Transition metal-catalyzed branch-selective hydroformylation of olefins in organic synthesis

Green Synthesis and Catalysis, Год журнала: 2021, Номер 2(3), С. 247 - 266

Опубликована: Май 7, 2021

Hydroformylation of olefins can generate linear and branched aldehydes, the aldehydes are attractive precursors for synthesis fine chemicals pharmaceuticals. is considered an important strategy green chemistry because its intrinsic atom economic nature recent development highly selective protocols. We herein summarize advances hydroformylation showing selectivity in organic synthesis. A mechanistic discussion provided prior to examples synthetically useful branch-selective reactions. Branch-selective further contribute construction chiral molecules design one-pot This review aims provide information about catalyst selection, reaction conditions, substrate scope hydroformylation, inspire this chemistry.

Язык: Английский

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Photoinduced Copper-Catalyzed Regio- and Enantioselective Alkynylation of Epoxides

ACS Catalysis, Год журнала: 2024, Номер 14(10), С. 7553 - 7561

Опубликована: Май 1, 2024

Epoxides are privileged and valuable electrophiles frequently utilized as versatile building blocks in synthetic chemistry to prepare diverse alcohols through ring-opening reactions. However, the catalytic stereoconvergent cross-coupling of racemic epoxides with electro- or nucleophiles has remained a persistent challenge. In this work, we present mild method achieve regio- enantioselective alkynylation various alkynes, resulting synthesis β-chiral homopropargyl via photoinduced copper-based system. The use monofluoro-substituted non-C2 symmetric bisoxazoline diphenylamine ligand played pivotal role success chemistry, its distinct electronic steric effects proving crucial enhancing both reactivity stereoselectivity. Mechanistic studies supported idea that reaction underwent regioselective nucleophilic iodides, followed by radical alkynes. Notably, hydroxyl group generated from epoxide may play an auxiliary achieving high enantioselectivity.

Язык: Английский

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Samarium(ii) iodide-mediated reactions applied to natural product total synthesis

RSC Advances, Год журнала: 2022, Номер 12(16), С. 9944 - 9994

Опубликована: Янв. 1, 2022

Natural product synthesis remains a field in which new synthetic methods and reagents are continually being evaluated.

Язык: Английский

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How to Break the Law: trans‐Hydroboration and gem‐Hydroboration of Alkynes

Israel Journal of Chemistry, Год журнала: 2023, Номер 63(7-8)

Опубликована: Март 9, 2023

Abstract Classical hydroboration is the textbook example of an organometallic reaction under rigorous frontier orbital control: a synergetic bonding mode between substrate and reagent evolves into four‐membered transition state that enforces syn /suprafacial delivery H−BR 2 to π‐system. This strict stereochemical “law” remained valid for decades, even after advent metal‐catalyzed hydroboration. During last decade, however, numerous possibilities emerged allow this paradigm be challenged. Thus, direct trans ‐hydroboration terminal as well internal alkynes was achieved through radical, ionic, organocatalytic, manifolds, which are summarized in review. Among them, pathways involving either metal vinylidenes (Rh, Ir, Ru, Fe) derived from or metallacyclopropenes (η ‐vinylmetal complexes) triple bond [Cp X Ru]‐based catalyst represent currently most widely applicable solutions. The latter type intermediates also accountable equally perplexing gem alkynes: geminal borane has no precedent classical canon. only forerunner ‐hydrogenation, represents unconventional yet highly useful entry discrete ruthenium carbene complexes. close mechanistic ties these transformations outlined, brief reference made remotely related reactions such ‐diboration ‐carboboration.

Язык: Английский

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Recent Advances in Catalytic Carbonylation Reactions in Alternative Reaction Media

Chinese Journal of Chemistry, Год журнала: 2023, Номер 42(4), С. 406 - 429

Опубликована: Окт. 3, 2023

Comprehensive Summary Since the discovery of hydroformylation (oxo‐synthesis or Roelen reaction) and Reppe‐reaction, transition metal‐catalyzed carbonylation reactions, providing versatile, facile, even atom‐economic methods for selective incorporation C=O functionality to various skeletons, have gained tremendous importance in synthetic organic chemistry from laboratories industrial applications. The carbon‐carbon multiple bonds, aromatic halides, triflates, etc ., presence nucleophiles has led way produce aldehydes, carboxylic acids, esters, amides, fine chemical industry. However, these protocols usually proceed conventional, fossil‐based, toxic reaction environments. Thus, several attempts been directed developing efficient alternative, less harmful, non‐fossil‐based renewable media. In this review, we overview recent applications alternative solvents such as water, biomass‐based alcohols, γ‐valerolactone (GVL), 2‐methyltetrahydrofuran (2‐MeTHF), ionic liquids (ILs), deep eutectic (DES), alkyl levulinates, limonene, α‐pinene, dimethyl carbonate well fluorous media improve efficiency, safety environmentally benign nature protocols.

Язык: Английский

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Wacker-type oxidation of styrenes with Markovnikov selectivity using copper as a site-selective sequential photooxidant–photoreductant

Catalysis Science & Technology, Год журнала: 2024, Номер 14(14), С. 4068 - 4074

Опубликована: Янв. 1, 2024

Copper acts as a site-selective photooxidant and photoreductant, thus enabling the Wacker-type oxidation of styrenes to acetophenones.

Язык: Английский

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Total Synthesis of Mycinolide IV and Path‐Scouting for Aldgamycin N

Angewandte Chemie International Edition, Год журнала: 2021, Номер 60(14), С. 7893 - 7899

Опубликована: Янв. 15, 2021

Abstract Proof‐of‐concept is provided that a large estate of 16‐membered macrolide antibiotics can be reached by “unified” approach. The key building block was formed on scale an asymmetric vinylogous Mukaiyama aldol reaction; its alkene terminus then converted either into the corresponding methyl ketone Wacker oxidation or chain‐extended aldehyde catalyst‐controlled branch‐selective hydroformylation. These transformations ultimately opened access to two structurally distinct series targets. Notable late‐stage maneuvers comprise rare example ruthenium‐catalyzed redox isomerization 1,3‐enyne‐5‐ol 1,3‐diene‐5‐one derivative, as well elaboration tertiary propargylic alcohol acyloin trans ‐hydrostannation/Chan‐Lam‐type coupling. Moreover, this case study illustrates underutilized possibility forging complex macrolactone rings transesterification under essentially neutral conditions.

Язык: Английский

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Ruthenium‐Catalyzed Butadiene‐Mediated Crotylation and Oxazaborolidine‐Catalyzed Vinylogous Mukaiyama Aldol Reaction for The Synthesis of C1–C19 and C23–C35 of Neaumycin B

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(52)

Опубликована: Ноя. 2, 2022

Neaumycin B is a femtomolar inhibitor of U87 human glioblastoma. Using newly developed anti-diastereoselective ruthenium-catalyzed butadiene-mediated crotylation primary alcohol proelectrophiles via hydrogen auto-transfer, as well novel variant the catalytic asymmetric vinylogous Mukaiyama aldol (VMA) reaction applicable to linear aliphatic aldehydes and terminally methylated dienyl ketene acetals, preparation key C1-C19 C23-C35 substructures neaumycin achieved in 12 7 steps (LLS), respectively.

Язык: Английский

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Structure revision of lagunamide C to odoamide by total synthesis and biological evaluation

Tetrahedron, Год журнала: 2024, Номер 154, С. 133871 - 133871

Опубликована: Фев. 8, 2024

Язык: Английский

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Bioinspired Syntheses of Seven Macrodiolide Analogs of Aplysiatoxin by the Late-Stage Functionalization of a Dehydroaplysiatoxin Derivative

The Journal of Organic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Июнь 1, 2025

Aplysiatoxin (ATX) is a bioactive polyketide natural product produced by cyanobacteria and characterized macrodiolide spiroacetal moieties. Many structurally diverse analogs of ATX have been reported but are little studied due to the minuscule quantities in which they isolated. We hypothesized that most these biosynthesized from anhydroATX, dehydrated form ATX, report de novo synthesis phenolic OMe ether anhydro-deBr-ATX, as well syntheses seven analogs, OTX-B1, B2, M, J, neo-deBr-ATX-A, G, according biosynthetic hypothesis. One highlights our neo-deBr-ATX-G radical cascade reaction involving 1,5-HAT an intramolecular conjugate addition efficiently construct its novel bicyclic structure. This work resulted revisions configurations neo-deBr-ATX-G, ring structure OTX-M.

Язык: Английский

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