Zirconium Catalyzed Transformations Using Organoboron DOI

Somenath Mahato,

S. K. NANDY,

Kanak Kanti Das

et al.

European Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 2022(25)

Published: May 30, 2022

Abstract Organoboron compounds have extreme potential for organic synthesis. Ready functionalization of organoboron intrigued people to develop various protocols their Over the last several decades, there has been a substantial development in synthesizing new using transition metals. Among metals, zirconium also found catalyze diverse reactions organoboron. The chemistry become more popular with metallocenes, particularly bis(cyclopentadienyl)zirconocene chloride hydride, well‐known Schwartz reagent. These metallocenes possess significant role hydrozirconation, hydroboration, hydrogenation, carbozirconation, and promising tri‐ n ‐butyl tin hydride alternative. This minireview focuses on transformations employing catalysts that developed so far.

Language: Английский

N-Heterocyclic carbenes as privileged ligands for nickel-catalysed alkene functionalisation DOI Creative Commons

Boon Chong Lee,

Chen‐Fei Liu,

Leroy Qi Hao Lin

et al.

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 52(9), P. 2946 - 2991

Published: Jan. 1, 2023

This review discusses the applications of N-heterocyclic carbene ligands and their influence on reactivity selectivity Ni-catalysed alkene functionalisations.

Language: Английский

Citations

71
Nickel/Brønsted acid dual-catalyzed regio- and enantioselective hydrophosphinylation of 1,3-dienes: access to chiral allylic phosphine oxides DOI Creative Commons
Jiao Long, Yuqiang Li, Weining Zhao

et al.

Chemical Science, Journal Year: 2021, Volume and Issue: 13(5), P. 1390 - 1397

Published: Dec. 28, 2021

While chiral allylic organophosphorus compounds are widely utilized in asymmetric catalysis and for accessing bioactive molecules, their synthetic methods still very limited. We report the development of nickel/Brønsted acid dual-catalyzed hydrophosphinylation 1,3-dienes with phosphine oxides. This reaction is characterized by an inexpensive catalyst, broad substrate scope, high regio- enantioselectivity. study allows construction oxides a highly economic efficient manner. Preliminary mechanistic investigations suggest that 1,3-diene insertion into Ni-H species regioselective process formation C-P bond irreversible step.

Language: Английский

Citations

47
Updated Progress of the Copper-Catalyzed Borylative Functionalization of Unsaturated Molecules DOI Creative Commons
Bingru Li,

Huayu Liang,

Arumugam Vignesh

et al.

Molecules, Journal Year: 2023, Volume and Issue: 28(5), P. 2252 - 2252

Published: Feb. 28, 2023

Borylation has become a powerful method to synthesize organoboranes as versatile building blocks in organic synthesis, medicinal chemistry, and materials science. Copper-promoted borylation reactions are extremely attractive due the low cost non-toxicity of copper catalyst, mild reaction conditions, good functional group tolerance, convenience chiral induction. In this review, we mainly updated recent advances (from 2020 2022) synthetic transformations C=C/C≡C multiple bonds, C=E bonds mediated by boryl systems.

Language: Английский

Citations

21
Nickel boryl complexes and nickel-catalyzed alkyne borylation DOI Creative Commons

Lukas Tendera,

Felipe Fantuzzi, Todd B. Marder

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 14(8), P. 2215 - 2228

Published: Jan. 1, 2023

The first nickel bis-boryl complexes cis-[Ni( i Pr2ImMe)2(Bcat)2], Pr2ImMe)2(Bpin)2] and Pr2ImMe)2(Beg)2] are reported, which were prepared via the reaction of a source [Ni( Pr2ImMe)2] with diboron(4) compounds B2cat2, B2pin2 B2eg2 ( Pr2ImMe = 1,3-di-iso-propyl-4,5-dimethylimidazolin-2-ylidene; B2cat2 bis(catecholato)diboron; bis(pinacolato)diboron; bis(ethylene glycolato)diboron). X-ray diffraction DFT calculations strongly suggest that delocalized, multicenter bonding scheme dictates situation NiB2 moiety in these square planar complexes, reminiscent "non-classical" H2 complexes. also efficiently catalyzes diboration alkynes using as boron under mild conditions. In contrast to known platinum-catalyzed diboration, system follows different mechanistic pathway, not only provides 1,2-borylation product excellent yields, but an efficient approach other products such C-C coupled borylation or rare tetra-borylated compounds. mechanism nickel-catalyzed alkyne was examined by means stoichiometric reactions calculations. Oxidative addition diboron reagent is dominant; steps catalytic cycle coordination subsequent at coordinated and, thus, activated yield type [Ni(NHC)2(η2-cis-(Bcat)(R)C[double bond, length m-dash]C(R)(Bcat))], exemplified isolation structural characterization Pr2ImMe)2(η2-cis-(Bcat)(Me)C[double m-dash]C(Me)(Bcat))] Pr2ImMe)2(η2-cis-(Bcat)(H7C3)C[double m-dash]C(C3H7)(Bcat))].

Language: Английский

Citations

20
Enantioselective Ni‐Catalyzed Three‐Component Dicarbofunctionalization of Alkenes DOI Open Access

Zhan Dong,

Liangliang Song, Liang‐An Chen

et al.

ChemCatChem, Journal Year: 2023, Volume and Issue: 15(18)

Published: Aug. 3, 2023

Abstract Asymmetric multicomponent reactions are considered as efficient protocols for constructing complex chiral molecules because of their step‐ and atom‐economy. Nickel‐catalyzed asymmetric three‐component dicarbofunctionalization alkenes has been well developed in recent years, which is used the area total synthesis natural products late‐stage modification drugs rapid incorporation sp 3 ‐enriched carbon centers. In this concept, significant breakthroughs field summarized, together with related mechanisms. Moreover, remaining challenges potential opportunities also highlighted.

Language: Английский

Citations

17
Enantioselective 1,4-Borylamination via Copper-Catalyzed Cascade Hydroborylation and Hydroamination of Arylidenecyclopropanes DOI

Yu-Shen Zhu,

Yuecong Guo, Yingying Zhu

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(47), P. 32283 - 32291

Published: Nov. 13, 2024

Compounds bearing both boryl and amino groups at distal positions are invaluable synthons for synthesizing pharmaceuticals, drug candidates, natural products, but their catalytic enantioselective synthesis remains rarely explored. We report the first 1,4-borylamination reaction through a copper-catalyzed cascade hydroborylation hydroamination of arylidenecyclopropanes. This combines four readily available components in highly chemo-, site-, fashion (>20:1 r.r. up to 99% ee), yielding diverse array synthetically valuable enantioenriched 4-amino alkylboronates. The versatile utility these products is highlighted by transformations wide applications pharmaceutical discovery. Preliminary mechanistic studies were conducted elucidate operative pathway, intermediates, origins its high chemo- site-selectivity.

Language: Английский

Citations

6
A Unified Synthetic Strategy to Introduce Heteroatoms via Electrochemical Functionalization of Alkyl Organoboron Reagents DOI
Su Yong Go, Hyunho Chung, Samuel Jaeho Shin

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(20), P. 9149 - 9160

Published: May 16, 2022

Based on systematic electrochemical analysis, an integrated synthetic platform of C(sp3)-based organoboron compounds was established for the introduction heteroatoms. The electrochemically mediated bond-forming strategy shown to be highly effective functionalization sp3-hybridized carbon atoms with significant steric hindrance. Moreover, virtually all nonmetallic heteroatoms could utilized as reaction partners using one unified protocol. observed reactivity stems from two consecutive single-electron oxidations substrate, which eventually generates extremely reactive carbocation key intermediate. detailed profile elucidated through multifaceted studies. Ultimately, a new dimension in activation strategies accomplished driven development.

Language: Английский

Citations

24
Synthesis, Structure, and Hydroboration Reactivity of Anionic Nickel(0) Complexes Supported by Bidentate NHC-Pyridone Ligands DOI Creative Commons
Medina Afandiyeva, Abhishek A. Kadam, Xijue Wu

et al.

Organometallics, Journal Year: 2022, Volume and Issue: 41(21), P. 3014 - 3023

Published: Oct. 28, 2022

A family of anionic, formally nickel(0) complexes supported by bidentate NHC–pyridone ligands is described. The unsymmetric chelating environment and capping [K(18-crown-6)]+ countercation allow isolation single-component, monometallic in high yield. steric electronic properties are assessed through a battery experimental (NMR, IR, UV–vis, X-ray diffraction) computational tools. Catalytic activity for highly branched-selective hydroboration styrene with HBpin demonstrated. Control experiments implicate an important role the pyridone establishing reactivity regioselectivity, suggesting potential to leverage secondary coordination sphere effects these single-component precatalysts reagent activation delivery.

Language: Английский

Citations

23
Modular and Fast Synthesis of Versatile Secondary α,α‐Dialkyl Boronates via Deoxygenative Alkylboration of Aldehydes DOI

Wenhao Xu,

Purui Zheng,

Jun Zhou

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(49)

Published: Oct. 12, 2022

Secondary α,α-dialkyl boronates are widely used due to their great versatility. Herein we report an unprecedented deoxygenative alkylboration of aldehydes, a facile method access this type products. A sequence difunctionalization can be obtained smoothly from the readily available aldehydes in only two steps. This rather than conventional alkenes also opens new possibilities within field.

Language: Английский

Citations

20
Recent Progress in NiH-Catalyzed Linear or Branch Hydrofunctionalization of Terminal or Internal Alkenes DOI
Huimin Yang, Yang Ye

Topics in Current Chemistry, Journal Year: 2023, Volume and Issue: 381(5)

Published: July 20, 2023

Language: Английский

Citations

11