Palladium-Catalyzed Carbonylations: Application in Complex Natural Product Total Synthesis and Recent Developments

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(8), P. 4925 - 4941

Published: Jan. 27, 2023

Carbon monoxide is a cheap and abundant C1 building block that can be readily incorporated into organic molecules to rapidly build structural complexity. In this Perspective, we outline several recent (since 2015) examples of palladium-catalyzed carbonylations in streamlining complex natural product total synthesis highlight the strategic importance these carbonylation reactions corresponding synthesis. The selected include spinosyn A, callyspongiolide, perseanol, schizozygane alkaloids, cephanolides, bisdehydroneostemoninine related stemona alkaloids. We also provide our perspective about advancements future developments carbonylations.

Language: Английский

---

Biocatalytic production of biolubricants: Strategies, problems and future trends

Biotechnology Advances, Journal Year: 2023, Volume and Issue: 68, P. 108215 - 108215

Published: July 18, 2023

The increasing worries by the inadequate use of energy and preservation nature are promoting an interest in production biolubricants. After discussing necessity producing biolubricants, this review focuses on these interesting molecules through lipases, different possibilities (esterification free fatty acids, hydroesterification or transesterification oils fats, biodiesel with more adequate alcohols, estolides production, modification acids). utilization discarded substrates has special due to double positive ecological impact (e.g., oil distillated, overused oils). Pros cons all possibilities, together general considerations optimize processes will be outlined. Some overcome some problems detected compounds also discussed.

Language: Английский

---

Stereospecific Acylative Suzuki–Miyaura Cross-Coupling: General Access to Optically Active α-Aryl Carbonyl Compounds

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(13), P. 7075 - 7083

Published: March 2, 2023

A novel strategy for the stereospecific Pd-catalyzed acylative cross-coupling of enantiomerically enriched alkylboron compounds has been developed. The protocol features an extremely high level enantiospecificity to allow facile access synthetically challenging and valuable chiral ketones carboxylic acid derivatives. use a sterically encumbered electron-rich phosphine ligand proved be crucial success reaction. Furthermore, on basis experimental computational studies, unique mechanism transmetalation, assisted by noncovalent interactions C(sp3)-based organoboron reagent, identified.

Language: Английский

---

Synthesize of β-Amino Esters from Enamides via 1,8-Diazabicyclo[5.4.0]undecane-7-ene-Mediated Hydroalkylation

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 13, 2025

A 1,8-diazabicyclo[5.4.0]undecane-7-ene (DBU)-mediated hydroalkylation of enamides with malonic acid diesters/β-carbonyl esters has been established, featuring no metal involvement, mild reaction conditions, and good functional group tolerance. The protocol enables the expedited preparation a variety β-amino esters. Preliminary mechanistic investigations, encompassing control experiments capture key intermediates, have substantiated proposed DBU-mediated pathway.

Language: Английский

---

Rh-catalyzed double carbonylation of cyclopropenes toward valerolactone derivatives via cleavage of carbon–carbon double bonds

Science China Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 25, 2025

Language: Английский

---

Palladium-catalyzed regiodivergent hydrochlorocarbonylation of alkenes for formation of acid chlorides

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: May 31, 2023

Novel strategy for acid chlorides formation that do not use carboxylic acids is particularly attractive in chemical synthesis but remains challenging. Herein, we reported the development of a highly effective Pd-catalyzed hydrochlorocarbonylation alkenes with CO alkyl chlorides. Chlorosilane and AcOH were found as mild HCl source reaction. The reaction shows broad substrate scope produces both branched linear good to high yields upon different ligands solvents. Cooperating follow-up acylation reactions, offers complementary platform diverse carbonyl compounds from alkenes. Mechanistic investigations suggested proceeded though palladium hydride pathway, prompted reductive elimination acyl-Pd-Cl intermediate.

Language: Английский

---

Palladium‐Catalyzed Enantioselective Hydrofunctionalization of Alkenes: Recent Advances

European Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 26(43)

Published: Sept. 8, 2023

Abstract Palladium‐catalyzed asymmetric hydrofunctionalization of alkenes is one the most powerful and straightforward methods to forge a new C−H bond C−X (X=C, N, O, F, Si etc) bond, which provides an efficient way obtain valuable enantioenriched molecules from cheap readily available feedstocks. Catalytic simple challenging but still highly sought after. This review will mainly focus on recent advances in Palladium catalyzed over past decade, including hydroamination, hydrooxygenation, hydrofluorination, hydrosilylation, hydroarylation, hydroalkenylation hydrocarbonylation.

Language: Английский

---

Synthesis of Chiral Polycyclic Indoles via Pd(II)-Catalyzed Sequential Cyclization and Carbonylation

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(11), P. 8739 - 8747

Published: May 21, 2024

Asymmetric tandem Heck and carbonylation reactions provide an efficient route to synthesize biologically important chiral cyclic compounds with a carbonyl group have attracted increasing research interests. However, this type of reaction relies on the initiation from oxidative addition aryl halides or pseudo halides, resulting in low atomic economy reaction. In addition, protocol has not adequately demonstrated reactivity generality heteroarene halides. Meanwhile, asymmetric Wacker-type cyclization are plagued by narrow substrate scope enantioselectivity remain underexplored. Herein, we describe Pd(II)-catalyzed sequential 1,6-enynes analogues carbon monoxide (CO). This catalytic system tolerates broad nucleophiles, including phenols, alcohols, amines. sequence forms four chemical bonds, two rings, up three stereocenters single step. strategy allows for convenient access variety polycyclic good yields enantio- diastereoselectivities, indoles, benzofurans, indole- benzofuran-fused bicyclo[3.2.1]octanes, indole-fused bicyclo[4.2.1]nonane.

Language: Английский

---

Enantioconvergent synthesis of axially chiral amides enabled by Pd-catalyzed dynamic kinetic asymmetric aminocarbonylation

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Aug. 23, 2024

Atropisomeric biaryls bearing carbonyl groups have attracted increasing attention due to their prevalence in diverse bioactive molecules and crucial role as efficient organo-catalysts or ligands asymmetric transformations. However, preparation often involves tedious multiple steps, the direct synthesis via carbonylation has scarcely been investigated. Herein, we report an palladium-catalyzed enantioconvergent aminocarbonylation of racemic heterobiaryl triflates with amines dynamic kinetic transformation (DyKAT). This protocol features a broad substrate scope excellent compatibility for rapid construction axially chiral amides good high yields enantioselectivities. Detailed mechanistic investigations discover that base can impede intramolecular hydrogen bond-assisted axis rotation products, thus allowing success achieve enantioselectivity. Moreover, achieved be directly utilized N,N,N-pincer copper-catalyzed enantioselective formation C(sp3)-N C(sp3)-P bonds. Axially containing not only exist various drug candidates but also serve authors transformation.

Language: Английский

---

Pd‐Catalyzed Asymmetric 5‐exo‐trig Cyclization/Cyclopropanation/Carbonylation of 1,6‐Enynes for the Construction of Chiral 3‐Azabicyclo[3.1.0]hexanes

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 62(4)

Published: Nov. 25, 2022

We herein disclose a mild and efficient access to chiral 3-azabicyclo[3.1.0]hexanes via Pd-catalyzed asymmetric 5-exo-trig cyclization/cyclopropanation/carbonylation of 1,6-enynes. Various nucleophiles, such as alcohols, phenols, amines water, are well compatible with the reaction system. This forms three C-C bonds, two rings, adjacent quaternary carbon stereocenters one C-O/C-N bond excellent regio- enantioselectivities. The products could be further functionalized generate library 3-azabicyclo[3.1.0]hexane frameworks.

Language: Английский

---