Stereospecific Conversion of Boronic Esters into Enones using Methoxyallene: Application in the Total Synthesis of 10‐Deoxymethynolide DOI Creative Commons

Kristian J. Chambers,

Patthadon Sanghong,

Daniel Carter Martos

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(50)

Published: Oct. 25, 2023

Abstract Enones are widely utilized linchpin functional groups in chemical synthesis and molecular biology. We herein report the direct conversion of boronic esters into enones using commercially available methoxyallene as a three‐carbon building block. Following boronate complex formation by reaction ester with lithiated‐methoxyallene, protonation triggers stereospecific 1,2‐migration before oxidation generates enone. The protocol shows broad substrate scope complete enantiospecificity is observed chiral migrating groups. In addition, various electrophiles could be used to induce give much broader range α‐functionalized enones. Finally, methodology was applied 14‐step enone‐containing polyketide 10‐deoxymethynolide.

Language: Английский

Cobalt-Catalyzed Enantioselective Reductive Arylation, Heteroarylation, and Alkenylation of Michael Acceptors via an Elementary Mechanism of 1,4-Addition DOI
Mengxin Zhao, Wenqiang Xu, Yun‐Dong Wu

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(29), P. 20477 - 20493

Published: July 10, 2024

Cobalt complexes with chiral quinox ligands effectively promote the enantioselective conjugate addition of enones using aryl, heteroaryl, and alkenyl halides sulfonates. Additionally, a cobalt complex strongly donating diphosphine, BenzP*, successfully catalyzes asymmetric reductive arylation alkenylation α,β-unsaturated amides. Both catalytic systems show broad scopes tolerance sensitive functional groups. reactions can be scaled up low loadings catalysts. Experimental results density theory (DFT) calculations suggest new mechanism elementary 1,4-addition aryl cobalt(I) complexes.

Language: Английский

Citations

3
Formation of Chiral All-Carbon Quaternary Stereocenters by Photoinduced Cobalt-Catalyzed Enantioselective Radical Coupling DOI
Yue Jia, Kai Zhang, Liang‐Qiu Lu

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(18), P. 13550 - 13556

Published: Aug. 28, 2024

Photoinduced enantioselective strategies provide an efficient way to access chiral all-carbon quaternary stereocenters. Compared with the well-developed metal-catalyzed asymmetric conjugate addition of organometallic reagents enones, construction stereocenters through a radical process still remains challenging, especially for acyclic enones due their enhanced conformational mobility. Herein, we disclose photoinduced cobalt-catalyzed coupling α,β-unsaturated 2-acyl imidazoles and α-silylamines give β,β-disubstituted γ-amino acid derivatives carbon The facile protocol shows good functional group tolerance broad substrate scope. corresponding products were obtained in generally yields (up 96%) high enantioselectivities 99:1 e.r.).

Language: Английский

Citations

3
Chiral Magnesium(II)-Catalyzed Asymmetric Hydroalkylation of Imine-Containing Vinylazaarenes through Conjugate Addition DOI
Dong Ye, Mingyi Jiang, Lichao Ning

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: March 29, 2025

The synthesis of chiral azaarenes is great importance for pharmaceutical development. A direct and versatile approach to obtaining such compounds the functionalization imine-containing 2-vinylazaarenes. We have developed a N,N'-dioxide/Mg(II) Lewis acid catalytic system control nucleophilic β-cyclic or acyclic ketone amides/esters overcome strong background reaction, enabling highly efficient enantioselective hydroalkylation 2-vinylazaarenes via conjugate addition. As result, library bearing an all-carbon quaternary stereocenter can be obtained in high yields with good excellent ee values. DFT calculations indicate assistances hydrogen transfer, CH-π interaction between substrate ligand's amide group differentiation.

Language: Английский

Citations

0
Conjugate Addition of Chiral Allenylcopper Species to Vinyl Bis(sulfone) To Access an All-Carbon Quaternary Center DOI
Wan Seok Yoon, Jaehyun You, Jin You

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: April 1, 2025

Asymmetric formation of all-carbon quaternary centers has been recognized as a challenging area in organic synthesis. Herein, we report copper-catalyzed approach toward coupling two alkenyl substrates, resulting the chiral center. In reaction, axially tetrasubstituted allenylcopper species were generated catalytically and chemoselectively, situ from substituted enynes, remarkably performed an efficient organometallic nucleophile conjugate addition to unsaturated sulfones.

Language: Английский

Citations

0
Recent Advances in the Construction of Quaternary Stereocenters via Palladium-Catalyzed Decarboxylative Asymmetric Allylic Alkylation DOI

Xinhui Yu,

Ting Zhang, Jitian Liu

et al.

Synthesis, Journal Year: 2021, Volume and Issue: 53(23), P. 4341 - 4352

Published: June 22, 2021

Abstract Palladium-catalyzed decarboxylative asymmetric allylic alkylation (DAAA) provides an efficient and powerful strategy to construct quaternary stereocenters, which are widely present in biologically active natural products approved drugs. In this short review, we summarize recent developments (since 2018) the facile synthesis of stereocenters via DAAA methods. Several representative examples use strategies for total complex further demonstrate its synthetic potential realm organic medicinal chemistry. 1 Introduction 2 Construction Quaternary Stereocenters Palladium Catalyzed 3 Pd-Catalyzed Interceptive 4 Application Natural Product Synthesis 5 Conclusion

Language: Английский

Citations

20
Metal/Metal Dual Catalysis in C−H Activation DOI

Qijing Zhang,

Chengming Wang

European Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 2022(22)

Published: May 11, 2022

Abstract Metal/metal dual catalysis provides new viewpoints and opportunities for C−H functionalization, especially in reactivity selectivity control aspects. It helps to realize sequential or cooperative catalytic transformations one‐pot, shortening the synthetic steps target molecules construction. This micro‐review summarizes most recent advances this research field, discusses related mechanism, collecting examples according role of metal species.

Language: Английский

Citations

13
Advances in Catalytic Asymmetric Construction of Quaternary Stereogenic Centers by Conjugate Addition to β,β‐Disubstituted Nitroalkenes DOI
Sushovan Paladhi, Jin Hyun Park,

Barnali Jana

et al.

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 365(17), P. 2789 - 2817

Published: July 6, 2023

Abstract Quaternary stereogenic centers are of great importance because their prevalence in a series bioactive natural products and pharmaceuticals. Although the catalytic asymmetric construction these highly congested poses formidable challenge, this field has been extensively explored past few decades, several elegant strategies, such as conjugate addition to β,β‐disubstituted nitroalkenes, have developed. The resultant β‐nitro quaternary stereocenters can be conveniently transformed into corresponding β‐amino commonly found compounds. This review summarizes recent advances all‐carbon or hetero‐carbon via metal‐catalyzed organocatalyzed focusing on scope, applications, mechanisms reactions.

Language: Английский

Citations

7
Phosphine‐Catalyzed Synthesis and Cytotoxic Evaluation of Michael Adducts of the Sesquiterpene Lactone Arglabin DOI
Alexey V. Salin,

Andrey A. Shabanov,

Khasan R. Khayarov

et al.

ChemMedChem, Journal Year: 2024, Volume and Issue: 19(12)

Published: March 22, 2024

A general method for chemo- and diastereoselective modification of anticancer natural product arglabin with nitrogen- carbon-centered pronucleophiles under the influence nucleophilic phosphine catalysts was developed. The locked s-cis-geometry α-methylene-γ-butyrolactone moiety favors additional stabilization zwitterionic intermediate by electrostatic interaction between phosphonium enolate oxygen centers, leading to unprecedentedly high efficiency phosphine-catalyzed Michael additions this sesquiterpene lactone. Using n-Bu

Language: Английский

Citations

2
Pd(II)/N,N′-Disulfonyl Bisimidazoline-Catalyzed Enantioselective Synthesis of Cyclic Quaternary Centers and Mechanistic Investigations DOI
Yuxin Wang, Chen‐Long Li, Yinping Liu

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(13), P. 9381 - 9388

Published: June 17, 2024

A Pd(II)/N,N′-disulfonyl bisimidazoline-catalyzed asymmetric 1,4-conjugate addition reaction of low-cost arylboronic acids with readily available β-substituted cyclic enones is described, providing a straightforward way constructing all-carbon quaternary stereocenters high enantioselectivity, in which ≥96% ee was obtained most cases. The proceeded without the protection inert gas, making operation process simple. Theoretical calculations have been applied to understand origins enantioselectivity.

Language: Английский

Citations

2
A Direct Organocatalytic Enantioselective Route to Functionalizedtrans‐Diels–Alder Products Having the Norcarane Scaffold DOI
Casper L. Barløse, Niklas L. Østergaard, René S. Bitsch

et al.

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(33), P. 18318 - 18327

Published: June 3, 2021

An enantioselective methodology to construct trans-Diels-Alder scaffolds by organocatalysis with excellent selectivity, high yield and up five contiguous stereocenters is presented. The reaction concept integrates the halogen effect a novel discovered pseudo-halogen direct an endo-selective, secondary-amine catalyzed Diels-Alder allowing for subsequent formation of cycloadducts featuring norcarene scaffold. relies on between in situ generated trienamine α-brominated or α-pseudo-halogenated enone form fleeting cis-Diels-Alder intermediate. endo-transition state-enhanced (pseudo-)halogen effect-sets stereochemistry that allows SN 2-like at tertiary center obtain mechanism was investigated supported experimental results as well computational studies.

Language: Английский

Citations

14