Construction of sulfur-containing moieties in the total synthesis of natural products

Natural Product Reports, Год журнала: 2019, Номер 37(2), С. 246 - 275

Опубликована: Июнь 17, 2019

Covering: January 2013 to September 2018Sulfur-containing natural products are a large class of significant functional molecules. Many these compounds exhibit potent biological activities and pharmacological properties; in fact, some them have been developed into important drugs. The total synthesis sulfur-containing is subject that has long attracted attention from synthetic organic chemists; achieve this goal, various methods over the past years. This review surveys syntheses introduce sulfur atoms using different sulfurization agents construct related moieties.

Язык: Английский

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Enzymatic Halogenation and Dehalogenation Reactions: Pervasive and Mechanistically Diverse

Chemical Reviews, Год журнала: 2017, Номер 117(8), С. 5619 - 5674

Опубликована: Янв. 20, 2017

Naturally produced halogenated compounds are ubiquitous across all domains of life where they perform a multitude biological functions and adopt diversity chemical structures. Accordingly, diverse collection enzyme catalysts to install remove halogens from organic scaffolds has evolved in nature. Accounting for the different properties four halogen atoms (fluorine, chlorine, bromine, iodine) reactivity their substrates, enzymes performing biosynthetic degradative halogenation chemistry utilize numerous mechanistic strategies involving oxidation, reduction, substitution. Biosynthetic reactions range simple aromatic substitutions stereoselective C–H functionalizations on remote carbon centers can initiate formation complex ring Dehalogenating enzymes, other hand, best known removing man-made organohalogens, yet also function naturally, albeit rarely, metabolic pathways. This review details scope mechanism nature's dehalogenation enzymatic strategies, highlights gaps our understanding, posits new advances field might arise near future.

Язык: Английский

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Development of Halogenase Enzymes for Use in Synthesis

Chemical Reviews, Год журнала: 2017, Номер 118(1), С. 232 - 269

Опубликована: Май 3, 2017

Nature has evolved halogenase enzymes to regioselectively halogenate a diverse range of biosynthetic precursors, with the halogens introduced often having profound effect on biological activity resulting natural products. Synthetic endeavors create non-natural bioactive small molecules for pharmaceutical and agrochemical applications have also arrived at similar conclusion: can dramatically improve properties organic selective modulation targets in vivo. Consequently, high proportion pharmaceuticals agrochemicals market today possess halogens. Halogenated compounds are common intermediates synthesis particularly valuable metal-catalyzed cross-coupling reactions. Despite potential utility organohalogens, traditional nonenzymatic halogenation chemistry utilizes deleterious reagents lacks regiocontrol. Reliable, facile, cleaner methods regioselective therefore essential development economical environmentally friendly industrial processes. A avenue toward such is use enzymes, responsible biosynthesis halogenated products, as biocatalysts. This Review will discuss advances developing halogenases biocatalysis, untapped sources biocatalysts how further optimization these required achieve goal scale biohalogenation.

Язык: Английский

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Electrocatalytic Radical Dichlorination of Alkenes with Nucleophilic Chlorine Sources

Journal of the American Chemical Society, Год журнала: 2017, Номер 139(43), С. 15548 - 15553

Опубликована: Окт. 8, 2017

We report a Mn-catalyzed electrochemical dichlorination of alkenes with MgCl2 as the chlorine source. This method provides operationally simple, sustainable, and efficient access to variety vicinally dichlorinated compounds. In particular, oxidatively labile functional groups, such alcohols, aldehydes, sulfides, amines, were transformed into desired vicinal dichlorides high chemoselectivity. Mechanistic data are consistent metal-mediated Cl atom transfer predominant pathway enabling dual C–Cl bond formation contradict an alternative involving evolution gas followed by Cl2-mediated electrophilic dichlorination.

Язык: Английский

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Recent Advances in the Intermolecular Oxidative Difunctionalization of Alkenes

The Chemical Record, Год журнала: 2018, Номер 19(2-3), С. 440 - 451

Опубликована: Июль 22, 2018

Abstract Functionalization of alkenes has been well investigated by chemists, thus it extensively applied in organic synthesis and industries. In the past few decades, transition‐metal, such as palladium, rhodium, gold, iridium, copper iron, catalyzed functionalization reactions have significantly developed played vital roles synthesis. The difunctionalization are appealing an important alternative to traditional approaches for construction useful carbon centers, particularly quaternary which commonly existed structural motifs numerous natural products, pharmaceuticals, biologically active molecules. This account will summarize our recent advances intermolecular alkenes, also highlight scope limitations mechanisms these reactions. general, this starting from dicarbofunctionalization be discussed. Then carboheterofunctionalization intensively reviewed, diheterofunctionalization highlighted.

Язык: Английский

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Automated iterative Csp3–C bond formation

Nature, Год журнала: 2022, Номер 604(7904), С. 92 - 97

Опубликована: Фев. 8, 2022

Язык: Английский

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Naturally Occurring Organohalogen Compounds—A Comprehensive Review

Fortschritte der Chemie Organischer Naturstoffe/Fortschritte der Chemie organischer Naturstoffe/Progress in the chemistry of organic natural products, Год журнала: 2023, Номер unknown, С. 1 - 546

Опубликована: Янв. 1, 2023

Язык: Английский

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Substrate Directed Asymmetric Reactions

Chemical Reviews, Год журнала: 2018, Номер 118(7), С. 3391 - 3446

Опубликована: Март 23, 2018

Historically, reagent controlled reactions (mechanism reactions) have played a significant role in the asymmetric synthesis of complex structures. In contrast, today's is greatly dependent on substrate directed approaches. this approach, polar functional group, namely, "directing group", vicinity reactive site inside has been documented to preassociate with chiral catalyst, which exerts stereodirecting influence by directing reacting partner toward one enantiotopic faces reaction center. Those usually proceed through exceptionally ordered transition states and result extraordinary levels stereoselection. Within last four decades, approach become an indispensible tool for preparation frameworks starting directly from relatively simple achiral molecules via induction or various resolution techniques both. Likewise, applied functionalize enantiopure substrates bearing pre-exisiting stereocenters into structures as single diastereomer. A classical example Sharpless epoxidation allylic alcohols free hydroxy function acts active anchor dimeric Ti-catalyst that controls stereochemical outcome process transferring oxidant enantioselectively. The principal aim present review give general overview transformations, topic not yet form concise recently developed Due large number related applications, only recent advances within two decades reviewed. Furthermore, current review, we mainly highlighted are abundant frequently used groups such hydroxy, amide, sulfonamide groups. addition, selected examples few important substrate-directed chemo-, regio-, diastereoselective also included review.

Язык: Английский

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Catalytic Enantioselective Dihalogenation in Total Synthesis

Accounts of Chemical Research, Год журнала: 2018, Номер 51(5), С. 1260 - 1271

Опубликована: Апрель 17, 2018

ConspectusTo date, more than 5000 biogenic halogenated molecules have been characterized. This number continues to increase as chemists explore chloride- and bromide-rich marine environments in search of novel bioactive natural products. Naturally occurring organohalogens span nearly all biosynthetic structural classes, exhibit a range unique biological activities, the subject numerous investigations. Despite abundance interest molecules, enantioselective methods capable forging carbon–halogen bonds synthetically relevant contexts remain scarce. Accordingly, syntheses often rely on multistep functional group interconversions establish stereocenters. Our has developed an dihalogenation reaction utilized it only reported examples catalytic halogenation product synthesis. In this Account, we describe our laboratory's development method for catalytic, application synthesis both mono- polyhalogenated first part, initial discovery TADDOL-mediated dibromination cinnamyl alcohols. Extension second-generation system selective bromochlorination, dichlorination, is then detailed. controlling enantioselectivity dihalide formation, chemoselectivity polyolefinic substrates, regioselectivity case bromochlorination. The ability exert control over halide delivery permits electronically nonbiased olefins required total synthesis.In second demonstrate how described provided efficient access host structurally diverse most direct methodology naturally vicinal dihalides. Chiral bromochlorides represent class >175 products; five members class, including its flagship member, (+)-halomon, accomplished through use Likewise, dichlorination two chlorosulfolipids, linear, acyclic polychlorides. Synthesis chiral monohalides achieved solvolysis enantioenriched bromochlorides; approach resulted bromocyclohexane-containing products enantiospecific bromopolyene cyclization. reviewing these syntheses, framework mediated by emerged.The highly enabling detail encourage further useful methodologies.

Язык: Английский

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Enantioselective Synthesis of Cyclobutenes by Intermolecular [2+2] Cycloaddition with Non-C₂ Symmetric Digold Catalysts

Journal of the American Chemical Society, Год журнала: 2017, Номер 139(39), С. 13628 - 13631

Опубликована: Сен. 19, 2017

The enantioselective intermolecular gold(I)-catalyzed [2+2] cycloaddition of terminal alkynes and alkenes has been achieved using non-C

Язык: Английский

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