Modular Access to Diverse Amphoteric α-Boryl Aldehydes or Borylated Heterocycles via Photoredox Catalysis

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(19), P. 12648 - 12655

Published: Sept. 13, 2023

The stable α-boryl aldehydes are important amphoteric synthetic intermediates that act as linchpins in organic synthesis. However, current approaches to these building blocks typically rely on oxidative processes, which might lead issues such lack of product diversity and functional group compatibility. Here, we report the design utilization 2-(BMIDA) acrylaldehyde a suitable coupling partner toward photoredox-catalyzed intermolecular radical addition reaction for rapid synthesis functionalized aldehydes. With commercially available photocatalyst readily accessible alkyltrifluoroborates precursors, wide range were obtained up 90% yield. Preliminary mechanistic studies suggested proceed through radical-polar crossover processes. potential method was further demonstrated by scale-up reactions, several transformations, derivatization bioactive molecules. Moreover, simply switching precursors α-amino acids, diverse 4-boryl 2,3-dihydropyrroles could be accessed via addition/cyclization sequence. Furthermore, MIDA boronate-bearing six- or seven-membered heterocycles also when corresponding β- γ-amino acid used. This strategy provides facile, robust, diversity-oriented approach borylated heterocycles.

Language: Английский

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Sigmatropic rearrangements of B(MIDA)-propargylic alcohols towards the diverse synthesis of α-functionalized organoborons

Science China Chemistry, Journal Year: 2023, Volume and Issue: 67(2), P. 568 - 575

Published: Oct. 30, 2023

Language: Английский

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Regioselective Electrophilic Addition to Propargylic B(MIDA)s Enabled by β‐Boron Effect

Advanced Science, Journal Year: 2023, Volume and Issue: 10(30)

Published: Aug. 26, 2023

Electrophilic addition reaction to alkynes is of fundamental importance in organic chemistry, yet the regiocontrol when reacting with unsymmetrical 1,2-dialkyl substituted often problematic. Herein, it demonstrated that rarely recognized β-boron effect can confer a high level site-selectivity several alkyne electrophilic reactions. A broad range highly functionalized and complex organoborons are thus formed under simple conditions starting from propargylic MIDA (N-methyliminodiacetic acid) boronates. These products be valuable building blocks synthesis. In regiocontrol, this study also observes drastic rate enhancement upon B(MIDA) substitution. Theoretical calculation reveals highest occupied molecular obital (HOMO) energy significantly raised by 0.3 eV, preferential γ position due its higher HOMO orbital coefficient more negative natural bond (NBO) charge compared β position. This demonstrates potential utilizing stereoelectronic control chemical transformations, which inspire further research area.

Language: Английский

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Visible-Light-Driven Decarboxylative Borylation: Rapid Access to α- and β-Amino-boronamides

Organic Letters, Journal Year: 2023, Volume and Issue: 25(51), P. 9249 - 9254

Published: Dec. 19, 2023

In this study, we described a two-step process involving an efficient visible-light-induced decarboxylative borylation of α- and β-amino redox-active esters with bis(catecholato)diboron, followed by transamination 1,8-diaminonapthalene (DANH2). A series boronamides were obtained in moderate to excellent yields one-pot procedure. The photochemical proved be very even when conducted under flow conditions shorter reaction durations scalable synthesis DAN boronates.

Language: Английский

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Derivatization of 2,1,3-Benzothiadiazole via Regioselective C–H Functionalization and Aryne Reactivity

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(9), P. 6138 - 6148

Published: April 22, 2024

Despite growing interest in 2,1,3-benzothiadiazole (BTD) as an integral component of many functional molecules, methods for the functionalization its benzenoid ring have remained limited, and even simply decorated BTDs required de novo synthesis. We show that regioselective Ir-catalyzed C–H borylation allows access to versatile 5-boryl or 4,6-diboryl BTD building blocks, which undergo at C4, C5, C6, C7 positions. The optimization regioselectivity are discussed. A broad reaction scope is presented, encompassing ipso substitution C–B bond, first examples ortho-directed BTD, closing reactions generate fused systems, well generation capture novel BTD-based heteroarynes. latter discussed with reference Aryne Distortion Model.

Language: Английский

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Nickel‐catalyzed Nucleophilic C‐Borylation of Imines

Chemistry - An Asian Journal, Journal Year: 2023, Volume and Issue: 18(18)

Published: Aug. 7, 2023

Abstract Application of bioisostere plays an important role in drug discovery. α‐Aminoboronic acid is the familiar α‐amino acid. Developing reactions for synthesis a wide variety α‐aminoboronic one task synthetic chemistry. Herein, we report development nucleophilic C ‐borylation chemistry N ‐arylimines catalyzed by nickel. The reaction proceeds through insertion borylnickel species into C=N bond to afford corresponding α‐aminoboronate, which was isolated as acetamide after trapping with acetic anhydride. ‐Benzyl imine also tolerated developed reaction.

Language: Английский

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