Copper-Catalyzed Functionalization of 1,3-Dienes: Hydrofunctionalization, Borofunctionalization, and Difunctionalization

ACS Catalysis, Journal Year: 2019, Volume and Issue: 10(2), P. 1485 - 1499

Published: Dec. 18, 2019

The catalytic conversion of chemical feedstocks into products medicinal and agricultural value is a key theme across modern synthetic chemistry. As 1,3-dienes are readily available from industrial cracking processes, there great interest in the development sustainable methods for functionalization these simple molecules. Although initial developments this field have required precious-transition-metal catalysts, has been push toward use inexpensive, nontoxic, more abundant copper catalysts to promote functionalization. This Perspective covers many area copper-catalyzed 1,3-dienes, particular hydrofunctionalization, borofunctionalization, difunctionalization (e.g., diamination).

Language: Английский

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Iron- and Cobalt-Catalyzed Asymmetric Hydrofunctionalization of Alkenes and Alkynes

Accounts of Chemical Research, Journal Year: 2021, Volume and Issue: 54(11), P. 2701 - 2716

Published: May 20, 2021

ConspectusTransition metal catalyzed asymmetric hydrofunctionalization of readily available unsaturated hydrocarbons presents one the most straightforward and atom-economic protocols to access valuable optically active products. For decades, noble transition catalysts have laid cornerstone in this field, on account their superior reactivity selectivity. In recent years, from an economical sustainable standpoint, first-row, earth-abundant metals received considerable attention, due high natural reserves, affordable costs, low toxicity. Meanwhile, reactions also gained much interest been investigated gradually. However, since chiral ligand libraries for transition-metal catalysis are limited date, development highly enantioselective versions remains a significant challenge.This Account summarizes our efforts developing suitable ligands iron cobalt applications (hydroboration hydrosilylation) alkenes alkynes. design, we envisioned that unsymmetric NNN-tridentate (UNT) scaffolds could promote these transformations with metals. Therefore, several types UNT were designed prepared laboratory, utilizing amino acids as sources. very beginning, oxazoline iminopyridine (OIP) proposed through rational combination nitrogen-containing scaffolds. After systematic survey effects, imine moiety rigid OIP was replaced by conformationally more flexible amine unit, leading construction reactive aminoisopropylpyridine (OAP) ligands. Subsequently, imidazoline (IIP) thiazoline (TIP) altering oxygen atom nitrogen sulfur linkers, respectively. To further expand library, other tridentate containing twisted pincer, anionic, nonrigid backbone synthesized, including iminophenyl oxazolinyl phenylamine (IPOPA) phenyl picolinamide (ImPPA). The efficacy induction has demonstrated sequential alkynes, which exhibit excellent well chemo-, regio-, stereoselectivity broad functional group tolerance. Notably, regio- challenging substrates, such 1,1-disubstituted aryl terminal aliphatic alkenes, achieved. Furthermore, isomerization/hydroboration internal alkynes demonstrates synthetic power catalytic systems. enantioenriched products obtained methodologies be potentially utilized organic synthesis, medicinal chemistry, materials science. We believe continuous field would beneficial catalysis.

Language: Английский

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C–C and C–X coupling reactions of unactivated alkyl electrophiles using copper catalysis

Chemical Society Reviews, Journal Year: 2020, Volume and Issue: 49(22), P. 8036 - 8064

Published: Jan. 1, 2020

Transition metal-catalysed cross-coupling reactions are widely used for construction of carbon-carbon and carbon-heteroatom bonds. However, compared to aryl or alkenyl electrophiles, the unactivated alkyl electrophiles containing β hydrogens remains a challenge. Over past few years, use suitable ligands such as bulky phosphines N-heterocyclic carbenes (NHCs) has enabled not only limited traditional with Grignard reagents, but also including diverse range organic transformations via either SN2 radical pathways. This review provides comprehensive overview recent development in copper-catalysed C-C, C-N, C-B, C-Si C-F bond-forming using electrophiles.

Language: Английский

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Nickel‐CatalyzedDicarbofunctionalization of Alkenes^†

Chinese Journal of Chemistry, Journal Year: 2020, Volume and Issue: 38(11), P. 1371 - 1394

Published: June 16, 2020

As a straightforward strategy for rapidly increasing molecular complexity, dicarbofunctionalization of alkenes has attracted substantial interests organic synthesis, medicine chemistry, and materials science. Nickel‐catalyzed cascade dicarbofunctionalizations have been flourished in this area recently, nickel‐mediated radical pathways particularly offer new opportunities conjunctive cross‐couplings with alkyl coupling partners. Herein, we give comprehensive review nickel‐catalyzed through historical perspective, including intermolecular three‐component reactions intramolecular reactions. Among the discussed review, carbometallation/cross‐coupling process addition/cross‐coupling are two major alkenes. The oxidative cyclization 1,2‐metallate shift processes also selectively discussed. These methods overcome limitations associated using noble metals field, providing an efficient access to structurally diversified molecules.

Language: Английский

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Recent advances in tridentate iron and cobalt complexes for alkene and alkyne hydrofunctionalizations

Coordination Chemistry Reviews, Journal Year: 2019, Volume and Issue: 386, P. 138 - 153

Published: Feb. 18, 2019

Language: Английский

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Transition-Metal-Catalyzed Functionalization of Alkynes with Organoboron Reagents: New Trends, Mechanistic Insights, and Applications

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(12), P. 7513 - 7551

Published: June 9, 2021

Catalytic functionalization of alkynes with organoboron reagents provides a straightforward access to stereochemically defined multisubstituted alkenes, which are structural motifs commonly found in bioactive compounds and organic materials. Recent progress has substantially broadened the scope this field on several fronts. Strategies for regioselectivity control 1,2-migratory insertion across unsymmetrical internal alkynes, as well direct products anti-insertion stereochemistry, have been devised. The alkenyl-to-aryl 1,4-metal migration upon metal recently exploited powerful cascade sequences leading complex polycyclic scaffolds, including development enantioselective processes. Elegant enantiospecific dynamic kinetic resolution methods developed accessing chiral allenes from propargylic alcohol derivatives. Mechanistic manifolds emerged based single-electron transfer (SET) that provided fresh impetus alkyne 1,2-difunctionalization complementary stereoselectivity processes relying 1,2-insertion R–M species. Herein, we discuss most recent advances transition-metal-catalyzed using reagents, categorized according type mechanistic outcome. Emphasis is placed aspects, synthetic utility, limitations, challenges future research.

Language: Английский

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NiH-Catalyzed Functionalization of Remote and Proximal Olefins: New Reactions and Innovative Strategies

Accounts of Chemical Research, Journal Year: 2022, Volume and Issue: 55(23), P. 3519 - 3536

Published: Nov. 9, 2022

Transition metal hydride catalyzed functionalization of remote and proximal olefins has many advantages over conventional cross-coupling reactions. It avoids the separate, prior generation stoichiometric amounts organometallic reagents use preformed reagents, which are sometimes hard to access may compromise functional group compatibility. The migratory insertion complexes generated in situ into readily available alkene starting materials, hydrometalation process, provides an attractive straightforward route alkyl intermediates, can undergo a variety sequential In particular, with synergistic combination chain-walking chemistry nickel, NiH-catalyzed undergone particularly intense development past few years. This Account aims chronicle progress made this arena terms activation modes, diverse functionalizations, chemo-, regio-, enantioselectivity.We first provide brief introduction general reaction mechanisms. Taking hydroarylation as example, four oxidation states Ni have allowed us develop two different strategies form final product: Ni(I)-H/X-Ni(II)-H platform that relies on reductants Ni(I/II/III) cycle redox-neutral or FG-Ni(II)-H reacts substrate forms products via Ni(0/II) pathway. We also demonstrate functionalization, including C-C bond-forming reactions more challenging C-N/C-S could be realized. Moreover, employment appropriate chiral ligands successfully realize corresponding asymmetric hydrofunctionalization olefins, hydroalkylation, hydroarylation, hydroalkenylation, hydroalkynylation, hydroamination. Interestingly, enantio-determining step enantioselective hydronickelation, selective oxidative addition, reductive elimination. To hydrofunctionalization, we developed ligand relay catalytic strategy simple ligands, for second coupling. novel design single, possibly structurally complex promote both steps success multicomponent convenient approach gain molecules. Finally, halides used olefin precursors cross-electrophile coupling Applications these discussed. hope will inspire future field overcome key challenges, conceptually new strategies, high-performance systems enhanced reactivity selectivity, cutting-edge catalyst design, further mechanistic studies.

Language: Английский

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Streamlined Alkylation via Nickel-Hydride-Catalyzed Hydrocarbonation of Alkenes

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(16), P. 7015 - 7029

Published: April 12, 2022

Compounds rich in sp3-hybridized carbons are desirable drug discovery. Nickel-catalyzed hydrocarbonation of alkenes is a potentially efficient method to synthesize these compounds. By using abundant, readily available, and stable as pro-nucleophiles, reactions can have broad scope high functional group tolerance. However, this methodology still an early stage development, the first examples were reported only 2016. Herein, we summarize progress emerging field, with emphasis on enantioselective reactions. We highlight major developments, critically discuss wide range possible mechanisms, offer our perspective state challenges field. hope Perspective will stimulate future works area, making widely applicable organic synthesis.

Language: Английский

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Intercepting Hydrogen Evolution with Hydrogen-Atom Transfer: Electron-Initiated Hydrofunctionalization of Alkenes

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(39), P. 17783 - 17791

Published: Sept. 22, 2022

Hydrogen-atom transfer mediated by earth-abundant transition-metal hydrides (M-Hs) has emerged as a powerful tool in organic synthesis. Current methods to generate M-Hs most frequently rely on oxidatively initiated hydride transfer. Herein, we report reductive approach Co-H, which allows for canonical hydrogen evolution reactions be intercepted hydrogen-atom an alkene. Electroanalytical and spectroscopic studies provided mechanistic insights into the formation reactivity of enabled development two new alkene hydrofunctionalization reactions.

Language: Английский

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Cobalt-Catalyzed Sequential Site- and Stereoselective Hydrosilylation of 1,3- and 1,4-Enynes

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(12), P. 5233 - 5240

Published: March 17, 2022

Catalytic sequential hydrosilylation of 1,3-enynes and 1,4-enynes promoted by cobalt complexes derived from bisphosphines are presented. Site- stereoselective Si–H addition primary silanes to followed intramolecular diastereo- enantioselective afforded enantioenriched cyclic alkenylsilanes with simultaneous construction a carbon-stereogenic center silicon-stereogenic center. Reactions proceeded through isomerization the alkene moiety site- hydrosilylation. A wide range were in high efficiency selectivity. Functionalization containing stereogenic at silicon delivered variety chiral building blocks that otherwise difficult access.

Language: Английский

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