4.4 Review

Recent Advances on the Synthesis of Nine-Membered N-Heterocycles

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Article Chemistry, Applied

Synthesis of Chiral Nine-Membered N-Heterocycles through Silver(I)-Promoted Cycloaddition and Rearrangement from N-Vinyl-α,β-Unsaturated Nitrones with Chiral 3-Propioloyloxazolidin-2-Ones

Xiao-Ting Qin et al.

Summary: A variety of chiral nine-membered N-heterocycles were prepared in moderate to good yields with high diastereoselectivity through a silver(I)-catalyzed reaction. Experimental studies showed that the silver catalyst promoted the cycloaddition and rearrangement process, and controlled the stereochemistry of the products.

ADVANCED SYNTHESIS & CATALYSIS (2022)

Article Chemistry, Applied

Sterically and Temperature Controlled Divergent Cycloadditions of α,β-Unsaturated Imines with Vinylethylene Carbonates: Insights from Experimental and DFT Studies

Xiaolong Xie et al.

Summary: This study presents a controllable divergent synthesis method for heterocycles, allowing the synthesis of different ring sizes from the same starting materials. By controlling the reaction conditions, selective synthesis of products can be achieved, and the reaction mechanism has been investigated.

ADVANCED SYNTHESIS & CATALYSIS (2022)

Article Chemistry, Organic

Asymmetric Total Synthesis and Structure Elucidation of Huperzine H

Shinya Shiomi et al.

Summary: A first asymmetric total synthesis of huperzine H has been achieved in a 12% overall yield from commercially available (+)-pulegone. The relative and absolute stereochemistry of huperzine H is established through key reactions including a highly diastereoselective Mukaiyama-Michael addition reaction and an intramolecular S(N)2 cyclization reaction.

JOURNAL OF ORGANIC CHEMISTRY (2022)

Article Chemistry, Multidisciplinary

Atroposelective Construction of Nine-Membered Carbonate-Bridged Biaryls

Shiqi Jia et al.

Summary: A highly efficient method for atroposelective construction of nine-membered carbonate-bridged biaryls through vinylidene ortho-quinone methide (VQM) intermediates was demonstrated. Diverse products with desirable pharmacological features were synthesized in satisfying yields and good to excellent enantioselectivities. In subsequent bioassays, several compounds showed significant antiproliferative activity via the mitochondrial-related apoptosis mechanism. Further transformations generated more structural diversity and may inspire novel ideas for developing functional molecules.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2022)

Article Chemistry, Multidisciplinary

A new type of δ-vinylvalerolactone for palladium-catalyzed cycloaddition: synthesis of nine-membered heterocycles

Kuan Li et al.

Summary: In this study, a new type of delta-vinylvalerolactone was designed and synthesized as a precursor in Pd-catalyzed [6+3] cycloaddition. The reaction resulted in nine-membered 1,2-dinitrogen-containing heterocycles in high yields with excellent diastereoselectivity. Further transformation of these ring-fused products led to the formation of unusual tetracyclic bridged-ring compounds without loss of diastereoselectivity.

CHEMICAL COMMUNICATIONS (2022)

Article Biochemistry & Molecular Biology

Antaroide, a Novel Natural Nine-Membered Macrolide, Inhibits Melanin Biosynthesis in B16F10 Murine Melanoma Cells

Min-Ji Ryu et al.

Summary: The demand for natural substances with anti-melanogenic activity is rising due to the growing interest in skin whitening. A new natural product named antaroide was isolated from the culture broth of a marine bacterium from the Antarctica coast, showing promising anti-melanogenic properties and potential for skin whitening cosmetics.

BIOMOLECULES & THERAPEUTICS (2021)

Article Multidisciplinary Sciences

Iridium-catalyzed Z-retentive asymmetric allylic substitution reactions

Ru Jiang et al.

Summary: The study introduces iridium-catalyzed asymmetric allylic substitution reactions that can preserve the Z-olefin geometries while establishing adjacent quaternary stereocenters. This method shows promise for the preparation of chiral Z-olefinic compounds.

SCIENCE (2021)

Article Chemistry, Organic

Access to Polycyclic Indole-3,4-Fused Nine-Membered Ring via Cascade 1,6-Hydride Transfer/Cyclization

Shuo Yang et al.

Summary: This study presents a novel method for one-step construction of a polycyclic indole-3,4-fused skeleton. By involving aldehydes and hydride transfer chemistry, the challenges of constructing medium-sized rings have been successfully addressed.

ORGANIC LETTERS (2021)

Article Chemistry, Multidisciplinary

Stereoselective Access to Polyfunctionalized Nine-Membered Heterocycles by Sequential Gold and Palladium Catalysis

Guoqiang Yang et al.

Summary: A gold and palladium sequential catalysis system has been reported for efficient and enantioselective access to furan-fused nine-membered heterocycles. In this one-pot procedure, easily accessible enynamides undergo cyclization to generate azadienes in situ, which then participate in enantioselective formal [5+4] cycloaddition with vinyl ethylene carbonates. Furthermore, conformation-controlled highly diastereoselective derivatizations of these medium-sized rings, coupled with oxidative furan cleavage, have enabled the access to diverse densely-functionalized nine-membered lactams.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2021)

Article Chemistry, Organic

Synergistic Pd(0)/Rh(II) Dual Catalytic [6+3] Dipolar Cycloaddition for the Synthesis of Monocyclic Nine-Membered N,O-Heterocycles and Their Alder-ene Rearrangement to Fused Bicyclic Compounds

Kyu Ree Lee et al.

Summary: The study presents a novel method for the synthesis of monocyclic nine-membered N,O-heterocycles through a synergistic palladium/rhodium dual catalytic cycloaddition of vinylpropylene carbonates with N-sulfonyl-1,2,3-triazoles. Furthermore, the resulting oxazonines can be transformed into cis-fused [4.3.0] bicyclic compounds via a transannular Alder-ene rearrangement.

ORGANIC LETTERS (2021)

Article Chemistry, Organic

Iron-catalyzed alkyne-carbonyl metathesis for the synthesis of 6,7-dihydro-5H-dibenzo[c,e]azonines

Baitan Chakraborty et al.

Summary: A method for synthesizing nine-membered rings via alkyne-carbonyl metathesis reaction is reported, resulting in the formation of unexplored 6,7-dihydro-5H-dibenzo[c,e]azonines. The use of cheap, non-toxic iron catalysts and milder conditions provides an alternative route to existing methods for synthesizing nine-membered rings.

ORGANIC & BIOMOLECULAR CHEMISTRY (2021)

Article Chemistry, Organic

Access to azonanes via Pd-catalyzed decarboxylative [5+4] cycloaddition with exclusive regioselectivity

Yin Liu et al.

Summary: The synthesis of azonanes via Pd-catalyzed decarboxylative [5 + 4] cycloaddition is highly efficient, utilizing methylene cyclic carbonates as a C5-dipole and 1-azadiene as a C4-synthon. The reactions can be performed at room temperature, showing wide functional group tolerance with exclusive regioselectivity and generating CO2 as the sole byproduct.

ORGANIC CHEMISTRY FRONTIERS (2021)

Article Chemistry, Organic

Diverse privileged N-polycyclic skeletons accessed from a metal-free cascade cyclization reaction

Wenzhong Li et al.

Summary: The metal-free cascade cyclization reaction offers an efficient and catalyst-free method for the one-pot synthesis of various isoindoloisoquinoline and benzoindolizinoindole derivatives, which can be further transformed into nitrogen-containing nine-membered ring compounds through Hofmann elimination with high yields. The resulting products with fused N-polycyclic skeletons are difficult to be synthesized using traditional methods and have wide applications in the pharmaceutical industry.

ORGANIC & BIOMOLECULAR CHEMISTRY (2021)

Review Chemistry, Organic

Recent Progress in the Synthesis of Medium-Sized Ring and Macrocyclic Compounds

Xinyuan Zhang et al.

Summary: Medium-sized rings and macrocycles, which are crucial components in drugs and natural products, have attracted significant attention from chemists in developing simple, green, and efficient synthesis methods. Recent advancements in ring expansion/cyclization reactions for these compounds have been reviewed to outline the future prospects and development in this field.

CHINESE JOURNAL OF ORGANIC CHEMISTRY (2021)

Article Chemistry, Multidisciplinary

Palladium-Catalyzed Asymmetric [8+2] Dipolar Cycloadditions of Vinyl Carbamates and Photogenerated Ketenes

Qun-Liang Zhang et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2020)

Article Chemistry, Organic

Divergent Strategy for Diastereocontrolled Synthesis of Small- and Medium-Ring Architectures

Vunnam Srinivasulu et al.

JOURNAL OF ORGANIC CHEMISTRY (2020)

Review Biochemistry & Molecular Biology

Strategies and Efforts towards the Total Synthesis of Palhinine Alkaloids

Yu-Yan Liang et al.

MOLECULES (2020)

Article Chemistry, Organic

Trapping rhodium vinylcarbenoids with aminochalcones for the synthesis of medium-sized azacycles

Kiran Chinthapally et al.

TETRAHEDRON LETTERS (2019)

Article Chemistry, Multidisciplinary

Pd-Catalyzed Enantioselective [6+4] Cycloaddition of Vinyl Oxetanes with Azadienes to Access Ten-Membered Heterocycles

Ya-Nong Wang et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2018)

Article Chemistry, Multidisciplinary

Synthesis of Benzannulated Medium-ring Lactams via a Tandem Oxidative Dearomatization-Ring Expansion Reaction

Tezcan Guney et al.

CHEMISTRY-A EUROPEAN JOURNAL (2018)

Review Chemistry, Organic

Biosynthesis of the teleocidin-type terpenoid indole alkaloids

Takayoshi Awakawa et al.

ORGANIC & BIOMOLECULAR CHEMISTRY (2018)

Article Chemistry, Multidisciplinary

Direct Photocatalytic Synthesis of Medium-Sized Lactams by C-C Bond Cleavage

Na Wang et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2018)

Article Chemistry, Multidisciplinary

Biomimetic Syntheses of (±)-Isopalhinine A, (±)-Palhinine A, and (±)-Palhinine D

Chih-Ming Chen et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2018)

Article Chemistry, Multidisciplinary

Nine-Membered Benzofuran-Fused Heterocycles: Enantioselective Synthesis by Pd-Catalysis and Rearrangement via Transannular Bond Formation

Zi-Qiang Rong et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2017)

Article Chemistry, Multidisciplinary

Ring-Expansion Approach to Medium-Sized Lactams and Analysis of Their Medicinal Lead-Like Properties

Laetitia G. Baud et al.

CHEMISTRY-A EUROPEAN JOURNAL (2017)

Article Chemistry, Multidisciplinary

Yttrium-Catalyzed Intramolecular Hydroalkoxylation/Claisen Rearrangement Sequence: Efficient Synthesis of Medium-Sized Lactams

Bo Zhou et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2017)

Article Chemistry, Multidisciplinary

Construction of Nine-Membered Heterocycles through Palladium-Catalyzed Formal [5+4] Cycloaddition

Li-Cheng Yang et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2017)

Article Chemistry, Multidisciplinary

Medium-Ring Nitrogen Heterocycles through Migratory Ring Expansion of Metalated Ureas

Jessica E. Hall et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2016)

Article Chemistry, Multidisciplinary

Enantioselective Synthesis of Indole-Annulated Medium-Sized Rings

Lin Huang et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2016)

Article Chemistry, Organic

Modular Total Synthesis of Protein Kinase C Activator (-)-Indolactam V

Jeremy Haynes-Smith et al.

ORGANIC LETTERS (2016)

Article Chemistry, Multidisciplinary

The Synthesis of Structurally Diverse Macrocycles By Successive Ring Expansion

Christiana Kitsiou et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2015)

Article Chemistry, Multidisciplinary

Near-Infrared Upconversion Controls Photocaged Cell Adhesion

Wen Li et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2014)

Article Chemistry, Multidisciplinary

Metal-Catalyzed [6+3] Cycloaddition of Tropone with Azomethine Ylides: A Practical Access to Piperidine-Fused Bicyclic Heterocycles

Honglei Liu et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2014)

Article Chemistry, Multidisciplinary

SnAP reagents for the one-step synthesis of medium-ring saturated N-heterocycles from aldehydes

Cam-Van T. Vo et al.

NATURE CHEMISTRY (2014)

Review Chemistry, Multidisciplinary

Importance and synthesis of benzannulated medium-sized and macrocyclic rings (BMRs)

Altaf Hussain et al.

RSC ADVANCES (2014)

Article Biochemistry & Molecular Biology

Biomimetic diversity-oriented synthesis of benzannulated medium rings via ring expansion

Renato A. Bauer et al.

NATURE CHEMICAL BIOLOGY (2013)

Article Chemistry, Organic

The Synthesis of Melohenine B and a Related Natural Product

Christopher S. Lancefield et al.

ORGANIC LETTERS (2012)

Article Chemistry, Organic

Palhinine A, a Novel Alkaloid from Palhinhaea cernua

Fu-Wei Zhao et al.

ORGANIC LETTERS (2010)

Article Chemistry, Organic

Melohenines A and B, Two Unprecedented Alkaloids from Melodinus henryi

Tao Feng et al.

ORGANIC LETTERS (2009)

Review Multidisciplinary Sciences

The remarkable metal-catalysed olefin metathesis reaction

Amir H. Hoveyda et al.

NATURE (2007)

Review Chemistry, Multidisciplinary

Synthesis of oxygen- and nitrogen-containing heterocycles by ring-closing metathesis

A Deiters et al.

CHEMICAL REVIEWS (2004)

Article Chemistry, Organic

Efficient medium-ring cyclization under non-high-dilution conditions using SMl2

H Tamiya et al.

ORGANIC LETTERS (2004)

Review Chemistry, Multidisciplinary

Metal-mediated synthesis of medium-sized rings

L Yet

CHEMICAL REVIEWS (2000)