A Pd-catalyzed organometallic-free homologation of arylboronic acids enabled by chemoselective transmetalation DOI Creative Commons

Kane C. Bastick,

Allan J. B. Watson

Опубликована: Фев. 28, 2023

A Pd-catalyzed homologation of arylboronic acids is reported. Halomethylboronic acid pinacol esters (BPin) undergo a remarkably facile, yet rare, oxidative addition enabled by an alpha-boryl effect. Simultaneous chemoselective transmetalation allows use these reagents for formal C1 insertion to deliver benzyl BPin products without the requirement stoichiometric organometallic reagents. The utility process demonstrated stepwise C(sp3)C(sp2) cross-coupling boronic ester into diarylmethane pharmacophores and electrophile/nucleophile cross-coupling. Control exper-iments that demonstrate reactivity enhancement provided -boryl effect are provided, along with description limitations process.

Язык: Английский

A General Three-Component Alkyl Petasis Boron–Mannich Reaction DOI
Chao Hu, Jet Tsien,

Si-Jie Chen

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(31), С. 21769 - 21777

Опубликована: Июль 29, 2024

Aryl amines are one of the most common moieties in biologically active molecules, and approximately 37% drug candidates contain aromatic amines. Recent advancements medicinal chemistry, coined "escaping from flatland", have led to a greater focus on accessing highly functionalized C (sp3)-rich improve physicochemical pharmacokinetic properties compounds. This article presents modular operationally straightforward three-component alkyl Petasis boron–Mannich (APBM) reaction that utilizes ubiquitous starting materials, including amines, aldehydes, boronates. By adaptation this transformation high-throughput experimentation (HTE), it offers rapid access an array diverse C(sp3)-rich complex amenable for identification candidates.

Язык: Английский

Процитировано

8

HighlyE‐Selective Olefin Synthesis Catalysed by Novel Quinoxalinone Photocatalyst under Visible Light Conditions DOI
Xin Xu, Jie Huang, Dandan Gao

и другие.

Chemistry - A European Journal, Год журнала: 2023, Номер 29(27)

Опубликована: Фев. 21, 2023

In photo-induced olefin synthesis, the photocatalysts with high triplet energy could cause isomerization of olefins. This study demonstrates a new quinoxalinone photocatalytic system for highly stereoselective alkenes preparation from alkenyl sulfones and alkyl boronic acids. Our photocatalyst not convert thermodynamically favored E-olefin to Z-olefin, guaranteeing E-configuration selectivity reaction. There is weak interaction between acids according NMR experiments, probably decreasing oxidation potential can be further extended allyl alkynyl give corresponding alkynes.

Язык: Английский

Процитировано

9

Effect of orbital hybridization inspired tessellation strategy on the mechanical properties of lattice structures DOI
Mohit Sood, Chang‐Mou Wu,

Chih-Wei Tang

и другие.

Thin-Walled Structures, Год журнала: 2024, Номер 205, С. 112396 - 112396

Опубликована: Авг. 31, 2024

Язык: Английский

Процитировано

2

Bromine Radical Release from Nickel-Complex Facilitates the Activation of Alkyl Boronic Acids: A Boron Selective Suzuki-Miyaura Cross Coupling DOI Creative Commons
Monica Oliva, Serena Pillitteri, Johannes Schörgenhumer

и другие.

Chemical Science, Год журнала: 2024, Номер unknown

Опубликована: Янв. 1, 2024

The release of bromine radicals from a nickel complex via homolytic cleavage under visible light allows the activation alkyl boronic acids, which participate in Suzuki–Miyaura cross-coupling process batch and continuous flow settings.

Язык: Английский

Процитировано

2

Boronic Acids and Their Derivatives as Continuous-Flow-Friendly Alkyl Radical Precursors DOI
Upendra K. Sharma, Monica Oliva,

Viktoriia V. Chernobrovkina

и другие.

Synlett, Год журнала: 2023, Номер 34(14), С. 1662 - 1677

Опубликована: Апрель 4, 2023

Abstract Since its recognition as an enabling tool to form challenging C–C and C–heteroatom bonds under mild sustainable conditions, photoredox catalysis has been in the spotlight within synthetic community. As a consequence, interest developing novel strategies spiked together with need define suitable technologies overcome scale-up issues dictated by Bouguer–Beer–Lambert law. In this context, continuous-flow reactors play major role increasing efficiency of given photocatalyzed reaction, thus rendering processes more accessible. alkyl radical precursor landscape, boron-based species have begun predominant role. Though reactivity trifluoroborates deeply investigated, using other boron precursors reactions recently arisen. This late exploration lies fact that high oxidation potential boronic acids (BAs) hinders their possible applications. Nevertheless, circumvent issue, diverse array activation modes developed, exploiting most cases inherent Lewis acidity acid. The aim Account is highlight our recent contribution vibrant field focus on broad applicability, selectivity, scalability via methodology. For sake clarity, discussed following sections. 1 Introduction 2 Why Photochemistry Flow? 2.1 Preliminary Considerations 2.2 Batch vs. Flow Photochemical Reactions 2.3 Commercially Available Lab-Scale Solutions for Photoflow Chemistry 3 Organoboron Compounds 3.1 Evolution Radical Precursors Photoredox Catalysis 3.2 4 Activation Boronic Acids towards Formation 4.1 Giese-Type Addition 4.2 Petasis Reaction 4.3 Light-Driven Four-Component 4.4 Minisci 5 Conclusion Future Perspective

Язык: Английский

Процитировано

5

Alkoxide-Assisted Stereoselective Functionalization of 1,2-Bis-boronic Esters Under Photoredox Catalysis DOI

Somenath Mahato,

Debraj Ghorai,

Kanak Kanti Das

и другие.

Organic Letters, Год журнала: 2024, Номер 26(31), С. 6760 - 6765

Опубликована: Июль 25, 2024

Site-specific functionalization of the secondary C–B bond 1,2-bis-boronic esters has been proven to be an important method for generation 1,2-bis-functionalized compounds in a highly stereoselective manner. We have explored previously unknown selective alkenylation, allylation, alkynylation and addition aryl vinyl trifluoromethane, which proceeds via novel reaction mechanism: alkoxide-mediated photoredox activation generate radicals over primary one.

Язык: Английский

Процитировано

0

A Pd-catalyzed organometallic-free homologation of arylboronic acids enabled by chemoselective transmetalation DOI Creative Commons

Kane C. Bastick,

Allan J. B. Watson

Опубликована: Фев. 28, 2023

A Pd-catalyzed homologation of arylboronic acids is reported. Halomethylboronic acid pinacol esters (BPin) undergo a remarkably facile, yet rare, oxidative addition enabled by an alpha-boryl effect. Simultaneous chemoselective transmetalation allows use these reagents for formal C1 insertion to deliver benzyl BPin products without the requirement stoichiometric organometallic reagents. The utility process demonstrated stepwise C(sp3)C(sp2) cross-coupling boronic ester into diarylmethane pharmacophores and electrophile/nucleophile cross-coupling. Control exper-iments that demonstrate reactivity enhancement provided -boryl effect are provided, along with description limitations process.

Язык: Английский

Процитировано

0