A General Method to Access Sterically Encumbered Geminal Bis(boronates) via Formal Umpolung Transformation of Terminal Diboron Compounds DOI

Peng‐Fei Ning,

Yi Wei, Xinyi Chen

et al.

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 136(4)

Published: Dec. 8, 2023

Abstract General methods for the preparation of geminal bis(boronates) are great interest due to their widespread applications in organic synthesis. While terminal gem ‐diboron compounds readily accessible, construction sterically encumbered, internal analogues has remained a prominent challenge. Herein, we report formal umpolung strategy access these valuable building blocks. The available 1,1‐diborylalkanes were first converted into corresponding α‐halogenated derivatives, which then serve as electrophilic components, undergoing substitution with diverse array nucleophiles form series C−C, C−O, C−S, and C−N bonds. This protocol features good tolerance steric hindrance wide variety functional groups heterocycles. Notably, this can also be extended synthesis diaryl compounds, therefore providing general approach various types bis(boronates).

Language: Английский

Diborodichloromethane as Versatile Reagent for Chemodivergent Synthesis of gem‐Diborylalkanes DOI

Tongchang Fang,

Liwei Wang, Miaomiao Wu

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(3)

Published: Dec. 8, 2023

Abstract The development of boron reagents is crucial for synthetic chemistry. Herein, we present a scalable and practical synthesis diborodichloromethane (DBDCM) through the reaction trichloromethyllithium with bis(pinacolato)diboron (B 2 pin ). resulting DBDCM reagent serves as basic unit construction various structurally diverse gem ‐diborylalkanes controllable C−Cl functionalizations. Moreover, have developed consecutive tetra‐functionalizations tertiary quaternary carbon containing molecules. use isotopically enriched 13 C‐chloroform 10 B enables C‐DBDCM B‐DBDCM reagents, which are beneficial convenient carbon‐13 boron‐10

Language: Английский

Citations

25
2-Aminophenanthroline Ligands Enable Mild, Undirected, Iridium-Catalyzed Borylation of Alkyl C–H Bonds DOI
Isaac Furay Yu, Kyan A. D’Angelo, Ángel D. Hernández-Mejías

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(11), P. 7124 - 7129

Published: March 8, 2024

The catalytic, undirected borylation of alkyl C–H bonds typically occurs at high reaction temperatures or with excess substrate, both, because the low reactivity bonds. Here we report a new iridium system comprising 2-anilino-1,10-phenanthroline as ligand that catalyzes little to no induction period and rates. This superior activation profile 2-aminophenanthroline-ligated catalysts leads broader scope, including reactions sensitive substrates, such epoxides glycosidic acetals, enhanced diastereoselectivity, higher yields borylated products. These also enable alkanes, amines, ethers room temperature for first time. Mechanistic studies imply facile N-borylation under conditions complexes containing N-boryl aminophenanthrolines are competent precatalysts reaction.

Language: Английский

Citations

10
A General Method to Access Sterically Encumbered Geminal Bis(boronates) via Formal Umpolung Transformation of Terminal Diboron Compounds DOI Open Access

Peng‐Fei Ning,

Yi Wei, Xinyi Chen

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(4)

Published: Dec. 8, 2023

Abstract General methods for the preparation of geminal bis(boronates) are great interest due to their widespread applications in organic synthesis. While terminal gem ‐diboron compounds readily accessible, construction sterically encumbered, internal analogues has remained a prominent challenge. Herein, we report formal umpolung strategy access these valuable building blocks. The available 1,1‐diborylalkanes were first converted into corresponding α‐halogenated derivatives, which then serve as electrophilic components, undergoing substitution with diverse array nucleophiles form series C−C, C−O, C−S, and C−N bonds. This protocol features good tolerance steric hindrance wide variety functional groups heterocycles. Notably, this can also be extended synthesis diaryl compounds, therefore providing general approach various types bis(boronates).

Language: Английский

Citations

21
Ir-Catalyzed, Nitrogen-Directed C(sp3)–H and C(sp2)–H Borylation with a Spiro-Fluorene-Indenoindenyl Ligand DOI Creative Commons

Tomonori Inoue,

Yu Sato, Yuki Nagashima

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 4061 - 4068

Published: Feb. 21, 2025

Language: Английский

Citations

0
Boron-Promoted Deprotonative Conjugate Addition: Geminal Diborons as Soft Pronucleophiles and Acyl Anion Equivalents DOI
Lucia Wang, Sheng‐Jia Lin,

Emmanuel Santos

et al.

The Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 87(15), P. 9896 - 9906

Published: July 12, 2022

Conjugate addition of α-boron-stabilized carbanions is an underexplored reaction modality. Existing methods require deborylation geminal di-/triboryl alkanes and/or the presence additional activating groups. We report 1,4-addition α,α-diboryl generated via deprotonation corresponding diborons. The methodology provided a general route to highly substituted and synthetically useful γ,γ-diboryl ketones. development diborons as soft pronucleophiles also enabled their use acyl anion equivalents one-pot tandem conjugate addition–oxidation sequence.

Language: Английский

Citations

10
Diborodichloromethane as Versatile Reagent for Chemodivergent Synthesis of gem‐Diborylalkanes DOI

Tongchang Fang,

Liwei Wang, Miaomiao Wu

et al.

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 136(3)

Published: Dec. 8, 2023

Abstract The development of boron reagents is crucial for synthetic chemistry. Herein, we present a scalable and practical synthesis diborodichloromethane (DBDCM) through the reaction trichloromethyllithium with bis(pinacolato)diboron (B 2 pin ). resulting DBDCM reagent serves as basic unit construction various structurally diverse gem ‐diborylalkanes controllable C−Cl functionalizations. Moreover, have developed consecutive tetra‐functionalizations tertiary quaternary carbon containing molecules. use isotopically enriched 13 C‐chloroform 10 B enables C‐DBDCM B‐DBDCM reagents, which are beneficial convenient carbon‐13 boron‐10

Language: Английский

Citations

0
A General Method to Access Sterically Encumbered Geminal Bis(boronates) via Formal Umpolung Transformation of Terminal Diboron Compounds DOI

Peng‐Fei Ning,

Yi Wei, Xinyi Chen

et al.

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 136(4)

Published: Dec. 8, 2023

Abstract General methods for the preparation of geminal bis(boronates) are great interest due to their widespread applications in organic synthesis. While terminal gem ‐diboron compounds readily accessible, construction sterically encumbered, internal analogues has remained a prominent challenge. Herein, we report formal umpolung strategy access these valuable building blocks. The available 1,1‐diborylalkanes were first converted into corresponding α‐halogenated derivatives, which then serve as electrophilic components, undergoing substitution with diverse array nucleophiles form series C−C, C−O, C−S, and C−N bonds. This protocol features good tolerance steric hindrance wide variety functional groups heterocycles. Notably, this can also be extended synthesis diaryl compounds, therefore providing general approach various types bis(boronates).

Language: Английский

Citations

0