Spiro Derivatives in the Discovery of New Pesticides: A Research Review

Journal of Agricultural and Food Chemistry, Journal Year: 2022, Volume and Issue: 70(35), P. 10693 - 10707

Published: Aug. 23, 2022

Spiro compounds are biologically active organic with unique structures, found in a wide variety of natural products and drugs. They do not readily lead to drug resistance due their mechanisms action have, therefore, attracted considerable attention regarding pesticide development. Analyzing structure-activity relationships (SARs) summarizing the characteristics spiro high activity crucial steps design development new pesticides. This review mainly summarizes insecticidal, bactericidal, fungicidal, herbicidal, antiviral, plant growth regulating functions provide insight for creation compound

Language: Английский

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Tailored Synthesis of Skeletally Diverse Stemona Alkaloids through Chemoselective Dyotropic Rearrangements of β‐Lactones

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(26), P. 14545 - 14553

Published: April 14, 2021

The collective synthesis of skeletally diverse Stemona alkaloids featuring tailored dyotropic rearrangements β-lactones as key elements is described. Specifically, three typical 5/7/5 tricyclic skeletons associated with stemoamide, tuberostemospiroline and parvistemonine were first accessed through chemoselective involving alkyl, hydrogen, aryl migration, respectively. By the rational manipulation substrate structures reaction conditions, these proceeded excellent efficiency, good chemoselectivity high stereospecificity. Furthermore, several polycyclic alkaloids, including saxorumamide, isosaxorumamide, stemonine bisdehydroneostemoninine, obtained from aforementioned late-stage derivatizations. A novel visible-light photoredox-catalyzed formal [3+2] cycloaddition was also developed, which offers a valuable tool for accessing oxaspirobutenolide related scaffolds.

Language: Английский

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Visible-Light-Mediated Vicinal Difunctionalization of Activated Alkynes with Boronic Acids: Substrate-Controlled Rapid Access to 3-Alkylated Coumarins and Unsaturated Spirocycles

Organic Letters, Journal Year: 2023, Volume and Issue: 25(5), P. 810 - 815

Published: Jan. 27, 2023

A visible-light-mediated difunctionalization of activated alkynes with boronic acid is unveiled to synthesize 3-alkylated coumarins and unsaturated spiro-lactones. The substituent at the para-position aryl ring alkynoate plays a pivotal role in selective formation chain-alkylated or spirocyclic compounds under mild conditions. reaction employs hypervalent iodine reagent ruthenium photocatalyst. spiro-lactones thus obtained were subjected another novel mode radical addition cascade cyclization (RACC) access various new fused compounds.

Language: Английский

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Diazo Tetramic Acids Provide Access to Natural-Like Spirocyclic Δ^α,β-Butenolides through Rh(II)-Catalyzed O–H Insertion/Base-Promoted Cyclization

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 89(11), P. 7366 - 7375

Published: Jan. 5, 2023

3-Diazotetramic acids were found to be valid substrates for the recently discovered approach toward natural-like Δα,β-spirobutenolides via Rh(II)-catalyzed O–H insertion into propiolic followed by base-promoted intramolecular Michael addition. The target obtained in generally high yields and, case of chiral 5-monosubstituted 3-diazotetramic acids, diastereoselectivity. synthesis that we report here was virtually insensitive structure though it somewhat sensitive thereby demonstrating quite a large scope. Thus, new class α-diazocarbonyl compounds suitable realization outlined above identified.

Language: Английский

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Utilizing Allenic Acids and Heterocyclic Diazo Compounds in the Synthesis of Polysubstituted Spirocyclic Butenolides and β-Methylidene 2-Furanones

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(4), P. 2782 - 2786

Published: Feb. 1, 2024

Herein, we report a novel approach for the assembly of spirocyclic Δ

Language: Английский

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Natural‐Like Spirocyclic Δ^α,β‐Butenolides Obtained from Diazo Homophthalimides

Chemistry - A European Journal, Journal Year: 2021, Volume and Issue: 27(31), P. 8221 - 8227

Published: April 14, 2021

Abstract α‐Diazo homophotalimides were reacted with various propiolic acids on Rh 2 (esp) catalysis. The resulting propiolate esters transformed into novel, heterocyclic Δ α,β ‐spirobutenolides in good to excellent product yields. approach represents a fundamentally novel entry natural‐like present many biologically active natural products as well fully synthetic compounds endowed diverse biological activities. thus obtained shown inhibit thioredoxin reductase, selenocysteine enzyme target for cancer. Moreover, the best compound series (TrxR IC 50 1.49±0.08 μM), by using MALDI‐TOF mass‐spectrometry it was that selectively binds presence of 10‐fold excess cysteine. This validates new promising lead anticancer therapy development.

Language: Английский

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Magnesium-catalyzed stereoselective transformations – A survey through recent achievements

Polyhedron, Journal Year: 2022, Volume and Issue: 219, P. 115790 - 115790

Published: March 23, 2022

Magnesium (Mg) constitutes one of the most abundant metal elements in Earth’s crust. The spectacular career magnesium organic chemistry has been initiated at beginning XX century and still lasting today. discovery organomagnesium compounds by Philippe A. Barbier Victor Grignard is commonly recognized as milestones development (organic) chemistry. subsequent applications reagents relatively easy generated synthons enantioselective reactions have opened new possibilities for acquiring enantiomerically enriched compounds. On other hand, asymmetric which plays a role catalyst can be considered limited, especially when their number compared to contributions aimed transition metal-catalyzed or organocatalyzed stereoselective transformations. However, taking into account current trends replacing expensive metals with cheaper counterparts making catalysis more environmentally (and user) friendly, modification known methods, employ Earth-abundant metals, very advisable. In this study we intend emphasize chemistry, mainly catalytic synthesis. Among already reported procedures, discussed recent examples, however, also mentioned some, groundbreaking previous ones. An exception pericyclic made, these constitute first examples use attention drawn some structural aspects, associated either experimentally-determined geometry species calculated state(s) given transformation.

Language: Английский

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Access to Spiropyrazolone-butenolides through NHC-Catalyzed [3 + 2]-Asymmetric Annulation of 3-Bromoenals and 1H-Pyrazol-4,5-diones

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(11), P. 6890 - 6900

Published: May 11, 2023

The stereoselective synthesis of spirocyclic pyrazolin-5-ones by N-heterocyclic carbene (NHC) organocatalysis has been less studied so far. For this reason and considering the interest class compounds, here, we present NHC-catalyzed [3 + 2]-asymmetric annulation β-bromoenals 1H-pyrazol-4,5-diones that achieves to produce chiral spiropyrazolone-butenolides. is general for aryl heteroaryl β-bromo-α,β-unsaturated aldehydes 1,3-disubstituted pyrazolones. spirobutenolides have obtained in good yields (up 88%) enantioselectivities 97:3 er). This constitutes first described example using pyrazoldiones as starting materials spiro compounds.

Language: Английский

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Synthesis of Spirolactones via a BF₃·Et₂O-Promoted Cascade Annulation of α-Keto Acids and 1,3-Enynes

Organic Letters, Journal Year: 2021, Volume and Issue: 23(15), P. 5698 - 5702

Published: July 15, 2021

A novel and effective method for the synthesis of spirolactones from readily available α-keto acids 1,3-enynes is developed via a BF3·Et2O-promoted cascade annulation. This sequential process conducted at room temperature, it provides functionalized in good to excellent yield under metal-free conditions.

Language: Английский

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Electrochemical oxidative dearomatization of 2-arylthiophenes

Organic Chemistry Frontiers, Journal Year: 2022, Volume and Issue: 9(11), P. 2921 - 2925

Published: Jan. 1, 2022

A green and sustainable electrochemical oxidative dearomatization of 2-arylthiophenes has been developed toward the preparation both C2/C3 C2/C5 difunctionalized thiophenones.

Language: Английский

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