HETEROCYCLES
An International Journal for Reviews and Communications in Heterocyclic ChemistryWeb Edition ISSN: 1881-0942
Published online by The Japan Institute of Heterocyclic Chemistry
Special Issue
Albert Padwa's Special Issues,Vol. 84, No. 2, 2012
Published online: 7th October, 2011
■ A New Derivative of Galanthamine: Methylene Insertion into the Aromatic Ring in Place of Cyclopropanation
Péter Keglevich, Péter Kovács, László Hazai, Zsuzsanna Sánta, Zsófia Dubrovay, Viktor Háda, Csaba Szántay, Jr., György Kalaus, and Csaba Szántay*
*Department of Organic Chemistry and Technology, Budapest University of Technology and Economics, H-1111 Budapest, Szt. Gellért tér 4, Hungary
Abstract
In the course of the reaction between galanthamine and diazomethane in the presence of a catalyst, such as palladium(II) acetate or copper(I) bromide, methylene insertion into the aromatic ring was observed instead of the expected cyclopropanation of the carbon-carbon double bond.
Published online: 20th October, 2011
■ Synthesis of Aza-Surfactin and 3-Epi-Aza-Surfactin
Yi-Lin Huang, Raphael Frey, M. Elisa Juarez-Garcia, and Jeffrey W. Bode*
*Laboratory of Organic Chemistry, Department of Chemistry and Applied Biosciences, ETH Zürich, Wolfgang-Pauli-Strasse 10, CH-8093 Zuerich, Switzerland
Abstract
Two synthetic approaches to aza-surfactins are reported. In the first, our recently developed synthesis of unnatural β3-amino acids was used to prepare the requisite monomer, which was used in solid phase peptide synthesis, and followed by macrolactamization of a partially protected precursor. In the second, the corresponding β3-N-hydroxyaminoacid was used to prepare a fully unprotected cyclization precursor that was closed to give 3-epi-aza-surfactin by the first example of cyclization by the α-ketoacid–hydroxylamine amide formation.
Published online: 28th October, 2011
■ Synthetic Studies on MPC1001: A Dipolar Cycloaddition Approach to the Pyrrolidine Ring System
Paul T. Schuber and Robert M. Williams*
*Department of Chemistry, Colorado State University, Fort Collins, CO 80523-1872, U.S.A.
Abstract
A novel [1,3]-dipolar azomethine ylide cycloaddition has been developed in an approach to the synthesis of the MPC1001 family of natural products.
Published online: 8th June, 2011
■ New Hydrazine-Based Organocatalyst for Asymmetric Diels-Alder Reaction of 1,2-Dihydropyridines
Yuko Okuyama, Kenichi Osone, Hiroto Nakano, and Mitsuhiro Takeshita*
*Tohoku Pharmaceutical University, 4-4-1 Komatsushima, Aoba-ku, Sendai 981-8558, Japan
Abstract
Chiral hydrazinoalcohol organocatalyst is designed and synthesized as a new organocatalyst for the enantioselective Diels-Alder reaction between 1,2-dihydropyridines and acrolein derivatives to produce an optical active isoquinuclidine derivative (up to 67% ee with up to 96% yield).
Published online: 26th May, 2011
■ Access to Some UV Chromophore-Containing Antimalarial Trioxanes Using Hydrogen Peroxide as Source of the Peroxy Bonds
Yun Li, Sergio Wittlin, and Yikang Wu*
*State Key Laboratory of Bioorganic and Natural Products Chemistry, Shanghai Institute of Organic Chemistry, 345 Lingling Road, Shanghai 200032, China
Abstract
Several trioxanes were synthesized through perhydrolysis of an allylic epoxide followed by ketal exchange with a proper dimethyl ketal.
Published online: 3rd June, 2011
■ Formal Synthesis of (-)-Clavepictine A and (+)-Clavepictine B from a Sulfinimine (N-Sulfinylimine)-Derived Chiral Building Block
Franklin A. Davis* and He Xu
*Department of Chemistry, Temple University, 1901 N. 13th Street, Philadelphia, PA 19122, U.S.A.
Abstract
The sulfinimine-derived chiral building block trans-2,6-disubstituted 1,2,5,6-tetrahydropiperidine (+)-5 was employed in a concise formal asymmetric synthesis of the cytotoxic marine alkaloids clavepictines (-)-A and (+)-B (1a and 1b). This synthesis is highlighted by a highly diastereoselective hydroboration-oxidation reaction to install the C-3 hydroxyl group.
Published online: 17th June, 2011
■ A New 3-(Ethoxycarbonylmethyl)isoxazolopyridone as a Precursor to Acylpyridones
Raymond C. F. Jones,* James N. Iley, and Georgia Loizou
*Department of Chemistry, Loughborough University, Leicestershire LE11 3TU, U.K.
Abstract
A new 3-(ethoxycarbonylmethyl)isoxazolo[4,3-c]pyridin-4-one has been prepared as a potential precursor to 3-acyl-4-hydroxypyridin-2-ones, by a route involving dipolar cycloaddition of nitrile oxides derived from β-alanine with an enamino-ester.
Published online: 22nd June, 2011
■ Nonactin and Related Compounds Found in a Screening Program for Wnt Signal Inhibitory Activity
Yuuya Tamai, Kazufumi Toume, Midori A. Arai, Akinori Hayashida, Hikaru Kato, Yoshikazu Shizuri, Sachiko Tsukamoto, and Masami Ishibashi*
*Department of Natural Products Chemistry, Graduate School of Pharmaceutical Science, Chiba University, 1-33 Yayoi-cho, Inage-ku, Chiba 263-8522, Japan
Abstract
A screening study using a luciferase assay to identify natural products with inhibitory activity against Wnt signaling was carried out. Fractionation of the culture extract of an actinomycete, strain CKK179, led to the identification of nonactin (1), monactin (2), and dinactin (3) as active compounds. We examined the effects of dimeric dinactin (4), isolated from another actinomycete, Streptomyces sp. (YM09-028), on Wnt signaling activity and found that 1 - 4 inhibited TCF/β-catenin transcriptional activity with IC50 values of 0.6 - 7.4 nM.
Published online: 16th June, 2011
■ Synthesis of Octahydroquinolizinones Aza-Analogues of Terpenoid Skeletons
Alberto Brandi,* Franca M. Cordero, Carolina Vurchio, Massimo Lucentini, and Stefano Cicchi
*Department of Chemistry "Ugo Schiff", University of Florence, Via della Lastruccia 13, 50019 Sesto Fiorentino (FI), Italy
Abstract
Two new ketones, 6,6,9a-trimethyl-octahydro-quinolizin-2-one and 4,4,9a-trimethyl-octahydro-quinolizin-2-one, were synthesized by regioselective 1,3-dipolar cycloaddition of tetrahydropyridine nitrones with methylenecyclopropanes followed by thermal rearrangement. The new ketones feature a structural analogy with the 5,5,8a-trimethyl-octahydro-2-naphthalene skeleton typical of terpenoid structures.
Published online: 14th July, 2011
■ Sabinaperins A and B, Two New Lignans from Juniperus sabina
Jenis Janar, Alfarius Eko Nugroho, Yusuke Hirasawa, Bahargul Konirhan, and Hiroshi Morita*
*Faculty of Pharmaceutical Sciences, Hoshi University, 2-4-41 Ebara, Shinagawa-ku, Tokyo 142-8501, Japan
Abstract
Two new lignans, sabinaperins A (1) and B (2), have been isolated from the aerial part of Juniperus sabina L. together with six known lignans. Their structures were established on the basis of 1D and 2D-NMR data analysis.
Published online: 1st August, 2011
■ Chisomicines D and E, Two New Limonoids from Chisocheton ceramicus
Ibrahim A. Najmuldeen, A. Hamid A. Hadi,* Khalit Mohamad, Khalijah Awang, Kamal Aziz Ketuly, Mat Ropi Mukhtar, Hairin Taha, Noraziah Nordin, Marc Litaudon, Françoise Guéritte, Alfarius Eko Nugroho, and Hiroshi Morita*
*Department of Chemistry, Faculty of Science, University of Malaya, Pantai Valley, 50603 Kuala Lumpur, Malaysia
Abstract
Two new limonoids, chisomicines D and E (1 – 2) have been isolated from the bark of Malaysian Chisocheton ceramicus (Miq.) C. DC. Their structures were elucidated on the basis of 1D and 2D-NMR data analysis.
Published online: 15th July, 2011
■ 2nd Generation Palladium-Catalyzed Cycloalkenylation in Iridoid Synthesis: Diastereoselective Total Synthesis of Isoiridomyrmecin and Isodihydronepetalactone
Kazutaka Takeda and Masahiro Toyota*
*Department of Chemistry, Graduate School of Science, Osaka Prefecture University, Sakai, Osaka 593-8531, Japan
Abstract
Two different types of iridoids, isoiridomyrmecin and isodihydronepetalactone, were diastereoselectively synthesized using a 2nd generation palladium-catalyzed cycloalkenylation as the key step.
Published online: 28th July, 2011
■ A Facile and Convenient Method for the Synthesis of 6,8-Bis(trifluoroacetyl)quinolin-5-amines
Dai Shibata, Maurice Médebielle, Mizuki Hatakenaka, and Etsuji Okada*
*Department of Chemical Science and Engineering, Graduate School of Engineering, Kobe University, 1-1 Rokkodai-cho, Nada-ku, Kobe 657-8501, Japan
Abstract
New 6,8-bis(trifluoroacetyl)quinolin-5-amines (6) were easily prepared in moderate to high yields by the aromatic nucleophilic nitrogen-nitrogen exchange reaction of N,N-dimethyl-6,8-bis(trifluoroacetyl)-quinolin-5-amine (5) with various aliphatic and aromatic amines.
Published online: 21st July, 2011
■ Reinvestigation of the Classical Total Synthesis of Makomakine
Makoto Furuya, Ayumi Nagatomo, and Masahiro Toyota*
*Department of Chemistry, Graduate School of Science, Osaka Prefecture University, 1-1 Gakuencho, Sakai, Osaka 593-8531, Japan
Abstract
Reinvestigation of the original Stevens synthesis of makomakine showed that the yield of the Ritter reaction of 3-indoylacetonitrile with (–)-β-pinene could be increased by employing Hg(OTf)2.
Published online: 29th August, 2011
■ An Improved Synthesis of Functionalized cis-Decahydroquinolines Using a Baylis-Hillman-Type Adduct
Junfeng Huang, Jeffrey Petersen, and Stephen C. Bergmeier*
*Department of Chemistry and Biochemistry, Ohio University, Clippinger Laboratories, Athens, OH 45701-2979, U.S.A.
Abstract
An efficient and diastereoselective method to synthesize highly functionalized cis-decahydroquinolines was reported. The addition of a vinyl aluminum reagent to an aldehyde followed by an intramolecular SN2’ Mitsunobu reaction gave the desired 3,7,8-trisubstituted product designed as methyllycaconitine analogs. An unexpected tandem vinylaluminum addition and Michael reaction to produce a 4-hydroxy cis-decahydroquinoline has also been reported.
Published online: 21st July, 2011
■ Practical Total Synthesis of Luotonin A by Intramolecular Double Hetero Diels-Alder Reaction
Ken Natsuki, Tadamichi Shindo, and Masahiro Toyota*
*Department of Chemistry, Graduate School of Science, Osaka Prefecture University, 1-1 Gakuencho, Sakai, Osaka 593-8531, Japan
Abstract
An intramolecular double hetero Diels–Alder reaction of N-(2-cyanoquinolin-3-ylmethyl)-2-tosyloxybenzamide (3c) provided luotonin A (2) in 82% yield. Surprisingly, N-(2-bromoquinolin-3-ylmethyl)-2-tosyloxybenzamide (4) directly provided luotonin A (2) in 78% yield in the presence of Pd2(dba)3 (5 mol %), dppf (20 mol %), and K2CO3 (6 eq).
Published online: 2nd August, 2011
■ Quinoline Fused Heterocycles from Intramolecular Cycloaddition Reactions
Giuseppe Cremonesi, Piero Dalla Croce,* Maddalena Gallanti, and Concetta La Rosa
*Department of Organic and Industrial Chemistry, Faculty of Pharmacy, University of Milano, Via Venezian 21, I-20133 Milano, Italy
Abstract
Ring fused quinoline heterocycles such as isoxazolo-, pyrrolo- and pyrazoloquinolines (7,9,11,14) have been prepared by intramolecular 1,3-dipolar cycloaddition reactions starting from the suitable intermediates. The structures of the products were assigned by means of analytical and spectroscopic data.
Published online: 11th August, 2011
■ Synthesis of Ruthenium(II) 2,6-Bis(imino)pyridyl Complexes for C-H Amination of Sulfamate Esters
Jennifer L. Bon and Simon B. Blakey*
*Department of Chemistry, Emory University, 1515 Dickey Drive, Atlanta, GA 30322, U.S.A.
Abstract
A family of ruthenium(II) 2,6-bis(imino)pyridyl complexes have been developed as a novel catalyst framework for C-H amination. Their synthesis and evaluation is herein described. The reactivity of these catalysts is heavily dependent upon the electronics of the ligand. These complexes are capable of functionalizing the benzylic protons of sulfamate esters with good conversion.
Published online: 8th August, 2011
■ Synthetic Studies on Paspaline: Lewis Acid-Mediated Sequential Construction of A-E Ring Skeleton
Kentaro Okano, Yu Yoshii, and Hidetoshi Tokuyama*
*Department of Organic Chemistry, Graduate School of Pharmaceutical Sciences, Tohoku University, Aramaki, Aoba-ku, Sendai 980-8578, Japan
Abstract
The common pentacyclic skeleton of indole diterpene alkaloids, paspaline and its derivatives was constructed by a sequential reaction. The appropriate choice of the protecting group on the indole nitrogen was critical for the formation of bis(methylthio)allylic alcohol, which then underwent sulfonium ion formation and intramolecular electrophilic C-C-bond formation at the indole 3-position.
Published online: 3rd August, 2011
■ A Synthetic Approach to Aromatic Aminoglycoside as a Neamine Mimic
Ryo Inoue, Sho Matsuda, Yoshiki Oda, Hirofumi Ooyama, Akihiro Yoshida, Keita Hamasaki, and Takashi Yamanoi*
*The Noguchi Institute, 1-8-1, Kaga, Itabashi-ku, Tokyo 173-0003, Japan
Abstract
This paper describes the synthetic approach to an aromatic α-glycoside as a mimic of neamine, which is a common core structure of some aminoglycoside antibiotics. We achieved the synthesis of the protected precursor of the neamine mimic, 4-(2,6-diamino-2,6-dideoxy-α-D-glucopyranosyloxy)-1,3-phenylenediamine, from N-acetyl-D-glucosamine and 2,4-diaminophenol as the starting materials using a glycosylation technique.
Published online: 24th August, 2011
■ Synthesis of Substituted Phenazines via Palladium-Catalyzed Aryl Ligation
Jeffrey D. Winkler,* Barry M. Twenter, and Thomas Gendrineau
*Department of Chemistry, University of Pennsylvania, 231 South 34th Street, Philadelphia
PA 19104-6323, U.S.A.
Abstract
A method for the “ligation” of two aromatic rings has been achieved via synthesis of functionalized phenazines by double Buchwald-Hartwig amination of a variety of substituted bromoanilines, followed by in situ oxidation.
Published online: 16th August, 2011
■ Deprotection of 3,4-Dimethoxybenzyl (3,4DMB) Group on γ-Lactam Nitrogen Using Phenyliodine(III) Bis(trifluoroacetate) (PIFA): Application to Isoindolinone Compounds
Kazuhiro Watanabe, Hiroaki Shibata, Yū Imai, and Tadashi Katoh*
*Department of Synthetic Organic Chemistry, Tohoku Pharmaceutical University, 4-4-1 Komatsushima, Aoba-ku, Sendai 981-8558, Japan
Abstract
The secondary amide (γ-lactam) moiety of an isoindolinone ring exhibits high polarity in an unprotected condition. Problems with solubility make handling difficult; therefore, introduction of a protective group is necessary. We discovered that the 3,4-dimethoxybenzyl (3,4DMB) group is an optimal protective group, and that the 3,4DMB group alone could be deprotected under mild conditions with the use of a hypervalent iodine(III) reagent, phenyliodine(III) bis(trifluoroacetate) (PIFA).
Published online: 26th September, 2011
■ Diastereoselective Synthesis of (±)-Deethyleburnamonine Using a Catalytic Cyclopropane Ring-Opening / Friedel-Crafts Alkylation Strategy
Dadasaheb V. Patil, Marchello A. Cavitt, and Stefan France*
*School of Chemistry and Biochemistry, Georgia Institute of Technology, 901 Atlantic Drive, Atlanta, Georgia 30332-0400, U.S.A.
Abstract
A short, diastereoselective synthesis of (±)-deethyleburnamonine is reported with an overall yield of ~18% over six steps. The key synthetic step involves an indium(III)-catalyzed tandem ring-opening/Friedel-Crafts alkylation of a donor-acceptor-acceptor amino cyclopropane to generate the ABDE portion of the target.
Published online: 12th September, 2011
■ Synthesis of Oxacalix[2]m-terphenyl[2]triazine and Its Functionalizations
Muhammad Moazzam Naseer, De-Xian Wang, and Mei-Xiang Wang*
*Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Molecular Recognition and Function, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China
Abstract
Oxacalix[2]m-terphenyl[2]triazine, a macrocyclic host molecule of an expanded cavity, was synthesized from 1,3-(4-hydroxyphenyl)benzene and cyanuric chloride using the fragment coupling strategy. Aromatic nucleophilic substitution reaction of chlorotriazine moieties with di(2-hydroxyethyl)amine and di(2-pyridylmethyl)amine afforded the corresponding upper-rim functionalized oxacalix[2]m-terphenyl[2]triazines in good yields.
Published online: 1st November, 2011
■ The Synthesis and Antimicrobial Evaluation of Some Spiro-Phthalidyl Benzoxazinones
Caterina Ferraro, István Lengyel, and Ralph Stephani*
*Department of Chemistry, St. John's University, 8000 Utopia Parkway, Jamaica, New York 11439, U.S.A.
Abstract
Five N-substituted spiro-phthalidyl benzoxazinones (5a-e) were prepared from anthranilic acid (1) and the appropriate alkyl or aryl halides (2), followed by condensation of the N-substituted anthranilic acids (3) with symmetrical phthaloyl dichloride (4). These compounds were then evaluated for antimicrobial activity against: E. coli, S. aureus, B. subtilis, P. aeruginosa, S. cerevisiae, and A. nidulans. Compound 5a was active against all the microbes tested, especially the A. nidulans. Compound 5c was active against all the bacteria, except the fungus A. nidulans. The N-benzyl (5b) and N-phenyl (5d) derivatives were not active at all. The N-4-fluorophenyl analog 5e showed activity against S. aureus and B. subtilis.