Kinetic Resolution of Azaarylethynyl Tertiary Alcohols by Chiral Brønsted Acid Catalysed Phosphine‐Mediated Deoxygenation DOI
Guanghui Wang, Lulu Li,

Yifeng Jiang

et al.

Angewandte Chemie, Journal Year: 2022, Volume and Issue: 135(4)

Published: Nov. 22, 2022

Abstract A chiral Brønsted acid catalysed phosphine‐mediated deoxygenation protocol is reported. This metal‐free method provides a precise kinetic resolution platform for azaarylethynyl tertiary alcohols, which are broad category of biologically and synthetically important azaarene derivatives. In addition to providing an efficient the first asymmetric preparation these strategy facilitates construction azaaryl‐functionalized allenes with good excellent enantioselectivities. The high selectivity factors ( s up 235), substrate scope, ability convert azaaryl compounds into both alcohols robustly underscore efficiency promising utility this method. practicability further validated by successful synthesis deuterated ee values substantial incorporation deuterium using inexpensive D 2 O as source.

Language: Английский

Diastereo- and atroposelective synthesis of N-arylpyrroles enabled by light-induced phosphoric acid catalysis DOI Creative Commons
Lei Dai, Xueting Zhou, Jiami Guo

et al.

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

Published: Aug. 9, 2023

The C-N axially chiral N-arylpyrrole motifs are privileged scaffolds in numerous biologically active molecules and natural products, as well ligands/catalysts. Asymmetric synthesis of N-arylpyrroles, however, is still challenging, the simultaneous creation contiguous axial central chirality remains unknown. Herein, a diastereo- atroposelective N-arylpyrroles enabled by light-induced phosphoric acid catalysis has been developed. key transformation one-pot, three-component oxo-diarylation reaction, which simultaneously creates quaternary stereogenic center. A broad range unactivated alkynes were readily employed reaction partner this transformation, products obtained good yields, with excellent enantioselectivities very diastereoselectivities. Notably, skeletons represent interesting structural that could be used ligands catalysts asymmetric catalysis.

Language: Английский

Citations

30
Visible Light-Mediated Heterodifunctionalization of Alkynylazobenzenes for 2H-Indazole Synthesis DOI Creative Commons
Clara Mañas, Estı́baliz Merino

Organic Letters, Journal Year: 2024, Volume and Issue: 26(9), P. 1868 - 1873

Published: Feb. 22, 2024

We disclose the heterodifunctionalization of alkynylazobenzenes promoted exclusively by visible light in absence any transition metal and/or photocatalyst. This reaction features excellent regioselectivity on a broad variety substrates with perfect atom economy. Alcohols, carboxylic acids, thiols, amides, heterocycles, and even water are suitable for promotion oxyamination, sulfenoamination, diamination reactions. In this manner, biologically active indazole scaffolds can be rapidly assembled from alkyne feedstocks.

Language: Английский

Citations

8
Copper‐Catalyzed Regiodivergent Asymmetric Difunctionalization of Terminal Alkynes DOI
Simin Wang, Kexin Chen,

Junbo Niu

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: June 25, 2024

We herein describe the first example of ligand-controlled, copper-catalyzed regiodivergent asymmetric difunctionalization terminal alkynes through a cascade hydroboration and hydroallylation process. The catalytic system, consisting (R)-DTBM-Segphos CuBr, could efficiently achieve 1,1-difunctionalization aryl alkynes, while ligand switching to (S,S)-Ph-BPE result in 1,2-difunctionalization exclusively. In addition, alkyl substituted especially industrially relevant acetylene propyne, were also valid feedstocks for 1,1-difunctionalization. This protocol is characterized by good functional group tolerance, broad scope substrates (>150 examples), mild reaction conditions. showcase value this method late-stage functionalization complicated bioactive molecules simplifying synthetic routes toward key intermediacy natural product (bruguierol A). Mechanistic studies combined with DFT calculations provide insight into mechanism origins ligand-controlled regio- stereoselectivity.

Language: Английский

Citations

6
Divergent Synthesis of Pentacyclic Isoindolinones Enabled by Sequential Insertion of Two Different Isocyanides and Acid Promoted Cyclization of Ketenimines DOI
Yiming Zhu, Xiaoping Xu, Shun‐Jun Ji

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(12), P. 2041 - 2046

Published: March 22, 2023

A palladium-catalyzed multicomponent reaction involving o-bromobenzaldehydes and two different isocyanides was developed to assemble series of isoindolinones with spiroindolenine or azepinoindole skeletons. This sequential insertion features mild conditions, a wide substrate scope, high efficiency. Preliminary mechanistic study indicated that the difference in steric hindrance between isocyanide components is crucial when regulating sequence, whereas ligand also played an important role during whole process.

Language: Английский

Citations

12
Enantioselective De Novo Synthesis of α,α‐Diaryl Ketones from Alkynes DOI Creative Commons
Xueting Zhou, Qingqin Huang, Jiami Guo

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(45)

Published: Sept. 19, 2023

Abstract Chiral α,α‐diaryl ketones are structural motifs commonly present in bioactive molecules, and they also valuable building blocks synthetic organic chemistry. However, catalytic asymmetric synthesis of bearing a tertiary stereogenic center remains largely unsolved. Herein, we report de novo enantioselective from simple alkynes via chiral phosphoric acid (CPA) catalysis. A broad range enolizable prepared good yields with excellent enantioselectivities. The described protocol serves as an efficient deuteration method for the preparation enantiomerically enriched deuterated ketones. Using methodology reported, including one best‐selling anti‐breast cancer drugs, tamoxifen, readily synthesized.

Language: Английский

Citations

12
Catalytic vs. uncatalyzed [2 + 2] photocycloadditions of quinones with alkynes DOI Creative Commons
Alexander A. Fadeev, Martin Kotora

Organic & Biomolecular Chemistry, Journal Year: 2023, Volume and Issue: 21(30), P. 6174 - 6179

Published: Jan. 1, 2023

Simple irradiation of quinones and alkynes with blue light is sufficient to trigger [2 + 2] photocycloadditions giving rise either fused cyclobutenes or reactive para -quinone methides depending on the quinone structure.

Language: Английский

Citations

11
Reduction of unactivated alkyl chlorides enabled by light-induced single electron transfer DOI
Lei Dai, Zhaofei Zhang, Xiang‐Yu Chen

et al.

Science China Chemistry, Journal Year: 2023, Volume and Issue: 67(2), P. 471 - 481

Published: Nov. 16, 2023

Language: Английский

Citations

10
Catalytic Asymmetric Construction of α,α‐Diaryl Aldehydes via Oxo‐Hydroarylation of Terminal Alkynes DOI Creative Commons
Xueting Zhou, Qingqin Huang, Jiami Guo

et al.

Advanced Science, Journal Year: 2024, Volume and Issue: 11(24)

Published: April 22, 2024

Abstract Chiral aldehydes containing a tertiary stereogenic center are versatile building blocks in organic chemistry. In particular, such structural motifs bearing an α,α‐diaryl moiety very challenging scaffolds and their efficient asymmetric synthesis is not reported. this work, phosphoric acid‐catalyzed enantioselective of from simple terminal alkynes presented. This approach yields wide range highly enolizable good with excellent enantioselectivities. Facile transformations the products, as well bioactive molecules, including effective anti‐smallpox agent FDA‐approved antidepressant drug (+)‐sertraline, demonstrated.

Language: Английский

Citations

4
Construction of axially chiral molecules enabled by photoinduced enantioselective reactions DOI Creative Commons
Zhaofei Zhang, Lei Dai

Chemical Science, Journal Year: 2024, Volume and Issue: 15(32), P. 12636 - 12643

Published: Jan. 1, 2024

Axially chiral molecular scaffolds are widely found in pharmaceutical molecules, functionalized materials, and ligands. The synthesis of these compounds has garnered considerable interest from both academia industry. construction such enabled by transition metal catalysis organocatalysis under thermodynamic conditions, been extensively studied well-reviewed. In recent years, photoinduced enantioselective reactions have emerged as powerful methods for the catalytic axial chirality. this review, we provide an overview various synthetic strategies chirality, with a specific focus on reaction design mechanisms. Additionally, discuss limitations current highlight future directions field.

Language: Английский

Citations

4
Kinetic Resolution of Azaarylethynyl Tertiary Alcohols by Chiral Brønsted Acid Catalysed Phosphine‐Mediated Deoxygenation DOI
Guanghui Wang, Lulu Li,

Yifeng Jiang

et al.

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

Published: Nov. 22, 2022

A chiral Brønsted acid catalysed phosphine-mediated deoxygenation protocol is reported. This metal-free method provides a precise kinetic resolution platform for azaarylethynyl tertiary alcohols, which are broad category of biologically and synthetically important azaarene derivatives. In addition to providing an efficient the first asymmetric preparation these strategy facilitates construction azaaryl-functionalized allenes with good excellent enantioselectivities. The high selectivity factors (s up 235), substrate scope, ability convert azaaryl compounds into both alcohols robustly underscore efficiency promising utility this method. practicability further validated by successful synthesis deuterated ee values substantial incorporation deuterium using inexpensive D2 O as source.

Language: Английский

Citations

15