Methoxide‐Enabled Zirconium‐Catalyzed Migratory Alkene Hydrosilylation DOI Creative Commons
Orsola A. Luongo, Miran Lemmerer,

Sanne L. Albers

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(46)

Published: July 24, 2024

A zirconocene dichloride-catalyzed alkene hydrosilylation is reported that can be applied to non-activated and conjugated terminal internal alkenes. It involves a catalytic Zr-walk process leads selective conversion the linear product. Lithium methoxide serves as mild catalyst activating agent, which significantly increases applicability operational simplicity in comparison earlier zirconium(II)-based protocols. Supported by additional experiments calculations, mechanism via zirconium(IV) intermediates proposed. Due benign nature ready-availability of zirconium catalyst, reaction an attractive alternative established methods.

Language: Английский

Stereodivergent 1,3-difunctionalization of alkenes by charge relocation DOI Creative Commons
Bogdan R. Brutiu, Giulia Iannelli, Margaux Riomet

et al.

Nature, Journal Year: 2024, Volume and Issue: 626(7997), P. 92 - 97

Published: Jan. 31, 2024

Abstract Alkenes are indispensable feedstocks in chemistry. Functionalization at both carbons of the alkene—1,2-difunctionalization—is part chemistry curricula worldwide 1 . Although difunctionalization distal positions has been reported 2–4 , it typically relies on designer substrates featuring directing groups and/or stabilizing features, all which determine ultimate site bond formation 5–7 Here we introduce a method for direct 1,3-difunctionalization alkenes, based concept termed ‘charge relocation’, enables stereodivergent access to 1,3-difunctionalized products either syn - or anti -configuration from unactivated without need features. The usefulness approach is demonstrated synthesis pulmonary toxin 4-ipomeanol and its derivatives.

Language: Английский

Citations

20
Ligand‐Controlled NiH‐Catalyzed Regiodivergent Chain‐Walking Hydroalkylation of Alkenes DOI
Lei Zhao,

Yuqin Zhu,

Mengyuan Liu

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(30)

Published: May 24, 2022

Abstract A NiH‐catalyzed migratory hydroalkylation of alkenyl amines with predictable and switchable regioselectivity is reported. By utilizing a ligand‐controlled, directing group‐assisted strategy, various alkyl units are site‐selectively installed at inert sp 3 C−H sites far away from the original C=C bonds. range structurally diverse α‐ β‐branched protected conveniently synthesized via stabilization 5‐ 6‐membered nickelacycles respectively. This method exhibits broad scope high functional group tolerance, can be applied to late‐stage modification medicinally relevant molecules.

Language: Английский

Citations

53
Enantioselective Cobalt-Catalyzed Hydroboration of Fluoroalkyl-Substituted Alkenes to Access Chiral Fluoroalkylboronates DOI Creative Commons
Ming Hu,

Boon Beng Tan,

Shaozhong Ge

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(33), P. 15333 - 15338

Published: Aug. 11, 2022

Selective defluoroborylation and asymmetric hydroboration reactions of fluoroalkyl-substituted terminal alkenes with pinacolborane (HBpin) have been developed cobalt catalysts generated from Co(acac)2 bisphosphine ligands. A variety undergo this enantioselective hydroboration, affording the corresponding chiral alkylboronates containing stereogenic carbon centers high enantioselectivity (up to 98% ee). This provides a versatile foundation for synthesis organofluorine compounds centers.

Language: Английский

Citations

41
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

28
Cobalt‐Catalyzed Asymmetric Sequential Hydroboration/Isomerization/Hydroboration of 2‐Aryl Vinylcyclopropanes DOI
Chen‐Hui Chen, Hongliang Wang, Tongtong Li

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(30)

Published: May 24, 2022

A cobalt-catalyzed asymmetric sequential hydroboration/isomerization/hydroboration of 2-aryl vinylcyclopropanes was for the first time reported preparation valuable chiral 1,5-bis(boronates) in good yields with excellent enantioselectivity via isomerization/hydroboration a trisubstituted alkene intermediate. The reaction carried out smoothly and this protocol used syntheses (-)-preclamol gram-scale. two primary C(sp3) -B bonds could be distinguished iterative Suzuki-Miyaura cross-coupling reaction, delivering 1,2,5-triaryl alkanes enantioselectivity. Based on experimental computational studies, cobalt-hydride species proposed as active intermediate hydroboration, isomerization, second hydroboration reactions.

Language: Английский

Citations

38
Remote Site‐Selective Asymmetric Protoboration of Unactivated Alkenes Enabled by Bimetallic Relay Catalysis DOI
Qiao Zhang, Simin Wang, Jianjun Yin

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(23)

Published: March 17, 2022

Abstract A remote C(sp 3 )−H bond asymmetric borylation of unactivated alkenes was achieved by bimetallic relay catalysis. The reaction proceeded through reversible and consecutive β‐H elimination/olefin insertion promoted CoH species generated in situ, followed copper‐catalyzed protoboration. use this synergistic Co/Cu catalysis protocol allowed the enantioselective protoboration various terminal internal alkenes, as well an unrefined mixture olefin isomers, at distal less‐reactive β‐position to a functional group, leading chiral organoboronates.

Language: Английский

Citations

37
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

22
Ligand-Controlled NiH-Catalyzed Regiodivergent and Enantioselective Hydroamination of Alkenyl Amides DOI

Leipeng Xie,

Jimin Liang,

Haohao Bai

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(15), P. 10041 - 10047

Published: July 18, 2023

Transition-metal-catalyzed remote hydrofunctionalization of alkenes remains an efficient but challenging protocol in chemical synthesis. Herein, we reported a ligand-controlled, directing-group-assisted strategy to promote NiH-catalyzed site-selective (α, β, or γ) hydroamination unactivated with weakly coordinating amide groups. The key success lies the employment proper yet commercially available bidentate nitrogen-containing ligands, which enables delivery 1,1-, 1,2-, and 1,3-diamines good-to-excellent regioselectivity starting from same substrates. A broad range O-benzoylhydroxylamine electrophiles different functional groups can be installed via Ni migration nonmigration. Moreover, these predicable positionally selective protocols provide method for enantioselective synthesis highly valued 1,2-diamines (via aliphatic C–H amination) 1,3-diamines.

Language: Английский

Citations

21
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
Chemo-, regio- and stereoselective access to polysubstituted 1,3-dienes via Nickel-catalyzed four-component reactions DOI Creative Commons
Shanglin Chen, Yanan Wang,

Jinhui Xie

et al.

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

Published: June 28, 2024

1,2-Difunctionalization of alkynes offers a straightforward approach to access polysubstituted alkenes. However, simultaneous multi-component cascade transformations including difunctionalization two with both syn- and anti-selectivity in one catalyst system is undeveloped proves be significant challenge. Herein, we report Nickel-catalyzed four-component reaction 1,3-dienes using terminal alkynes, aryl boroxines, perfluoroalkyl iodides, wherein the forms three new C-C bonds single vessel serve as modular strategy excellent chemoselectivity, good regioselectivity exclusive stereoselectivity. Control experiments reveal plausible mechanism DFT calculations explain cause for formation this unusual reaction. Furthermore, successfully incorporate biologically active units into 1,2,3,4-tetrasubstituted 1,3-dienes, which greatly increases diversity molecular scaffolds brings more potential values medicinal chemistry, synthetic utility our protocol further demonstrated by late-stage transformations.

Language: Английский

Citations

9