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

Cu-Catalyzed Asymmetric Dicarboxylation of 1,3-Dienes with CO2 DOI
Yong‐Yuan Gui, Xiao‐Wang Chen,

Xiao-Yan Mo

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(5), P. 2919 - 2927

Published: Jan. 26, 2024

Dicarboxylic acids and derivatives are important building blocks in organic synthesis, biochemistry, the polymer industry. Although catalytic dicarboxylation with CO2 represents a straightforward sustainable route to dicarboxylic acids, it is still highly challenging limited generation of achiral or racemic acids. To date, asymmetric give chiral has not been reported. Herein, we report first 1,3-dienes via Cu catalysis. This strategy provides an efficient environmentally benign high regio-, chemo-, enantioselectivities. The copper self-relay catalysis, that is, Cu-catalyzed boracarboxylation carboxylated allyl boronic ester intermediates subsequent carboxylation C–B bonds dicarboxylates, key success this dicarboxylation. Moreover, protocol exhibits broad substrate scope, good functional group tolerance, easy product derivatizations, facile synthesis liquid crystalline polyester drug-like scaffolds.

Language: Английский

Citations

30
Catalytic Regio- and Enantioselective Boracarboxylation of Arylalkenes with CO2 and Diboron DOI

Sudong Zhang,

Liping Li,

DingXi Li

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(5), P. 2888 - 2894

Published: Jan. 26, 2024

Catalytic asymmetric carboxylation of readily available alkenes with CO2, an abundant and sustainable one-carbon building block, that gives access to value-added α-stereogenic carboxylic acids in atom- step-economic manner is highly attractive. However, it has remained a formidable challenge for the synthetic community. Here, first example Cu-catalyzed regio- enantioselective boracarboxylation reaction on various arylalkenes diboron under atmospheric pressure CO2 described, which afforded variety chiral β-boron-functionalized α-aryl up 87% yield 97% ee mild conditions. Importantly, α-substituted could also be subject this protocol excellent enantiopurities, thereby rendering efficient approach generation enantioenriched α-chiral all-carbon quaternary center. Moreover, high functional group tolerance, scalable synthesis, facile bioactive compounds, like (−)-scopolamine, (−)-anisodamine, (−)-tropicamide, further demonstrated utility strategy.

Language: Английский

Citations

26
BrCF2CN for photocatalytic cyanodifluoromethylation DOI Creative Commons

Xinjun Yang,

Jin‐Hong Lin, Ji‐Chang Xiao

et al.

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: Jan. 7, 2025

Considering the unique electronic properties of CF2 and CN groups, CF2CN group has significant potential in drug agrochemical development, as well material sciences. However, incorporating a remains considerable challenge. In this work, we disclose use bromodifluoroacetonitrile (BrCF2CN), cost-effective readily available reagent, radical source for cyanodifluoromethylation alkyl alkenes, aryl alkynes, (hetero)arenes under photocatalytic conditions. This protocol demonstrates an exceptionally broad substrate scope remarkable tolerance to various functional groups. Notably, alkynes predominantly provides sterically hindered thermodynamically unfavorable outcome, (hetero)arene C-H bonds are directly amenable without pre-functionalization. Here, authors report (BrCF2CN)

Language: Английский

Citations

5
Cu-Catalyzed Diastereo- and Enantioselective Synthesis of Borylated Cyclopropanes with Three Contiguous Stereocenters DOI
Chao Gao, Kai Tang, Xi Yang

et al.

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

Published: Jan. 17, 2025

Direct synthesis of enantioenriched scaffolds with multiple adjacent stereocenters remains an important yet challenging task. Herein, we describe a highly diastereo- and enantioselective Cu-catalyzed alkylboration cyclopropenes, less reactive alkyl iodides as electrophiles, for the efficient tetra-substituted borylated cyclopropanes bearing three consecutive stereocenters. This protocol features mild conditions, broad substrate scope, good functional group tolerance, affording array chiral in to high yields excellent enantioselectivities. Detailed mechanistic experiments kinetic studies were conducted elucidate reaction pathway rate-determining step reaction. DFT calculations revealed that π···π stacking interaction between phenyl groups on phosphorus ligand, along smaller distortion CuL-Bpin part, contributed The synthetic utility was showcased by facile some valuable centers.

Language: Английский

Citations

5
Recent advances in the stereoselective synthesis of acyclic all-carbon tetrasubstituted alkenes DOI
Floris Buttard, Jyoti Sharma, Pier Alexandre Champagne

et al.

Chemical Communications, Journal Year: 2021, Volume and Issue: 57(34), P. 4071 - 4088

Published: Jan. 1, 2021

Acyclic all-carbon tetrasubstituted alkenes are still some of the most challenging functional groups to access selectively. This Highlights reports on significant solutions toward this problem that were published between 2007 and 2020.

Language: Английский

Citations

69
Allenes and Dienes as Chiral Allylmetal Pronucleophiles in Catalytic Enantioselective C=X Addition: Historical Perspective and State‐of‐The‐Art Survey DOI
Ming Xiang, Dana E. Pfaffinger, Michael J. Krische

et al.

Chemistry - A European Journal, Journal Year: 2021, Volume and Issue: 27(52), P. 13107 - 13116

Published: June 29, 2021

Abstract The use of allenes and 1,3‐dienes as chiral allylmetal pronucleophiles in intermolecular catalytic enantioselective reductive additions to aldehydes, ketones, imines, carbon dioxide other C=X electrophiles is exhaustively catalogued together with redox‐neutral hydrogen auto‐transfer processes. Coverage limited processes that result both C−H C−C bond formation. alkynes latent multicomponent allylations involving dienes not covered. As illustrated this review, the ability serve tractable non‐metallic has evoked many useful transformations have no counterpart traditional chemistry.

Language: Английский

Citations

67
Saturated Boronic Acids, Boronates, and Trifluoroborates: An Update on Their Synthetic and Medicinal Chemistry DOI
Dmitriy M. Volochnyuk, Alina O. Gorlova, Oleksandr O. Grygorenko

et al.

Chemistry - A European Journal, Journal Year: 2021, Volume and Issue: 27(62), P. 15277 - 15326

Published: Sept. 9, 2021

Abstract This review discusses recent advances in the chemistry of saturated boronic acids, boronates, and trifluoroborates. Applications title compounds design boron‐containing drugs are surveyed, with special emphasis on α‐amino derivatives. A general overview as modern tools to construct C(sp 3 )−C )‐heteroatom bonds is given, including developments Suzuki‐Miyaura Chan‐Lam cross‐couplings, single‐electron‐transfer processes metallo‐ organocatalytic photoredox reactions, transformations boron “ate” complexes. Finally, an attempt summarize current state art synthesis trifluoroborates made, a brief mention “classical” methods (transmetallation organolithium/magnesium reagents species, anti‐Markovnikov hydroboration alkenes, modification alkenyl compounds) focus methodologies (boronation alkyl (pseudo)halides, derivatives carboxylic alcohols, primary amines, boronative C−H activation, novel approaches alkene hydroboration, 1,2‐metallate‐type rearrangements).

Language: Английский

Citations

65
Recent advances in the synthesis of 1,1-diarylalkanes by transition-metal catalysis DOI

Md. Belal,

Zheqi Li, Xiuqiang Lu

et al.

Science China Chemistry, Journal Year: 2021, Volume and Issue: 64(4), P. 513 - 533

Published: Jan. 12, 2021

Language: Английский

Citations

61
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

57
Cooperative Pd/Cu Catalysis for Alkene Arylboration: Opportunities for Divergent Reactivity DOI
Stanna K. Dorn, M. Kevin Brown

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(3), P. 2058 - 2063

Published: Jan. 24, 2022

A preeminent challenge in alkene difunctionalization is the control of regio-, diastereo-, and enantioselectivity. In this Perspective, a Pd/Cu-cooperative catalytic system for arylboration highlighted that allows controlled introduction substituents. particular, examples allowed divergent reactivity from single substrate based on tuning catalysts reaction conditions are emphasized.

Language: Английский

Citations

57