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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Palladium-catalyzed enantioselective carbonylation reactions

Science China Chemistry, Год журнала: 2022, Номер 65(3), С. 441 - 461

Опубликована: Янв. 5, 2022

Abstract Carbonylation, one of the most powerful approaches to preparation carbonylated compounds, has received significant attention from researchers active in various fields. Indeed, impressive progress been made on this subject over past few decades. Among types carbonylation reactions, asymmetric is a straightforward methodology for constructing chiral compounds. Although rhodium-catalyzed enantioselective hydroformylations have discussed several elegant reviews, general review palladium-catalyzed carbonylations still missing. In review, we summarize and discuss recent achievements reactions. Notably, review’s contents are categorized by reaction type.

Язык: Английский

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Palladium-Catalyzed Difluorocarbene Transfer Enabled Divergent Synthesis of γ-Butenolides and Ynones from Iodobenzene and Terminal Alkynes

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(2), С. 1722 - 1731

Опубликована: Янв. 4, 2024

Herein, we report a ligand-controlled palladium-catalyzed method that enables the synthesis of ynones and γ-butenolides with excellent regioselectivity from same set readily available aryl iodides, acetylenes, BrCF2CO2K. In this reaction, [PdII]═CF2 does demonstrate electrophilicity can generate CO when reacting H2O. It is environmentally friendly safe compared to traditional methods, current protocol us afford in high yields functionality tolerance. Moreover, esters also be obtained corresponding phenols alcohols utilizing strategy. The success late-stage functionalization bioactive compounds further illustrates synthetic utility material development drug discovery.

Язык: Английский

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Enantioselective NiH‐Catalyzed Reductive Hydrofunctionalization of Alkenes

Chinese Journal of Chemistry, Год журнала: 2021, Номер 40(5), С. 651 - 661

Опубликована: Дек. 3, 2021

Comprehensive Summary Enantioselective NiH‐catalyzed reductive hydrofunctionalization of olefins has attracted much attention in recent years. Using simple chiral ligands, a wide array functionalized and electrophiles can undergo diverse transformations to afford hydrofunctionalized products, regio‐ enantioselectively. These processes avoid the prior preparation organometallic reagents, construct stereogenic center at carbon originating either from olefin or electrophile. This review discusses background, major progress mechanistic investigations this reaction.

Язык: Английский

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A relay catalysis strategy for enantioselective nickel-catalyzed migratory hydroarylation forming chiral α-aryl alkylboronates

Chem, Год журнала: 2021, Номер 7(11), С. 3171 - 3188

Опубликована: Ноя. 1, 2021

Язык: Английский

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Facile Synthesis of Chiral Arylamines, Alkylamines and Amides by Enantioselective NiH‐Catalyzed Hydroamination

Angewandte Chemie International Edition, Год журнала: 2021, Номер 60(44), С. 23584 - 23589

Опубликована: Авг. 27, 2021

Regio- and enantioselective hydroarylamination, hydroalkylamination hydroamidation of styrenes have been developed by NiH catalysis with a simple bioxazoline ligand under mild conditions. A wide range enantioenriched benzylic arylamines, alkylamines amides can be easily accessed nitroarenes, hydroxylamines dioxazolones, respectively as amination reagents. The chiral induction in these reactions is proposed to proceed through an enantiodifferentiating syn-hydronickellation step.

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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Ligand Relay Catalysis Enables Asymmetric Migratory Reductive Acylation of Olefins or Alkyl Halides

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(47), С. 21448 - 21456

Опубликована: Ноя. 17, 2022

Design of ligands in transition-metal catalyzed reactions is challenging, especially asymmetric transformations. With each step the catalytic cycle promoted by its privileged ligand and different steps well-connected dynamic exchange, synergistic combination multiple could potentially enhance efficiency selectivity. Now, this concept has been applied to NiH-catalyzed remote hydroacylation olefins migratory acylation alkyl halides with excellent regio- enantioselectivity, utilizing two simple ligands, one for chain-walking other acylation. Starting from abundant alkenes/alkyl carboxylic acids, a wide range enantioenriched chiral α-aryl ketones can be efficiently accessed under mild conditions.

Язык: Английский

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Nickel‐Catalyzed Asymmetric Hydroaryloxy‐ and Hydroalkoxycarbonylation of Cyclopropenes

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(36)

Опубликована: Июль 15, 2022

Abstract The asymmetric Reppe carbonylation reactions provide a straightforward access to α ‐chiral carbonyl compounds. reported paradigms predominantly adopted precious palladium as the catalyst. Here we report nickel‐catalyzed of cyclopropenes with phenyl formate and CO/ROH, respectively. This asymmetrical synthetic protocol features high atom economy, good functional group tolerance, which rapidly constructs polysubstituted cyclopropanecarboxylic derivatives excellent diastereo‐ enantioselectivity. utility is demonstrated by facile conversion chiral products into bioactive molecules such (−)‐Tranylcypromine (−)‐Lemborexant.

Язык: Английский

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