Chemoselective Cu-Catalyzed Cross-Nucleophile Alkylarylation of Alkenes

ACS Catalysis, Journal Year: 2024, Volume and Issue: unknown, P. 14242 - 14250

Published: Sept. 11, 2024

Language: Английский

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Sequential Conversion of Vinyl Triflates to 1,2-Disilanes via Technical Control of Magnesium and Calcium Reducibility Differences

Organic Letters, Journal Year: 2025, Volume and Issue: 27(4), P. 948 - 953

Published: Jan. 17, 2025

Reductive direct substitution of α-arylvinyl triflates on the sp2 carbon atom by magnesium in presence chlorosilane proceeded to give corresponding α-silylstyrenes, which could not be reduced further, and reaction completely stopped because reduction potential α-silylstyrenes lies out reducible field magnesium. The subsequent calcium brought about second introduction another silyl group vicinal lead a selective simple route variety 1,2-disilanes from vinyl cooperative works with different potentiality.

Language: Английский

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Pd‐Catalyzed Cross‐Coupling of Alkylbisboronic Esters

ChemistryOpen, Journal Year: 2025, Volume and Issue: unknown

Published: April 10, 2025

A Pd-catalyzed cross-coupling between alkylbisboronic esters and aryl bromides is described. variety of are found to be competent substrates in the reaction. Different alkyl chain lengths examined, a two-carbon linker optimal length. Several competition experiments performed better understand mechanism

Language: Английский

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Interlocking Pseudorotaxanes through Borane- and Boronic Ester-Mediated Carbon–Carbon Bond Formation

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

Published: April 30, 2025

Employing 9-BBN and pinacol boronic ester as surrogate stoppers, pseudorotaxanes presenting terminal alkenes can be transformed into organoborane or organoboronate rotaxanes, respectively. Various boron-based reactions then used to replace these temporary stoppers with bulky derivatives of aromatic bromides, α-bromo ketones, 1-bromo-1-alkynes, facilitating the selective formation sp3-sp2, sp3-sp3, sp3-sp carbon-carbon single bonds,

Language: Английский

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Recent Advances in Catalytic Asymmetric Synthesis of Chiral 1,2-Bis(boronic) Esters

Chinese Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 44(5), P. 1385 - 1385

Published: Jan. 1, 2024

Chiral 1,2-bis(boronic) esters are essential building blocks in the field of synthetic chemistry, and their catalytic asymmetric synthesis has attracted significant interest chemists.Recently, diboration olefins, using transition metals chiral diols, emerged as straightforward atom-economical methods for producing highly valuable esters.Asymmetric hydrogenation vinyl bis(boronic) can be a complementary approach to synthesizing these products.Additionally, borofunctionalization alkenes or alkynes represents another effective strategy constructing scaffolds.A recent innovation involves migratory coupling reactions with gem-diborylalkanes, offering new avenues esters.The latest developements challenges moleculeshis summarized, potential future research directions this prospected.

Language: Английский

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Stereospecific Phosphination and Thioetherification of Organoboronic Esters

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(28), P. 18873 - 18878

Published: July 2, 2024

Alkyllithium-activated organoboronic esters are found to undergo stereospecific phosphination with copper chloride and chlorophosphines. They also react thiolsulfonate electrophiles under catalysis. These reactions enable thiolation of esters, which further applied in preparation chiral ligands biologically active molecules.

Language: Английский

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Catalytic Selective Functionalization of Poly(organoborons)^†

Chinese Journal of Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 28, 2024

Comprehensive Summary Organoborons are commonly used building blocks for rapidly increasing molecular complexity. Although significant progress has been made in the selective functionalization of mono‐organoborons, site‐selective poly(organoborons) attracted substantial interest organic synthesis, pharmaceuticals, and agrochemicals due to presence multiple potential reaction sites. This review discusses various activation modes target C–B bond, with diverse transformations being achieved both a efficient manner. Recent advances catalytic 1, n ‐diboronates through ionic radical pathways highlighted. Furthermore, we summarize existing challenges future research directions this field. Key Scientists In 1993, Suzuki, Miyaura coworkers developed pioneering example arylation towards cis‐1,2‐bis(boryl) alkenes, marking inception The Morken group contributions asymmetric diboration alkenes realized elegant these compounds since 2004. 2016, Fernández colleagues internal bond tri(boronates). Since 2019, Aggarwal Giese‐type addition at more substituted 1,2‐bis(boronic) esters photoredox catalysis. controllable regiodivergent alkynylation 1,3‐bis(boronic) was by Gao 2023. Recently, Qin conducted on programmable late‐stage bridge‐substituted bicyclo[1.1.1]pentane (BCP) bis‐boronates. 2013, stereoselective have several groups, including those led Chen. summarizes latest most developments field 1993.

Language: Английский

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Iridium-Catalyzed Stereocontrolled C(sp³)–C(sp³) Cross-Coupling of Boronic Esters and Allylic Carbonates Enabled by Boron-to-Zinc Transmetalation

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 6, 2025

The stereocontrolled C(sp3)–C(sp3) cross-coupling represents a considerable challenge of great contemporary interest. While this has been achieved through the reactions boronate complexes with π-allyl iridium complexes, such suffered from limited substrate scope. We now report that following transmetalation to organozinc reagents enables previously unreactive substrates engage in cross-coupling. broader scope enabled their application synthesis biologically active molecules. react stereoinvertive coupling pathway contrast other electrophiles occur retention stereochemistry. reaction uniquely combines enantiospecific reactivity an enantioenriched organometallic nucleophile enantioselective engagement racemic electrophile, enabling access all stereoisomers.

Language: Английский

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Ligand-Controlled Enantioselective Copper-Catalyzed Hydroboration and Ring-Opening Dihydroboration of Arylidenecyclobutanes

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: March 25, 2025

Arylidenecyclobutanes are readily accessible and versatile reagents in synthetic chemistry due to the multifaceted reactivity exhibited by their alkene strained cyclobutane moieties. However, metal-catalyzed enantioselective functionalization of arylidenecyclobutanes, particularly controllable ring-retaining ring-opening reactions, is rarely explored. Considering utility enantioenriched organoboronate compounds, herein we report ligand-controlled copper-catalyzed hydroboration dihydroboration reactions arylidenecyclobutanes that afford chiral α-cyclobutyl benzylboronate 1,5-diboronate compounds with high enantioselectivity when (S)-DTBM-Segphos (S,S)-Ph-BPE employed, respectively. Mechanistic studies reveal process via β-C elimination significantly slower than arylidenecyclopropanes presence CuOAc (S,S)-Ph-BPE. The these two protocols further demonstrated through conducting various stereospecific site-selective transformations organoboron products, including concise synthesis bioactive molecules.

Language: Английский

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Site‐Selective Activation and Stereospecific Functionalization of Bis(boronic esters) Derived from 2‐Alkenes: Construction of Propionates and Other 1,2‐Difunctional Motifs

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

Published: Aug. 13, 2024

Non-directed regioselective activation of bis(boronic esters), followed by functionalization, is reported. A bulky activator shown to selectively activate the less hindered boronic ester enabling it undergo stereospecific cross-coupling a variety electrophiles. This steric-based regioselectivity provides simple and efficient method prepare highly functionalized, enantiomerically enriched products starting from alkenes.

Language: Английский

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