Stereodivergent Total Synthesis of Tacaman Alkaloids DOI
Xiangtao Chen, Huijing Wang, Jie Zeng

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(38)

Published: July 1, 2024

This paper describes a concise, asymmetric and stereodivergent total synthesis of tacaman alkaloids. A key step in this is the biocatalytic Baeyer-Villiger oxidation cyclohexanone, which was developed to produce seven-membered lactones establish required stereochemistry at C14 position (92 % yield, 99 ee, 500 mg scale). Cis- trans-tetracyclic indoloquinolizidine scaffolds were rapidly synthesized through an acid-triggered, tunable acyl-Pictet-Spengler type cyclization cascade, serving as pivotal reaction for building alkaloid skeleton. Computational results revealed that hydrogen bonding crucial stabilizing intermediates inducing different addition reactions during cascade. By strategically using these two late-stage diversification functionalized core, syntheses eight alkaloids achieved. study may potentially advance research related medicinal chemistry

Language: Английский

Palladium-Catalyzed Carbonylations: Application in Complex Natural Product Total Synthesis and Recent Developments DOI Creative Commons
Hunter S. Sims, Mingji Dai

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

Citations

39
Vallesamidine and schizozygane alkaloids: rearranged monoterpene indole alkaloids and synthetic endeavours DOI
Xiangyu Zhang

Natural Product Reports, Journal Year: 2024, Volume and Issue: 41(5), P. 784 - 812

Published: Jan. 1, 2024

Unusual and unique vallesamidine schizozygane alkaloids. This review showcases their structural determination strategies, potential bioactivities, total synthesis studies.

Language: Английский

Citations

9
Enantioselective Total Syntheses of Vallesamidine and Schizozygane Alkaloids DOI

Gujjula V. Ramakrishna,

Zurwa Latif,

Filippo Romiti

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 27, 2025

A general streamlined strategy for the enantioselective total syntheses of schizozygane family natural products and related alkaloid vallesamidine is described. Specifically, a catalytic enantioconvergent cross-coupling sets quaternary stereogenic center in pluripotent intermediate adorned with an olefin three orthogonal carboxylate groups, upon which modularity synthesis relies. late-stage oxidative lactamization alkyne instrumental first-generation alkaloids. In second-generation approach, novel application van Leusen reaction generation lactams pivotal to accessing alkaloids from common intermediate. The strategies outlined here are expected enable detailed biological investigations as well facilitate access provide solutions modification bioactive

Language: Английский

Citations

1
Recent advances using cyclopropanols and cyclobutanols in ring-opening asymmetric synthesis DOI
Hong Yan, Gregory S. Smith, Fen‐Er Chen

et al.

Green Synthesis and Catalysis, Journal Year: 2022, Volume and Issue: 3(3), P. 219 - 226

Published: May 23, 2022

Language: Английский

Citations

35
Rapid Access to 2,2-Disubstituted Indolines via Dearomative Indolic-Claisen Rearrangement: Concise, Enantioselective Total Synthesis of (+)-Hinckdentine A DOI Creative Commons
Daler Baidilov, Pavel K. Elkin, Sudhakar Athe

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(27), P. 14831 - 14838

Published: June 26, 2023

The construction of 2,2-disubstituted indolines has long presented a synthetic challenge without any general solutions. Herein, we report robust protocol for the dearomative Meerwein-Eschenmoser-Claisen rearrangement 3-indolyl alcohols that provides efficient access to 2-substituted and indolines. These versatile subunits are useful natural product synthesis medicinal chemistry. title [3,3] sigmatropic proceeds in generally excellent yield transfers C3-indolic alcohol chirality C2 position with high fidelity, thus providing reliable method enantioenriched power this methodology is demonstrated through concise strategically unique total marine hinckdentine A, which features Claisen rearrangement, diastereocontrolled hydrogenation alkene product, one-pot amide-to-oxime conversion using Vaska's complex, regioselective late-stage tribromination.

Language: Английский

Citations

21
A Homo‐Mannich Reaction Strategy Enables Collective Access to Ibophyllidine, Aspidosperma, Kopsia, and Melodinus Alkaloids DOI Open Access
Dan Jiang, Peng Tang, Hongbing Xiong

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(37)

Published: July 25, 2023

We report here a homo-Mannich reaction of cyclopropanol with an iminium ion, generated by asymmetric allylic dearomatization indole, to construct tricyclic hydrocarbazole core, which is shared variety monoterpenoid indole alkaloids across families. Through this approach, all-carbon quaternary stereogenic center as well allyl and ketone group were installed. Using functionalized the structural platform, D ring E rings different sizes (i.e., five-, six-, seven-membered) successively or simultaneously assembled, leading collective synthesis seven belonging ibophyllidine, Aspidosperma, Kopsia, Melodinus alkaloid

Language: Английский

Citations

15
Strained cycloalkanols in C–C bond formation reactions: a boon in disguise! DOI
Neha Jha, P. Mishra, Manmohan Kapur

et al.

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(19), P. 4941 - 4971

Published: Jan. 1, 2023

A summary of the various ring opening reactions strained and unstrained cycloalkanols is elaborated in present review. Key emphasis on reactivities pertaining to cyclopropanols, cyclobutanols higher analogues provided.

Language: Английский

Citations

14
Synthesis of Chiral Polycyclic Indoles via Pd(II)-Catalyzed Sequential Cyclization and Carbonylation DOI
Long Chen,

Hengrui Zhou,

Yiji Xue

et al.

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

Citations

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

Pengyun Liu

et al.

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

Citations

21
Arylation of Cyclopropanol with Pyrrole: Asymmetric Synthesis of Indolizidine 167B, Indolizidine 209D, and Monomorine I DOI

Shuangwei Liu,

Xiaojiao Su,

Dan Jiang

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(12), P. 2058 - 2062

Published: March 17, 2023

A Fe(NO3)3-mediated ring-opening arylation of cyclopropanol with the electron-rich pyrrole has been developed, which might proceed through oxidative radical ring opening followed by cyclization to motif and then aromatization. This method enables direct without prefunctionalization thus allows rapid access a diverse array chiral 5,6,7,8-tetrahydroindolizines from easily available amino acid esters. The synthetic utility demonstrated asymmetric synthesis alklaoids (-)-indolizidine 167B, (+)-indolizidine 209D, (+)-monomorine I, natural product analogue.

Language: Английский

Citations

11