Enantioselective and Enantiospecific Transition-Metal-Catalyzed Cross-Coupling Reactions of Organometallic Reagents To Construct C–C Bonds

Chemical Reviews, Journal Year: 2015, Volume and Issue: 115(17), P. 9587 - 9652

Published: Aug. 13, 2015

ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTEnantioselective and Enantiospecific Transition-Metal-Catalyzed Cross-Coupling Reactions of Organometallic Reagents To Construct C–C BondsAlan H. Cherney, Nathaniel T. Kadunce, Sarah E. Reisman*View Author Information The Warren Katharine Schlinger Laboratory for Chemistry Chemical Engineering, Division California Institute Technology, Pasadena, 91125, United States*E-mail: [email protected]Cite this: Chem. Rev. 2015, 115, 17, 9587–9652Publication Date (Web):August 13, 2015Publication History Received17 March 2015Published online13 August inissue 9 September 2015https://doi.org/10.1021/acs.chemrev.5b00162Copyright © 2015 American SocietyRIGHTS & PERMISSIONSACS AuthorChoiceArticle Views40232Altmetric-Citations603LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum full text article downloads since November 2008 (both PDF HTML) across all institutions individuals. These metrics regularly updated to reflect usage leading up last few days.Citations number other articles citing this article, calculated by Crossref daily. Find more information about citation counts.The Altmetric Attention Score is a quantitative measure attention that research has received online. Clicking on donut icon will load page at altmetric.com with additional details score social media presence given article. how calculated. Share Add toView InAdd Full Text ReferenceAdd Description ExportRISCitationCitation abstractCitation referencesMore Options onFacebookTwitterWechatLinked InReddit (12 MB) Get e-AlertsSUBJECTS:Cross coupling reaction,Electrophiles,Ligands,Reagents,Substitution reactions e-Alerts

Language: Английский

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Single-Electron Transmetalation via Photoredox/Nickel Dual Catalysis: Unlocking a New Paradigm for sp³–sp² Cross-Coupling

Accounts of Chemical Research, Journal Year: 2016, Volume and Issue: 49(7), P. 1429 - 1439

Published: July 5, 2016

The important role of transition metal-catalyzed cross-coupling in expanding the frontiers accessible chemical territory is unquestionable. Despite empowering chemists with Herculean capabilities complex molecule construction, contemporary protocols are not without their Achilles' heel: Csp(3)-Csp(2)/sp(3) coupling. underlying challenge sp(3) cross-couplings 2-fold: (i) methods employing conventional, bench-stable precursors universally reliant on extreme reaction conditions because high activation barrier transmetalation; (ii) circumvention this invariably relies use more reactive precursors, thereby sacrificing functional group tolerance, operational simplicity, and broad applicability. ubiquity problem, nature transmetalation step has remained unchanged from seminal reports Negishi, Suzuki, Kumada, Stille, thus suggesting that challenges coupling result inherent mechanistic constraints traditional paradigm. Rather than submitting to limitations conventional approach, we envisioned a process rooted single-electron reactivity could furnish same key metalated intermediate posited two-electron transmetalation, while demonstrating entirely complementary patterns. Inspired by literature susceptibility organoboron reagents toward photochemical, oxidative fragmentation, realization conceptually novel open shell framework was achieved facile benzylic trifluoroborates aryl halides via cooperative visible-light activated photoredox Ni catalysis. Following study, disclosed suite for secondary alkyl, α-alkoxy, α-amino, α-trifluoromethylbenzyltrifluoroborates. Furthermore, selective Csp(3) moieties presence Csp(2) motifs also demonstrated, highlighting nuances approach transmetalation. Computational modeling mechanism uncovered useful details about intermediates transition-state structures involved nickel catalytic cycle. Most notably, unique dynamic kinetic resolution process, characterized radical homolysis/recombination equilibrium Ni(III) intermediate, discovered. This ultimately found be responsible stereoselectivity an enantioselective variant these cross-couplings. Prompted intrinsic organotrifluoroborates, sought other feedstocks quickly identified alkylbis(catecholato)silicates as viable Ni/photoredox dual These hypervalent silicate species have several notable benefits, including favorable redox potentials allow extension primary alkyl systems incorporating unprotected amines well compatibility less expensive Ru-based photocatalysts. Additionally, exhibit amenability alkenyl halide simultaneously scope. In exploring reagents, serendipitously discovered method effect thioetherification H atom transfer mechanism. latter discovery emphasizes robust paradigm "blind" origins radical, opening opportunities wealth new discoveries. Taken together, our studies area photoredox/nickel catalysis validated powerful platform enabling conventionally challenging Csp(3)-Csp(2) More broadly, findings represent power rational design strategic knowledge manipulation development synthetic methods.

Language: Английский

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Alkyl Carbon–Carbon Bond Formation by Nickel/Photoredox Cross‐Coupling

Angewandte Chemie International Edition, Journal Year: 2018, Volume and Issue: 58(19), P. 6152 - 6163

Published: Oct. 6, 2018

The union of photoredox and nickel catalysis has resulted in a renaissance radical chemistry as well the use nickel-catalyzed transformations, specifically for carbon-carbon bond formation. Collectively, these advances address longstanding challenge late-stage cross-coupling functionalized alkyl fragments. Empowered by notion that photocatalytically generated radicals readily undergo capture Ni complexes, wholly new feedstocks have been realized. Herein, we highlight recent developments several types cross-couplings are accessible exclusively through this approach.

Language: Английский

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Nickel-Catalyzed Cross-Coupling of Photoredox-Generated Radicals: Uncovering a General Manifold for Stereoconvergence in Nickel-Catalyzed Cross-Couplings

Journal of the American Chemical Society, Journal Year: 2015, Volume and Issue: 137(15), P. 4896 - 4899

Published: April 2, 2015

The cross-coupling of sp3-hybridized organoboron reagents via photoredox/nickel dual catalysis represents a new paradigm reactivity for engaging alkylmetallic in transition-metal-catalyzed processes. Reported here is an investigation into the mechanistic details this important transformation using density functional theory. Calculations bring to light reaction pathway involving alkylnickel(I) complex generated by addition alkyl radical Ni(0) that likely operate simultaneously with previously proposed mechanism. Analysis enantioselective variant reveals unexpected manifold stereoinduction dynamic kinetic resolution (DKR) Ni(III) intermediate wherein stereodetermining step reductive elimination. Furthermore, calculations suggest DKR-based may be responsible stereoselectivity observed numerous other stereoconvergent Ni-catalyzed cross-couplings and couplings.

Language: Английский

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Stereospecific functionalizations and transformations of secondary and tertiary boronic esters

Chemical Communications, Journal Year: 2017, Volume and Issue: 53(40), P. 5481 - 5494

Published: Jan. 1, 2017

The formation of highly enantioenriched boronic esters through both stoichiometric and catalytic methods has received much attention over the past decade. Accordingly, transformations ester moiety into other functional groups is considerable interest in synthesis. Specifically, which retain high enantioenrichment starting ester, either a stereoretentive or stereoinvertive pathway, lead to new C-C, C-O, C-N, C-X, C-H bonds at stereogenic centres. This feature article summarises current state art stereospecific secondary tertiary functionalities groups, whilst considering critically that are currently unattainable would represent future advances field.

Language: Английский

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Single-Electron Transmetalation: An Enabling Technology for Secondary Alkylboron Cross-Coupling

Journal of the American Chemical Society, Journal Year: 2015, Volume and Issue: 137(6), P. 2195 - 2198

Published: Feb. 4, 2015

Single-electron-mediated alkyl transfer affords a novel mechanism for transmetalation, enabling cross-coupling under mild conditions. Here, general conditions are reported of secondary alkyltrifluoroborates with an array aryl bromides mediated by Ir photoredox catalyst and Ni catalyst.

Language: Английский

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Stereospecific Couplings of Secondary and Tertiary Boronic Esters

Angewandte Chemie International Edition, Journal Year: 2014, Volume and Issue: 54(4), P. 1082 - 1096

Published: Nov. 20, 2014

This Minireview highlights advances in the Suzuki-Miyaura cross-coupling of secondary boron reagents for creation C-C bonds with control stereochemistry. It also includes non-transition-metal coupling and tertiary boronic esters to electron-rich aromatics.

Language: Английский

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Copper‐Catalyzed Enantioselective 1,6‐Boration of para‐Quinone Methides and Efficient Transformation of gem‐Diarylmethine Boronates to Triarylmethanes

Angewandte Chemie International Edition, Journal Year: 2015, Volume and Issue: 54(41), P. 12134 - 12138

Published: Aug. 28, 2015

Presented is the first enantioselective copper-catalyzed 1,6-conjugate addition of bis(pinacolato)diboron to para-quinone methides. The reaction proceeds with excellent yields and good enantioselectivities, provides an attractive approach construction optically active gem-diarylmehtine boronic esters. Additionally, subsequent conversion derived potassium trifluoroborates into triarylmethanes highly enantiospecificity was realized.

Language: Английский

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Stereospecific Nickel-Catalyzed Cross-Coupling Reactions of Benzylic Ethers and Esters

Accounts of Chemical Research, Journal Year: 2015, Volume and Issue: 48(8), P. 2344 - 2353

Published: July 21, 2015

ConspectusThis Account presents the development of a suite stereospecific alkyl–alkyl cross-coupling reactions employing nickel catalysts. Our complement related nickel-catalyzed stereoconvergent from stereochemical and mechanistic perspective. Most alkyl electrophiles with low-valent complexes proceed through radicals thus are stereoablative; correct enantioselective catalyst can favor formation one enantiomer. reactions, in contrast, stereospecific. Enantioenriched ethers esters cleanly converted to cross-coupled products high fidelity. While details still be refined, our results consistent polar, two-electron oxidative addition that avoids radical intermediates. This reactivity is unusual for first-row transition metal.The engage range benzylic esters, including methyl ethers, tetrahydropyrans, tetrahydrofurans, lactones. Coordination arene substituent accelerates reactions. Arenes low aromatic stabilization energies, such as naphthalene, benzothiophene, furan, serve best ligands provide highest reactivity. Traceless directing groups accelerate sluggish substrates described, providing partial compensation coordination.Kumada, Negishi, Suzuki incorporation broad transmetalating agents. In Kumada coupling full Grigard reagents, methyl, n-alkyl, aryl Grignard employed. methylmagnesium iodide, ligation by rac-BINAP or DPEphos provides yield stereospecificity. For all other Ni(dppe)Cl2 has emerged catalyst. Negishi dimethylzinc reported strategy increase functional group tolerance reaction. We also describe using arylboronic esters. These provided first example series switch outcome. The maintain stereospecificity, but different achiral opposite enantiomers product. Use an N-heterocyclic carbene ligand, SIMes, inversion, prior work electron-rich phosphine PCy3, however, retention signaling change details.Potential applications include synthesis medicinal agents containing 2-arylalkane 1,1-diarylalkane moieties, which pharmacophores chemistry. moieties found compounds activity against indications, cancer, heart disease, diabetes, osteoporosis, smallpox, tuberculosis, insomnia. highlight representative examples bioactive we have prepared enantioselectivity methods, well discovery new anti-cancer agent.

Language: Английский

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Pd(II)-Catalyzed Enantioselective C(sp³)–H Borylation

Journal of the American Chemical Society, Journal Year: 2017, Volume and Issue: 139(9), P. 3344 - 3347

Published: Feb. 17, 2017

Pd(II)-catalyzed enantioselective borylation of C(sp3)–H bonds has been realized for the first time using chiral acetyl-protected aminomethyl oxazoline ligands. This reaction is compatible with carbocyclic amides containing α-tertiary as well α-quaternary carbon centers. The β-borylated are useful synthons synthesis β-hydroxylated, β-fluorinated, and β-arylated carboxylic acids.

Language: Английский

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