Visible-Light-Mediated Radical trans-Hydroboration of Alkynes with NHC Borane DOI

Xin Wu,

Zhang Chen, Peng Xue

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 19, 2024

Although the radical hydroboration of alkenes with N-heterocyclic carbene (NHC) borane is well documented, alkynes, especially terminal remains challenging. Herein, a photoredox-catalyzed trans-hydroboration alkynes NHC has been developed, which provided various alkenyl boron compounds in moderate to good yields. This protocol exhibits broad substrate scope, as both internal and were compatible. The synthetic value this method was further demonstrated by its applicability late-stage modification bioactive molecules. A preliminary mechanism for reaction proposed.

Language: Английский

Lewis Base–Boryl Radicals Enabled Borylation Reactions and Selective Activation of Carbon–Heteroatom Bonds DOI

Tianyu Peng,

Feng‐Lian Zhang, Yi‐Feng Wang

et al.

Accounts of Chemical Research, Journal Year: 2022, Volume and Issue: 56(2), P. 169 - 186

Published: Dec. 26, 2022

ConspectusThe past decades have witnessed tremendous progress on radical reactions. However, in comparison with carbon, nitrogen, oxygen, and other main group element centered radicals, the synthetic chemistry of boron radicals was less studied, mainly due to high electron-deficiency instability such 3-center-5-electron species. In 1980s, Roberts co-workers found that coordination a Lewis base (amines or phosphines) center could form 4-center-7-electron boryl (Lewis base-boryl LBRs) are be more stable. only limited applications were developed. 2008, Curran achieved breakthrough discovery N-heterocyclic carbene (NHC) which enable range reduction polymerization Despite these exciting findings, powerful valuable LBRs would expected, given structures reactivities easily modulated, provide ample opportunities discover new this Account, summary our key contributions LBR-enabled borylation reactions selective activation inert carbon-heteroatom bonds will presented.Organoboron compounds shown versatile chemical society, their syntheses rely principally ionic The development mechanistically different allows synthesizing products inaccessible by traditional methods. For purpose, we progressively developed series NHC-boryl mediated chemo-, regio-, stereoselective alkenes alkynes, wide variety structurally diverse organoboron molecules successfully prepared. utility borylated also demonstrated. Furthermore, disclosed photoredox protocol for oxidative generation enabled useful defluoroborylation arylboration reactions.Selective bond is an ideal way convert simple starting materials value-added products, while cleavage bonds, particular chemoselectivity control when multiple identical present similar environments, remains long-standing challenge. We envisaged finely tuning properties might solution address Recently, 4-dimethylaminopyridine (DMAP)-boryl promoted sequential C-F functionalization trifluoroacetic acid derivatives, α-C-F selectively snipped via spin-center shift mechanism. This strategy enables facile conversion abundantly available highly mono- difluorinated molecules. Encouraged finding, further three-step sequence construct all-carbon quaternary centers from trichloromethyl groups, where three C-Cl cleaved rational choice suitable precursors each step. dehydroxylative alkylation α-hydroxy carboxylic derivatives achieved, allowing efficient some biomass platform value products.

Language: Английский

Citations

73
Radical hydroboration for the synthesis of organoboron compounds DOI
Yee Lin Phang, Ji‐Kang Jin, Feng‐Lian Zhang

et al.

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(32), P. 4275 - 4289

Published: Jan. 1, 2024

This review describes the recent research on radical hydroboration, which covers different boron sources including N-heterocyclic carbene borane, bis(pinacolato)diboron and pinacolborane, as well strategies in boryl generation.

Language: Английский

Citations

12
Diastereoselective dearomatization of indoles via photocatalytic hydroboration on hydramine-functionalized carbon nitride DOI Creative Commons
Qiao Zhang, Wengang Xu, Qiong Liu

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: May 22, 2024

Abstract A protocol for trans -hydroboration of indole derivatives using heterogeneous photocatalysis with NHC-borane has been developed, addressing a persistent challenge in organic synthesis. The protocol, leveraging high crystalline vacancy-engineered polymeric carbon nitride as catalyst, enables diastereoselective synthesis, expanding substrate scope and complementing existing methods. approach emphasizes eco-friendliness, cost-effectiveness, scalability, making it suitable industrial applications, particularly renewable energy contexts. catalyst’s superior performance, attributed to its rich carbon-vacancies well-ordered structure, surpasses more expensive homogeneous alternatives, enhancing viability large-scale use. This innovation holds promise synthesizing bioactive compounds materials relevant medicinal chemistry beyond.

Language: Английский

Citations

8
Transition metal-free radicaltrans-hydroboration of alkynes with NHC-boranesviavisible-light photoredox catalysis DOI

Dingchang Li,

Jia‐Hao Zeng, Yuhang Yang

et al.

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(8), P. 2075 - 2080

Published: Jan. 1, 2023

Visible-light-induced 4-CzIPN-catalyzed trans-hydroboration of alkynes with NHC-boranes to generate diverse ( E )-alkenylboranes high selectivity.

Language: Английский

Citations

13
Selective multifunctionalization ofN-heterocyclic carbene boranesviathe intermediacy of boron-centered radicals DOI Creative Commons

Feng‐Xing Li,

Xinmou Wang,

Jiaxin Lin

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 14(23), P. 6341 - 6347

Published: Jan. 1, 2023

The selective difunctionalization of N-heterocyclic carbene (NHC) boranes with alkenes has been achieved via decatungstate and thiol synergistic catalysis. catalytic system also allows stepwise trifunctionalization, leading to complex NHC three different functional groups which are challenging prepare by other methods. strong hydrogen-abstracting ability the excited enables generation boryl radicals from mono- di-substituted for realizing borane multifunctionalization. This proof-of-principle research provides a new chance fabricating unsymmetrical developing boron-atom-economic synthesis.

Language: Английский

Citations

13
Synthesis of 1,1-Diarylvinylsulfides via Visible-Light-Promoted Cascade Reaction of Alkynoates with Phenyl Disulfides DOI
Tao Jiang, Long Chen,

Shimei Wen

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(2), P. 1296 - 1300

Published: Jan. 4, 2024

Without any additives and photocatalysts, the visible-light-promoted radical cascade reaction between alkynoates phenyl disulfides has been developed at room temperature. Through S–S bond photolysis homolytic cleavage, addition of a sulfur radical, aryl migration, decarboxylation, H atom abstraction, provides an efficient practical route to trisubstituted 1,1-diarylvinylsulfides with wide scope substrates good excellent yields.

Language: Английский

Citations

5
Metal-Free One-Pot Multi-Functionalization of Unsaturated Compounds with Interelement Compounds by Radical Process DOI Creative Commons
Yuki Yamamoto, Akiya Ogawa

Molecules, Journal Year: 2023, Volume and Issue: 28(2), P. 787 - 787

Published: Jan. 12, 2023

In recent years, the importance of “environmentally friendly manufacturing” has been increasing toward establishment a resource-recycling society. organic synthesis, as well, it is becoming increasingly important to develop new synthetic strategies with resource conservation and recycling elemental resources in mind, rather than just only synthesis. Many studies on construction frameworks functional molecules using ionic reactions transition-metal-catalyzed have reported, but most them focused formation carbon–carbon bonds. However, essential introduce appropriate groups at positions order for express their functions, furthermore, highly selective preparation multiple considered creation molecules. this review, we focus radical high group selectivity overview progress practical methods simultaneous introduction propose future that emphasize environmental friendliness.

Language: Английский

Citations

11
Switchable Access to Mono‐ and Di‐Alkylated Boranes via Visible‐Light‐Induced Hydroboration of Alkenes with NHC‐Borane DOI Open Access

Xin Wu,

Yue Wang,

Ming‐Xi Zhou

et al.

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 365(22), P. 3824 - 3829

Published: Sept. 23, 2023

Abstract A photo‐induced metal‐free radical hydroboration of various styrenes with NHC‐borane has been developed, which can provide mono‐ and di‐alkylated boranes in a selective manner. Besides, this strategy also be applied to prepare di‐functionalized two different alkyl groups. Mild reaction conditions good functional groups compatibility were observed. Preliminary mechanism for was proposed.

Language: Английский

Citations

9
Photoredox dearomative β-hydroborylation of indoles for the synthesis of borylated indolines DOI

Yongchan Jian,

Fei Wen, Jianping Shang

et al.

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 11(1), P. 149 - 155

Published: Nov. 15, 2023

A photocatalysed dearomative β-hydroborylation reaction of indoles and NHC-boranes was developed for the construction borylated indolines.

Language: Английский

Citations

9
Catalyst-free racemic and H2O/CPA-catalyzed asymmetric regio-reversed domino processes of triketone enones with azlactones DOI

Yun-Dong Fu,

Xiang Gao, Shi‐Kun Jia

et al.

Green Chemistry, Journal Year: 2023, Volume and Issue: 25(14), P. 5692 - 5697

Published: Jan. 1, 2023

The first regio-reversed domino processes of triketone enones with azlactones are established leading to the formation a variety bicyclic furofurans bearing vicinal quaternary carbons in good excellent yields.

Language: Английский

Citations

8