptides. With this method the exchange proceeds significantly faster than previously described methods. Detail analysis of the exchange revealed that the method was controllable by temperature-, time-, and dose- dependent manner.
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  • The Chemistry of Polymerase Chain Reaction—Development of the PCR Method Using New Modified Primers—
    Fumie Takei, Kazuhiko Nakatani
    2014 Volume 72 Issue 4 Pages 370-381
    Published: April 01, 2014
    Released on J-STAGE: May 16, 2014
    DOIhttps://doi.org/10.5059/yukigoseikyokaishi.72.370
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    DNA is a typical chemical compound consisted of carbon, hydrogen, oxygen, nitrogen, and phosphorus atoms. But the marked difference of DNA from other chemicals and biopolymers is that DNA can be amplified by polymerase. No matter how small amount of DNA can be in principle amplified. This has been achieved by polymerase chain reaction (PCR). PCR needs polymerase, templates, and primers. In this review, we focused our attention on the chemical probing of PCR primers. Because PCR is a basic technology in biology research fields, we sometime uses chemically labeled primers without any consciousness on its chemistry behind. We would like to emphasize that chemically labeled primers contained a lot of chemistry ideas and much study is still necessary for advancing the PCR for SNP typing and genetic diagnosis, and other fields. Here, we focus the affinity-capture primers and signaling primers. The former is used for purification, isolation and manipulation of PCR product by high specificity and affinity to the cognate molecules by the molecular-molecular interaction. The latter has fluorescent molecule or fluorescence binding sites in hairpin primers, and the fluorescence emitted from the primer is used for a PCR monitoring system.
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  • Synthetic Reactions Using a Low-Valent Titanium Reagent Ti(OR)4/Me3SiCl/Mg
    Sentaro Okamoto
    2014 Volume 72 Issue 4 Pages 382-392
    Published: April 01, 2014
    Released on J-STAGE: May 16, 2014
    DOIhttps://doi.org/10.5059/yukigoseikyokaishi.72.382
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    In the presence of Me3SiCl or MgCl2, Ti(OR)4 was reduced by Mg powder in THF to gradually generate a specific low-valent titanium species, which mediated or catalyzed several synthetic reactions such as C-O bond-cleavage of allyl and propargyl ethers and esters, intra- and intermolecular cyclotrimerization of alkynes, reduction of epoxides and oxetanes via homolytic ring-opening, McMurry coupling reaction of aryl aldehydes, imino-pinacol coupling and reductive N-S or O-S bond-cleavage of sulfonamides or sulfonyl esters.
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  • Analysis of Fundamental Organic Reaction Mechanisms by Using Molecular Dynamics Simulations: The Dynamics Effect on the Reaction Pathway
    Makoto Sato, Hiroshi Yamataka
    2014 Volume 72 Issue 4 Pages 393-404
    Published: April 01, 2014
    Released on J-STAGE: May 16, 2014
    DOIhttps://doi.org/10.5059/yukigoseikyokaishi.72.393
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    Recently, dynamics effect is claimed to be a very important factor in determining the reaction mechanisms. In molecular dynamics (MD) simulations of the Beckmann rearrangement/fragmentation, E2/E1cb, and carbonyl addition/substitution, the dynamic path bifurcation was observed, where two reaction products were obtained dynamically depending on the shape of the potential energy surface after passing through the corresponding transition state (TS). This is a very significant problem because the strategies of organic syntheses are generally based on the transition state theory, intending to stabilize/destabilize the TS of a desired/undesired reaction relative to the other ones. As applications of the MD simulations in solution chemistry, fundamental organic reactions (SN2 reaction of the methyl diazonium ion, hydration and amination of formaldehyde) in water solution were examined by using the fragment molecular orbital method with MD, FMO-MD. These simulations revealed that the reactions in solution are more complicated and various than one would expect.
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  • Development of Catalytic Asymmetric Reactions Based on Conformational Control
    Kazuhiro Kondo
    2014 Volume 72 Issue 4 Pages 405-417
    Published: April 01, 2014
    Released on J-STAGE: May 16, 2014
    DOIhttps://doi.org/10.5059/yukigoseikyokaishi.72.405
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    In this review, our studies in relation to development of catalytic asymmetric reactions based on conformational control, are embodied, which are divided by content into four sections as follows: (1) asymmetric Grignard cross-coupling reaction with Pd and a N-Ar axially chiral mimetic-type ligand catalyst; (2) asymmetric intramolecular α-arylation of N-(2-bromophenyl)-2-arylpropanamides with Pd and a chiral mimetic-type N-heterocyclic carbene ligand catalyst; (3) asymmetric arylation of aromatic aldehydes using phenylboronic acid with Rh and a hemilabile phosphorus ligand based on conformational control; (4) asymmetric arylation of conformatinally fixed aromatic aldehydes bearing an ortho-Me2PhSi group, using potassium 1-aryl-4-methyl-2,6,7-trioxa-1-boranuidabicylo[2.2.2]octanes as aryl sources with Ni and a (R,R)-Et-duphos ligand catalyst.
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  • New Development of Base-Induced Sommelet-Hauser Rearrangement of Ammonium Ylides
    Eiji Tayama
    2014 Volume 72 Issue 4 Pages 418-428
    Published: April 01, 2014
    Released on J-STAGE: May 16, 2014
    DOIhttps://doi.org/10.5059/yukigoseikyokaishi.72.418
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    The Sommelet-Hauser rearrangement of N-benzylic ammonium ylides generated from tetraalkylammonium salts is an interesting and useful transformation in organic synthesis that can provide easy access to ortho-substituted aromatic compounds. The base-induced rearrangement of an N-chiral-N-benzylic proline-derived ammonium salt or N-benzylic amino acid (−)-8-phenylmenthol ester-derived ammonium salts is shown to proceed in excellent yields with perfect levels of diastereoselectivity without any detectable amount of the [1,2]Stevens rearrangement product. A solution of potassium tert-butoxide in THF was shown to remarkably enhance the base-induced Sommelet-Hauser rearrangement of N-benzylic amino acid-derived ammonium salts. The reaction proceeds under mild conditions with minimal competition from the [1,2]Stevens rearrangement. These methods provide efficient access to α-aryl-α-amino acid, α-aryl-β-amino acid, and α-arylpipecolinic acid derivatives.
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