Nickel-catalyzed remote and proximal Wacker-type oxidation DOI Creative Commons
Binbin Liu, Penghui Hu, Fangning Xu

et al.

Communications Chemistry, Journal Year: 2019, Volume and Issue: 2(1)

Published: Jan. 4, 2019

Abstract Wacker oxidation chemistry is widely applied to of olefins carbonyls in the synthesis pharmaceuticals, natural products, and commodity chemicals. However, this efficient internal highly selective unbiased without reliance upon suitable coordinating groups have remained significant challenges. Here we report a nickel-catalyzed remote Wacker-type where reactions occur at less-reactive sp 3 C–H sites presence priori more reactive ones through chain-walking mechanism with excellent regio- chemo- selectivity. This transformation has attractive features including use ambient air as sole oxidant, naturally-abundant nickel catalyst, polymethylhydrosiloxane hydride source room temperature, allowing for effective challenging olefins. Notably, approach enables direct access broad array complex, medicinally relevant molecules from structurally complex substrates chemical feedstocks.

Language: Английский

γ-Selective C(sp3)–H amination via controlled migratory hydroamination DOI Creative Commons
Changseok Lee, Huiyeong Seo, Jinwon Jeon

et al.

Nature Communications, Journal Year: 2021, Volume and Issue: 12(1)

Published: Sept. 27, 2021

Abstract Remote functionalization of alkenes via chain walking has generally been limited to C(sp 3 )–H bonds α and β polar-functional units, while γ -C(sp through controlled alkene transposition is a longstanding challenge. Herein, we describe NiH-catalyzed migratory formal hydroamination alkenyl amides achieved chelation-assisted control, whereby various amino groups are installed at the -position aliphatic chains. By tuning olefin isomerization ligand directing group optimization, -selective amination can be stabilization 6-membered nickellacycle by an 8-aminoquinoline subsequent interception aminating reagent. A range amines bond unactivated with varying alkyl lengths, enabling late-stage access value-added -aminated products. Moreover, employing picolinamide-coupled substrates, this approach further extended δ amination. The chain-walking mechanism pathway selectivity investigated experimental computational methods.

Language: Английский

Citations

73
Chain-walking reactions of transition metals for remote C–H bond functionalization of olefinic substrates DOI
Soumen Ghosh, Sandeep Patel, Indranil Chatterjee

et al.

Chemical Communications, Journal Year: 2021, Volume and Issue: 57(85), P. 11110 - 11130

Published: Jan. 1, 2021

Transition metal-assisted remote C–H bond activation at the non-classical reaction sites of various olefinic substrates with aid a chain-walking process is depicted in this feature article.

Language: Английский

Citations

70
Enantio‐ and Diastereodivergent Sequential Catalysis Featuring Two Transition‐Metal‐Catalyzed Asymmetric Reactions DOI
Jeanne Masson‐Makdissi, Liher Prieto, Xavier Abel‐Snape

et al.

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(31), P. 16932 - 16936

Published: May 28, 2021

Abstract This study demonstrates the feasibility and inherent benefits of combining two distinct asymmetric transition‐metal‐catalyzed reactions in one pot. The reported transformation features a Pd‐catalyzed allylic alkylation Rh‐catalyzed enantioselective 1,4‐conjugate addition, effectively converting simple allyl enol carbonate precursors into enantioenriched cyclic ketones with remote stereocenters. Despite anticipated challenges associated controlling stereoselectivity such complex system, products are obtained enantiomeric excesses ranging up to >99 % ee , exceeding those from either individual reactions. In since both steps is under catalyst control, this one‐pot reaction enantio‐ diastereodivergent, enabling facile access all stereoisomers same set starting materials.

Language: Английский

Citations

59
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
Development and Mechanistic Interrogation of Interrupted Chain-Walking in the Enantioselective Relay Heck Reaction DOI

Sean P. Ross,

Ajara A. Rahman,

Matthew S. Sigman

et al.

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(23), P. 10516 - 10525

Published: May 15, 2020

The formation of alkyl–palladium complexes via the nucleopalladation alkenes is entry point for a wide range diverse reactions. One possibility that intermediate alkyl–Pd can undergo "chain-walking" event, to allow remote functionalization through various termination processes. However, there are few methods selectively interrupt chain-walking process at prescribed location. Herein, we demonstrate variety homoallylic protected amines an interrupted enantioselective relay Heck reaction give enantioenriched allylic amine products. selectivity this be diverted exclusively yield ene-amide products by virtue changing nature protecting group. To rationalize observation, combine experiment and computation investigate mechanism events. Isotopic labeling experiments computed pathways suggest system likely under thermodynamic control, with being driven relative stability intermediates encountered during chain-walking. These results illustrate controlled alteration processes provides roadmap exploiting these in future development.

Language: Английский

Citations

61
Remote Functionalization of α,β-Unsaturated Carbonyls by Multimetallic Sequential Catalysis DOI
Ciro Romano, Daniele Fiorito, Clément Mazet

et al.

Journal of the American Chemical Society, Journal Year: 2019, Volume and Issue: 141(42), P. 16983 - 16990

Published: Oct. 6, 2019

The remote functionalization of α,β-unsaturated carbonyls by an array multimetallic sequential catalytic systems is described. reactions are triggered hydrometalation using [Pd–H] or [Ru–H] isomerization catalysts and driven the formation thermodynamically more stable 1,2-vinyl arenes. Pd-catalyzed deconjugative was combined with a Cu-catalyzed β-borylation transiently generated styrenyl derivatives to deliver range products that would not be accessible use single catalyst. [Pd/Cu] were also identified for highly enantioselective α-hydroboration α-hydroamination intermediates. Difunctionalization simultaneously at benzylic homobenzylic positions achieved combining process Sharpless asymmetric dihydroxylation (SAD) [Pd/Os] [Ru/Os] couples. Starting from simple ester, isomerization/dihydroxylation/lactonization sequence gave access naturally occurring γ-butyrolactone in good yield, excellent diastereo- enantioselectivity.

Language: Английский

Citations

59
Recent Developments in Enantioselective Multicatalyzed Tandem Reactions DOI

Hélène Pellissier

Advanced Synthesis & Catalysis, Journal Year: 2020, Volume and Issue: 362(12), P. 2289 - 2325

Published: March 26, 2020

Abstract This review presents an update on the emerging field of enantioselective multicatalyzed tandem reactions published since beginning 2015. It illustrates how much combination different types catalyst allows unprecedented one‐pot many to be achieved, allowing a direct access variety very complex chiral molecules. Abbreviations : acac: acetylacetonate; Ar: aryl; Bn: benzyl; Boc: tert ‐butoxycarbonyl; BPE: 1,2‐bis(2‐pyridyl)ethane; Bz: benzoyl; CAPT: anion phase‐transfer; Cbz: benzyloxycarbonyl; cod: cyclooctadiene; Cy: cyclohexyl; dba: ( E,E )‐dibenzylideneacetone; DBU: 1,8‐diazabicyclo[5.4.0]undec‐7‐ene; DCE: dichloroethane; de diastereomeric excess; DIPEA: diisopropylethylamine; dme: 1,2‐dimethoxyethane; DPG: 1,3‐diphenylguanidine; dppe: 1,2‐bis(diphenylphosphino)ethane; ee enantiomeric EWG: electron‐withdrawing group; Hept: heptyl; Hex: hexyl; L: ligand; MTBE: methyl ‐butyl ether; MOM: methoxymethyl; MS: molecular sieves; Naph: naphthyl; NHC: N ‐ heterocyclic carbene; Pent: pentyl; Phth: phthaloyl; pin: pinacolato; Pybox: 2,6‐bis(2‐oxazolyl)pyridine; r.t.: room temperature; TEMPO: 2,2,6,6‐tetramethylpiperidine 1‐oxyl; Tf: trifluoromethanesulfonyl; THF: tetrahydrofuran; TMP: 2,2,6,6‐tetramethylpiperidine; TMS: trimethylsilyl; Tol: tolyl; triphos: bis(diphenylphosphinoethyl)phenylphosphine; Ts: 4‐toluenesulfonyl (tosyl). magnified image

Language: Английский

Citations

58
Palladium-Catalyzed Remote 1,n-Arylamination of Unactivated Terminal Alkenes DOI
Chunhua Han, Zhiyuan Fu,

Songjin Guo

et al.

ACS Catalysis, Journal Year: 2019, Volume and Issue: 9(5), P. 4196 - 4202

Published: March 29, 2019

A palladium-catalyzed remote 1,n-arylamination (from 1,3- to 1,11-arylamination) of unactivated terminal alkenes with aryl iodides and arylamines has been realized. This three-component reaction proceeded via Pd-catalyzed Heck arylation, alkene isomerization, aza-Michael addition, exhibiting good regio- chemoselectivity, wide substrate scope. Preliminary mechanistic studies indicated that the in situ generated ortho/para-quinone methide intermediates served as driving force for isomerization promoted rearomatization upon nucleophilic amination.

Language: Английский

Citations

57
Nickel‐Catalyzed Migratory Hydrocyanation of Internal Alkenes: Unexpected Diastereomeric‐Ligand‐Controlled Regiodivergence DOI

Jihui Gao,

Mingdong Jiao,

Jie Ni

et al.

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 60(4), P. 1883 - 1890

Published: Oct. 6, 2020

Abstract A regiodivergent nickel‐catalyzed hydrocyanation of a broad range internal alkenes involving chain‐walking process is reported. When appropriate diastereomeric biaryl diphosphite ligands are applied, the same starting materials can be converted to either linear or branched nitriles with good yields and high regioselectivities. DFT calculations suggested that catalyst architecture determines regioselectivity by modulating electronic steric interactions. In addition, moderate enantioselectivities were observed when produced.

Language: Английский

Citations

57
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