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

Accounts of Chemical Research, Год журнала: 2022, Номер 55(23), С. 3519 - 3536

Опубликована: Ноя. 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.

Язык: Английский

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N-Heterocyclic carbenes as privileged ligands for nickel-catalysed alkene functionalisation

Chemical Society Reviews, Год журнала: 2023, Номер 52(9), С. 2946 - 2991

Опубликована: Янв. 1, 2023

This review discusses the applications of N-heterocyclic carbene ligands and their influence on reactivity selectivity Ni-catalysed alkene functionalisations.

Язык: Английский

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Dual Nickel/Photoredox-Catalyzed Asymmetric Carbosulfonylation of Alkenes

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(23), С. 12532 - 12540

Опубликована: Май 30, 2023

An asymmetric three-component carbosulfonylation of alkenes is presented here. The reaction, involving the simultaneous formation a C-C and C-S bond across π-system, uses dual nickel/photoredox catalytic system to produce both β-aryl β-alkenyl sulfones in high yields with excellent levels stereocontrol (up 99:1 er). This protocol exhibits broad substrate scope functional group tolerance its synthetic potential has been demonstrated by successful applications toward pharmacologically relevant molecules. A array control experiments supports involvement secondary alkyl radical intermediate generated through addition sulfonyl double bond. Moreover, stoichiometric cross-over further suggest an underlying Ni(0)/Ni(I)/Ni(III) pathway operative these transformations.

Язык: Английский

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Nickel-Catalyzed Remote Asymmetric Hydroalkylation of Alkenyl Ethers to Access Ethers of Chiral Dialkyl Carbinols

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(18), С. 10411 - 10421

Опубликована: Апрель 26, 2023

Site- and enantio-selective alkyl-alkyl bond formation is privileged in the retrosynthetic analysis due to universality of sp3-hybridized carbon atoms organic molecules. Herein, we report a nickel-catalyzed remote asymmetric hydroalkylation alkenyl ethers via synchronous implementation alkene isomerization enantioselective C(sp3)-C(sp3) formation. Regression catalyst structure-activity relationships accelerates rational ligand modification through modular regulation. This reaction has several advantages for synthesizing chiral dialkyl carbinols their ether derivatives, including broad substrate scope, good functional group tolerance, excellent regioselectivity (>20:1 regioisomeric ratio), high enantioselectivity (up 95% enantiomeric excess).

Язык: Английский

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Ligand-Controlled Cobalt-Catalyzed Regio-, Enantio-, and Diastereoselective Oxyheterocyclic Alkene Hydroalkylation

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(5), С. 3405 - 3415

Опубликована: Янв. 29, 2024

Metal-hydride-catalyzed alkene hydroalkylation has been developed as an efficient method for C(sp

Язык: Английский

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Ligand-Controlled Cobalt-Catalyzed Regiodivergent Alkyne Hydroalkylation

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(30), С. 13961 - 13972

Опубликована: Июль 22, 2022

Regiodivergent alkyne hydroalkylation to generate different isomers of an alkene from the same starting material would be beneficial; however, it remains a challenge. Herein, we report ligand-controlled cobalt-catalyzed regiodivergent hydroalkylation. The sensible selection bisoxazoline (L1) and pyridine-oxazoline (L8) ligands led reliable predictable protocols that provided (E)-1,2-disubstituted 1,1-disubstituted alkenes with high E/Z stereoselectivity regioisomeric ratio identical terminal alkyl halide substrates produced trisubstituted in case internal alkynes. This method exhibits broad scope for alkynes wide range activated unactivated halides shows excellent functional group compatibility.

Язык: Английский

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Recent advances in nickel-catalyzed asymmetric hydrofunctionalization of alkenes

Chem Catalysis, Год журнала: 2022, Номер 2(11), С. 3140 - 3162

Опубликована: Ноя. 1, 2022

Язык: Английский

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Nickel‐Catalyzed Switchable Site‐Selective Alkene Hydroalkylation by Temperature Regulation**

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(31)

Опубликована: Май 25, 2022

Regiodivergent alkene functionalization that produces either regioisomer starting from the same raw materials is desirable. Herein, we report a nickel-catalyzed switchable site-selective hydroalkylation. The selection of reaction temperatures leads to protocols provide regiodivergent hydroalkylated products single substrate. This protocol allows convenient synthesis α- and β-branched protected amines, both which are important fields pharmaceutical chemistry biochemistry. In addition, enantioenriched alkylamines can be accessed in catalytic asymmetric variant. Preliminary mechanistic studies indicate formation more stable nickelacycle provides driving force migration. thermodynamic kinetic properties different reduction elimination intermediates responsible for site-selectivity.

Язык: Английский

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Remote and Proximal Hydroaminoalkylation of Alkenes Enabled by Photoredox/Nickel Dual Catalysis

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(39), С. 17776 - 17782

Опубликована: Сен. 22, 2022

A mild and site-selective hydroaminoalkylation of activated unactivated alkenes via dual photoredox/Ni catalysis is developed. This catalytic strategy enables exclusive access to α-selective products, which complementary previously reported photocatalytic that provides the β-selective products. The chain-walking a Ni–H intermediate toward carbonyl allows for at remote sp3 C–H sites. method tolerates broad substrate scope both amines as well providing streamlined synthesis value-added β-amino acid derivatives from readily available starting materials.

Язык: Английский

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The Merger of Benzophenone HAT Photocatalysis and Silyl Radical-Induced XAT Enables Both Nickel-Catalyzed Cross-Electrophile Coupling and 1,2-Dicarbofunctionalization of Olefins

ACS Catalysis, Год журнала: 2022, Номер 12(18), С. 11216 - 11225

Опубликована: Сен. 1, 2022

A strategy for both cross-electrophile coupling and 1,2-dicarbofunctionalization of olefins has been developed. Carbon-centered radicals are generated from alkyl bromides by merging benzophenone hydrogen atom transfer (HAT) photocatalysis silyl radical-induced halogen (XAT) subsequently intercepted a nickel catalyst to forge the targeted C(sp3)-C(sp2) C(sp3)-C(sp3) bonds. The mild protocol is fast scalable using flow technology, displays broad functional group tolerance, amenable wide variety medicinally relevant moieties. Mechanistic investigations reveal that ketone catalyst, upon photoexcitation, responsible direct activation silicon-based XAT reagent (HAT-mediated XAT) furnishes radical ultimately involved in turnover catalytic cycle.

Язык: Английский

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