1,2‐Aryl Migration Induced by Amide C−N Bond‐Formation: Reaction of Alkyl Aryl Ketones with Primary Amines Towards α,α‐Diaryl β,γ‐Unsaturated γ‐Lactams DOI
Rong Hu,

Yigao Tao,

Xiaofeng Zhang

et al.

Angewandte Chemie, Journal Year: 2021, Volume and Issue: 133(15), P. 8506 - 8511

Published: Jan. 15, 2021

Abstract Rearrangement reactions incorporated into cascade play an important role in rapidly increasing molecular complexity from readily available starting materials. Reported here is a Cu‐catalyzed reaction of α‐(hetero)aryl‐substituted alkyl (hetero)aryl ketones with primary amines that incorporates unusual 1,2‐aryl migration induced by amide C−N bond formation to produce class structurally novel α,α‐diaryl β,γ‐unsaturated γ‐lactams generally good‐to‐excellent yields. This has broad substrate scope respect amines, allows wide spectrum groups smoothly undergo 1,2‐migration, and tolerates electronically diverse α‐substituents on the ring ketones. Mechanistically, this may stem intramolecular which induces nucleophilic aryl group acyl carbon center electrophilic conjugated resulting iminium moiety.

Language: Английский

Cobalt‐Catalyzed Regiodivergent Ring‐Opening Dihydroboration of Arylidenecyclopropanes to Access Skipped Diboronates DOI Creative Commons

Boon Beng Tan,

Ming Hu, Shaozhong Ge

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(32)

Published: June 7, 2023

Ligand-controlled regiodivergent cobalt-catalyzed ring-opening dihydroboration of arylidenecyclopropanes is developed to access synthetically versatile skipped diboronates with catalysts generated in situ from Co(acac)2 and dpephos or xantphos. A variety reacted pinacolborane (HBpin) form the corresponding 1,3- 1,4-diboronates high isolated yields regioselectivity. Skipped diboronate products these reactions can undergo various transformations allow selective installation two different functional groups along alkyl chains. Mechanistic studies suggest that combine hydroboration homoallylic allylic boronate intermediates.

Language: Английский

Citations

24
Cyclic (Alkyl)(amino)carbene Ligands Enable Cu‐Catalyzed Markovnikov Protoboration and Protosilylation of Terminal Alkynes: A Versatile Portal to Functionalized Alkenes** DOI
Yang Gao, S Yazdani, Aaron Kendrick

et al.

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(36), P. 19871 - 19878

Published: June 23, 2021

Abstract Regioselective hydrofunctionalization of alkynes represents a straightforward route to access alkenyl boronate and silane building blocks. In previously reported catalytic systems, high selectivity is achieved with limited scope substrates and/or reagents, general solutions lacking. Herein, we describe selective copper‐catalyzed Markovnikov terminal that facilitated by strongly donating cyclic (alkyl)(amino)carbene (CAAC) ligands. Using this method, both alkyl‐ aryl‐substituted are coupled variety boryl silyl reagents α‐selectivity. The reaction scalable, the products versatile intermediates can participate in various downstream transformations. Preliminary mechanistic experiments shed light on role CAAC ligands process.

Language: Английский

Citations

56
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
Decarboxylation of β-boryl NHPI esters enables radical 1,2-boron shift for the assembly of versatile organoborons DOI Creative Commons
Yu Guo,

Xiaosha Wang,

Chengbo Li

et al.

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

Published: Sept. 14, 2023

In recent years, numerous 1,2-R shift (R = aliphatic or aryl) based on tetracoordinate boron species have been well investigated. the contrary, corresponding radical migrations, especially 1,2-boryl for construction of organoborons is still in its infancy. Given paucity and significance such strategies chemistry, it urgent to develop other efficient alternative synthetic protocols enrich these underdeveloped 1,2-boron before their fundamental potential applications could be fully explored at will. Herein, we demonstrated a visible-light-induced photoredox neutral decarboxylative cross-coupling reaction, which undergoes give translocated C-radical further capture versatile acceptors. The mild reaction conditions, good functional-group tolerance, broad β-boryl NHPI esters scope as acceptors make this protocol applicable modification bioactive molecules. It can expected that methodology will very useful tool an strategy primary via novel mode.

Language: Английский

Citations

18
Visible-Light-Triggered Sulfonylation/Aryl Migration/Desulfonylation and C–S/Se Bond Formation Reaction: 1,2,4-Trifunctionalization of Butenyl Benzothiazole Sulfone with Thiosulfonate/Selenosulfonates DOI
Xinyu Liu,

Shi‐Yin Tian,

Yi‐Fan Jiang

et al.

Organic Letters, Journal Year: 2021, Volume and Issue: 23(21), P. 8246 - 8251

Published: Oct. 15, 2021

A visible-light-triggered radical cascade sulfonylation/aryl migration/desulfonylation and C-S/Se bond formation reaction of butenyl benzothiazole sulfone with thiosulfonates or selenosulfonates is developed. This study affords the 1,2,4-trifunctionalization derivatives under mild conditions.

Language: Английский

Citations

37
N -Heterocyclic carbene catalytic 1,2-boron migrative acylation accelerated by photocatalysis DOI Creative Commons
Huang Hua, Zhaoyuan Yu,

Luyao Han

et al.

Science Advances, Journal Year: 2024, Volume and Issue: 10(30)

Published: July 24, 2024

The transformation of organoboron compounds plays an important role in synthetic chemistry, and recent advancements boron-migration reactions have garnered considerable attention. Here, we report unprecedented 1,2-boron migrative acylation upon photocatalysis-facilitated

Language: Английский

Citations

5
Synthesis of 1,3‐Bis‐(boryl)alkanes through Boronic Ester Induced Consecutive Double 1,2‐Migration DOI Creative Commons
Cai You, Armido Studer

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(39), P. 17245 - 17249

Published: June 24, 2020

A general and efficient approach for the preparation of 1,3-bis-(boryl)alkanes is introduced. It shown that readily generated vinylboron ate complexes react with commercially available ICH

Language: Английский

Citations

39
Regio‐ and Stereoselective 1,2‐Carboboration of Ynamides with Aryldichloroboranes DOI Creative Commons
Cai You,

Mika Sakai,

Constantin G. Daniliuc

et al.

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(40), P. 21697 - 21701

Published: July 26, 2021

Abstract Catalyst‐free 1,2‐carboboration of ynamides is presented. Readily available aryldichloroboranes react with alkyl‐ or aryl‐substituted in high yields complete regio‐ and stereoselectivity to valuable β‐boryl‐β‐alkyl/aryl α‐aryl substituted enamides which belong the class trisubstituted alkenylboronates. The reaction experimentally easy conduct, shows functional group tolerance broad substrate scope. Gram‐scale reactions diverse synthetic transformations convincingly demonstrate potential this method. can also be used access 1‐boraphenalenes, a boron‐doped polycyclic aromatic hydrocarbons.

Language: Английский

Citations

32
Construction of α-Halogenated Boronic Esters via Visible Light-Induced C–H Bromination DOI

Feng‐Chen Gao,

Ming Li,

Heng-Yu Gu

et al.

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(19), P. 14246 - 14254

Published: Sept. 21, 2023

α-Halogenated boronic esters are versatile building blocks that can be diversified into a wide variety of polyfunctionalized molecules. However, their synthetic potential has been hampered by limited preparation methods. Herein, we report visible light-induced C-H bromination reaction readily available benzyl esters. This method features high yields, mild conditions, simple operation, and good functional group tolerance. The analogous chlorides iodides accessed via Finkelstein reaction. Synthesis halogenated geminal diborons also demonstrated.

Language: Английский

Citations

11
Substituent Effects of Tetracoordinate Boron in Organic Synthesis DOI
Tsuyoshi Taniguchi

Chemistry - A European Journal, Journal Year: 2022, Volume and Issue: 28(19)

Published: Jan. 4, 2022

Abstract The present review focuses on recent examples of tetracoordinate boryl groups greatly influencing reactions in organic synthesis. Electron‐rich stabilize or activate reactive intermediates such as cations, radicals and π‐conjugation systems, interaction the with carbon‐boron heteroatom‐boron bonds is origin substituent effects. Unique effects often promote desired affect results yield selectivity products.

Language: Английский

Citations

18