53463-68-6Relevant articles and documents
Hydroxyl-Assisted trans-Reduction of 1,3-Enynes: Application to the Formal Synthesis of (+)-Aspicilin
Schaubach, Sebastian,Michigami, Kenichi,Fürstner, Alois
, p. 202 - 208 (2017)
1,3-Enynes are hardly amenable to trans-hydrometalation reactions, because they tend to bind the standard ruthenium catalysts too tightly. However, catalysts comprising a [Cp?Ru-Cl] unit allow such compounds to be used, provided they contain an OH group next to the triple bond. This aspect is illustrated by a formal synthesis of the lichen-derived macrolide aspicilin. The required macrocyclic enyne precursor was formed by an efficient ring-closing alkyne metathesis reaction.
Synthesis of ent-BE-43547A 1 reveals a potent hypoxia-selective anticancer agent and uncovers the biosynthetic origin of the APD-CLD natural products
Villadsen, Nikolaj L.,Jacobsen, Kristian M.,Keiding, Ulrik B.,Weibel, Esben T.,Christiansen, Bj?rn,Vosegaard, Thomas,Bjerring, Morten,Jensen, Frank,Johannsen, Mogens,T?rring, Thomas,Poulsen, Thomas B.
, p. 264 - 272 (2017)
Tumour hypoxia is speculated to be a key driver of therapeutic resistance and metastatic dissemination. Consequently, the discovery of new potent agents that selectively target the hypoxic cell population may reveal new and untapped antitumour mechanisms. Here we demonstrate that the BE-43547 subclass of the APD-CLD (amidopentadienoate-containing cyclolipodepsipeptides) natural products possesses highly hypoxia-selective growth-inhibitory activity against pancreatic cancer cells. To enable this discovery, we have developed the first synthesis of the BE-43547-macrocyclic scaffold in 16 steps (longest linear sequence), which also allowed access to the full panel of relative stereoisomers and ultimately to the assignment of stereochemical configuration. Discrepancies between the spectroscopic signatures of the synthetic compounds with that originally reported for the BE-43547 members stimulated us to re-isolate the natural product from a BE-43547-producing microorganism during which we elucidated the biosynthetic gene clusters for the BE-43547 family as well as for all other known APD-CLDs. Our studies underline the exciting possibilities for the further development of the anticancer activities of these natural products.
Improvement of antimalarial activity of a 3-alkylpiridine alkaloid analog by replacing the pyridine ring to a thiazole-containing heterocycle: Mode of action, mutagenicity profile, and Caco-2 cell-based permeability
Guimar?es, Daniel Silqueira Martins,de Sousa Luz, Letícia Silveira,do Nascimento, Sara Batista,Silva, Lorena Rabelo,de Miranda Martins, Natália Rezende,de Almeida, Heloísa Gon?alves,de Souza Reis, Vitória,Maluf, Sarah El Chamy,Budu, Alexandre,Marinho, Juliane Aparecida,Abramo, Clarice,Carmona, Adriana Karaoglanovic,da Silva, Marina Goulart,da Silva, Gisele Rodrigues,Kemmer, Victor Matheus,Butera, Anna Paola,Ribeiro-Viana, Renato Márcio,Gazarini, Marcos Leoni,Júnior, Clébio Soares Nascimento,Guimar?es, Luciana,dos Santos, Fabio Vieira,de Castro, Whocely Victor,Viana, Gustavo Henrique Ribeiro,de Brito, Cristiana Ferreira Alves,de Pilla Varotti, Fernando
, (2019)
The development of new antimalarial drugs is urgent to overcome the spread of resistance to the current treatment. Herein we synthesized the compound 3, a hit-to?lead optimization of a thiazole based on the most promising 3-alkylpyridine marine alkaloid analog. Compound 3 was tested against Plasmodium falciparum and has shown to be more potent than its precursor (IC50 values of 1.55 and 14.7 μM, respectively), with higher selectivity index (74.7) for noncancerous human cell line. This compound was not mutagenic and showed genotoxicity only at concentrations four-fold higher than its IC50. Compound 3 was tested in vivo against Plasmodium berghei NK65 strain and inhibited the development of parasite at 50 mg/kg. In silico and UV–vis approaches determined that compound 3 acts impairing hemozoin crystallization and confocal microscopy experiments corroborate these findings as the compound was capable of diminishing food vacuole acidity. The assay of uptake using human intestinal Caco-2 cell line showed that compound 3 is absorbed similarly to chloroquine, a standard antimalarial agent. Therefore, we present here compound 3 as a potent new lead antimalarial compound.
Toward the synthesis of the hypoxia selective anticancer agent BE-43547 A2
Kranthikumar, Ramagonolla
supporting information, p. 9833 - 9839 (2021/12/07)
A short and enantioselective synthesis of the 19-epi-BE-43547 A2 chiral framework has been achieved in a high yield. The challenging key C15 tertiary stereocenter was derived from d-glucose. The synthetic strategy involves a Julia-Kocienski olefination to install the lipophilic side chain. An efficient protocol for Z to E isomerization of olefin was developed using a novel UV flow reactor. In addition, an unprecedented oxygen mediated hydroboration and the Krapcho decarboxylation of β-keto lactone were observed. This journal is
A New Asymmetric Synthesis of (S)-14-Methyloctadec-1-ene, the Sex Pheromone of the Peach Leafminer Moth
Bai, Hongjin,Du, Zhen-Ting,He, Guo-Guo,Liu, Lu,Tang, Meng,Wei, Liang,Zhang, Tao
, p. 1089 - 1095 (2020/07/25)
Abstract: An asymmetric synthesis of 14-methyl-1-octadecene, the sex pheromone of thepeach leafminer moth has been achieved. Based on the asymmetric methylation ofchiral (S)-4-benzyloxazolidin-2-one, thecarbon chain of the target molecule was assembled through aC1+C10+C4+C3procedure. The γ-lactone was transformed into 4-(benzyloxy)butanoic acid andthen, with the induction of Evan’s template, a chiral methyl group wasintroduced to the position of the carboxylic group in 97percent de. After reduction and a couple of chemicaloperations, the designed key intermediate A1was obtained. The synthesis of another moiety was started from decane-1,10-diolwhich was selectively protected and oxidized. The long carbon chain wasinstalled according to a Wittig protocol. After deprotection, oxidization, andmethylenation, the target molecule was synthesized in 7 linear steps with anoverall yield of 30.3percent.
Synthesis method of sex pheromone (S)-14-methyl-1-octadecene of lepidoptera pest peach leaf miners
-
Paragraph 0047; 0065-0066, (2020/08/02)
The invention discloses a synthesis method of a sex pheromone (S)-14-methyl-1-octadecene of peach leaf miners, which comprises the following steps: carrying out ring opening on gamma-butyrolactone asa raw material, reacting the gamma-butyrolactone with benzyl chloride to generate 4-benzyloxybutyric acid, and reacting the 4-benzyloxybutyric acid with (S)-4-benzyl-2-oxazolidinone; performing reaction with methyl iodide under the action of organic base to induce chiral methyl; reducing the chiral methyl into alcohol under the action of lithium aluminum hydride, oxidizing the alcohol into aldehyde, and carrying out wittig reaction with triphenylpropylphosphonium bromide; after the Wittig reaction, using a Pt/C as a catalyst for catalytic hydrogenation to remove double bonds, removing benzyl with Pd/C as a catalyst to form alcohol, and oxidizing the alcohol into aldehyde; carrying out monobromination on 1, 10-decanediol, carrying out single protection by using TBSCl, and performing reaction with triphenylphosphine to obtain quaternary phosphonium salt; carrying out Wittig reaction on the aldehyde and the quaternary phosphonium salt, and using Pt/C as a catalyst for catalytic hydrogenation to eliminate double bonds; removing TBS single protection to form alcohol, and then oxidizing the alcohol into aldehyde; and reacting the aldehyde with methyltriphenylphosphonium bromide wittig toobtain the pheromone (S)-14-methyl-1-octadecene. According to the method, the reaction conditions are mild, chiral methyl is kept in the reaction process, and racemization is avoided.
Industrial synthesis method of dichocrocis punctiferalis sex pheromone
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Paragraph 0023-0025, (2020/06/30)
The invention belongs to the field of chemical synthesis, and particularly relates to an industrial synthesis method of a dichocrocis punctiferalis sex pheromone. The method comprises the following steps: taking 1, 10-decanediol as a raw material; carrying out a single-side bromination reaction to prepare 10-bromodecanol; then reacting the 10-bromodecanol with triphenylphosphine to obtain 10-hydroxydecyltriphenylphosphine salt; performing a Wittig reaction with n-hexaldehyde under the action of alkali to obtain cis-based 10-hexadecene-1-ol; performing isomerization on the cis-based enol underthe action of p-methylthiophenol to obtain trans-based 10-hexadecene-1-ol; and finally performing oxidation under the action of an oxidant to obtain the final product 10-hexadecenal. The method is mild in reaction condition and suitable for large-scale production.
Supramolecular organogels based on mesogenic 2,7-difunctionalized triphenylenes as a simple system for water content assessment in light alcohols
Vadra, Nahir,Huck-Iriart, Cristián,Giovanetti, Lisandro J.,Di Chenna, Pablo H.,Cukiernik, Fabio D.
, p. 2423 - 2434 (2020/02/20)
A series of three triphenylene compounds-denoted 2,7-THTP-DiCnOH-bearing four hexyloxy ancillary chains and two variable-length alkoxy chains terminally functionalized with hydroxyl groups have been synthesized and characterized. The studied compounds exhibited thermotropic mesomorphism; the detailed nature of the mesophases was found to depend on the relative positions of the terminal functional groups relative to the crown formed by the ancillary chains. All the studied compounds were able to act as supramolecular gelators in a variety of alcohols; their organogelating ability has been rationalized in terms of physicochemical parameters like the dielectric constant, which allowed us to establish very precise predictive "solvent gelation windows" for each compound. Remarkably stable gels have been detected for 2,7-THTP-DiC6OH in methanol. As a proof of principle, we present the water sensing performance as a rapid method for the assessment of water content in alcohol samples based on the influence that the water content exerts on the gels' thermostability.
Practical Synthesis and Field Application of the Synthetic Sex Pheromone of Rice Stem Borer, Chilo suppressalis (Lepidoptera: Pyralidae)
Chien, Wei-Jynn,Gupta, Sachin,Liu, Bin,Lou, Da Wei,Shen, Yu-Jhe,Syu, Kun-Jie,Tseng, Jui-Chang,Zhang, Yuan-Xin
, (2020/03/11)
Rice stem borer, Chilo suppressalis, is a common and major serious pest of rice, maize, and wheat crops across Asia, Europe, and Oceania countries. Its sex pheromone consists of three analogously compounds, i.e., (Z)-hexadec-11-enal (1), (Z)-octadec-13-enal (2), and (Z)-hexadec-9-enal (3), as long-chain aliphatic internal cis-alkenyl aldehydes. In order to perform an economic and widespread pest control management of rice stem borer, a versatile and efficient synthetic strategy is required. A versatile and efficient synthesis using a common synthetic route for cis-alkenals with high overall yields is described. Commercially available inexpensive aliphatic diols were chosen as starting materials. Two key steps were employed to synthesize the long-chain aliphatic internal cis-alkenes in excellent yields, including the alkylation of terminal alkynes without the utilization of a highly polar aprotic cosolvent and the versatile cis-selective semihydrogenation for the reduction of internal alkynes with excellent stereoselectivity. The results of field tests showed that the synthetic sex pheromone blend was highly effective for the capture of rice stem borer.
Binding orientation and reactivity of alkyl α,ω-dibromides in water-soluble cavitands
Angamuthu, Venkatachalam,Petroselli, Manuel,Rahman, Faiz-Ur,Yu, Yang,Rebek, Julius
supporting information, p. 5279 - 5282 (2019/06/07)
Host-guest complexation of long chain α,ω-dibromides was evaluated in deep water-soluble cavitands 1 and 2. The bound dibromides (C7-C12) tumble rapidly on the NMR timescale and averaged signals were observed. The complexation allows mono hydrolysis of dibromides in aqueous solution. The arrangement of the products in the host-guest complex was fixed in an unsymmetrical manner that protects the guest from further reaction. Up to 93% yields of the mono-alcohols were obtained. The α,ω-dibromides formed a capsule with cavitand 2 and remained unreactive to hydrolysis.
