Recent Advances in Alkenyl sp² C–H and C–F Bond Functionalizations: Scope, Mechanism, and Applications

Chemical Reviews, Год журнала: 2022, Номер 122(24), С. 17479 - 17646

Опубликована: Окт. 14, 2022

Alkenes and their derivatives are featured widely in a variety of natural products, pharmaceuticals, advanced materials. Significant efforts have been made toward the development new practical methods to access this important class compounds by selectively activating alkenyl C(sp2)–H bonds recent years. In comprehensive review, we describe state-of-the-art strategies for direct functionalization sp2 C–H C–F until June 2022. Moreover, metal-free, photoredox, electrochemical also covered. For clarity, review has divided into two parts; first part focuses on currently available using different alkene as starting materials, second describes bond easily accessible gem-difluoroalkenes material. This includes scope, limitations, mechanistic studies, stereoselective control (using directing groups well metal-migration strategies), applications complex molecule synthesis where appropriate. Overall, aims document considerable advancements, current status, emerging work critically summarizing contributions researchers working fascinating area is expected stimulate novel, innovative, broadly applicable functionalizations coming

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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Catalytic Asymmetric Hydroalkylation of α,β-Unsaturated Amides Enabled by Regio-Reversed and Enantiodifferentiating syn-Hydronickellation

ACS Catalysis, Год журнала: 2021, Номер 11(14), С. 8766 - 8773

Опубликована: Июль 2, 2021

Here, we report an enantioselective nickel-hydride catalyzed hydroalkylation of readily accessible β-alkyl-α,β-unsaturated amides to form structurally diverse β-chiral amides. This process was proposed proceed through enantiodifferentiating syn-hydrometalation nickel hydride, forming chiral alkylnickel at the β-position in which regioselectivity is different from that with copper hydride. regio-reversed hydronickellation provides a complementary approach access enantioenriched β-functionalization stereocenter β-position.

Язык: Английский

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The Linkage of Sulfonimidoyl Fluorides and Unactivated Alkenes via Hydrosulfonimidoylation

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(44)

Опубликована: Сен. 15, 2022

Abstract Sulfur(VI) fluoride cleavage and exchanging linkage, a new generation of linkage chemistry, exhibits enormous potential for combining range functional molecules in an increasing number fields. Herein, we established metal‐free unactivated alkenes sulfonimidoyl fluorides via hydrosulfonimidoylation to construct sulfoximines within minutes. An intermolecular hydride transfer process is the key step, it occurs overlap LUMO cation HOMO alkene, which was confirmed control experiments with deuterated compounds. DFT calculations further demonstrated concerted involving formation S−C( sp 3 ) bond transfer. Remarkably, abundant natural products pharmaceuticals multiple heteroatoms sensitive groups have been subjected current reaction achieve various sulfoximine linkages, furnishing basis drug discovery conjugation.

Язык: Английский

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Divergent Access to Chiral C2- and C3-Alkylated Pyrrolidines by Catalyst-Tuned Regio- and Enantioselective C(sp³)–C(sp³) Coupling

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(28), С. 15456 - 15464

Опубликована: Июнь 12, 2023

Novel-substituted pyrrolidine derivatives are widely used in drugs and bioactive molecules. The efficient synthesis of these valuable skeletons, especially enantiopure derivatives, is still recognized as a key bottleneck to overcome chemical synthesis. Herein, we report highly catalyst-tuned regio- enantioselective hydroalkylation reaction for the divergent chiral C2- C3-alkylated pyrrolidines through desymmetrization readily available 3-pyrrolines. catalytic system consists CoBr2 with modified bisoxazoline (BOX) ligand, which can achieve asymmetric C(sp3)-C(sp3) coupling via distal stereocontrol, providing series high efficiency. Moreover, nickel allows synthesize C2-alkylated tandem alkene isomerization/hydroalkylation reaction. This method uses catalysts, BOX ligands, reagents, delivering enantioenriched 2-/3-alkyl substituted excellent enantioselectivity (up 97% ee). We also demonstrate compatibility this transformation complex substrates derived from molecules good efficiency, offers distinct entry more functionalized N-heterocycles.

Язык: Английский

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Asymmetric alkyl-alkyl cross-coupling enabled by earth-abundant metal-catalyzed hydroalkylations of olefins

Chem Catalysis, Год журнала: 2023, Номер 3(4), С. 100508 - 100508

Опубликована: Янв. 30, 2023

Язык: Английский

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Low-temperature hydroformylation of ethylene by phosphorous stabilized Rh sites in a one-pot synthesized Rh-(O)-P-MFI zeolite

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Ноя. 7, 2023

Zeolites containing Rh single sites stabilized by phosphorous were prepared through a one-pot synthesis method and are shown to have superior activity selectivity for ethylene hydroformylation at low temperature (50 °C). Catalytic is ascribed confined Rh2O3 clusters in the zeolite which evolve under reaction conditions into Rh3+ sites. These effectively Rh-(O)-P structure using tetraethylphosphonium hydroxide as template, generates situ phosphate species after H2 activation. In contrast Rh2O3, Rh0 appear less active propanal production ultimately transform Rh(I)(CO)2 similar conditions. As result, we show that it possible reduce of with solid catalyst down 50 °C, good high selectivity, controlling electronic morphological properties

Язык: Английский

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Cobalt-Catalyzed Desymmetric Isomerization of Exocyclic Olefins

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(49), С. 20633 - 20639

Опубликована: Дек. 6, 2021

Chiral cyclic olefins, 1-methylcyclohexenes, are versatile building blocks for the synthesis of pharmaceuticals and natural products. Despite prevalence these structural motifs, development efficient synthetic methods remains an unmet challenge. Herein we report a novel desymmetric isomerization exocyclic olefins using series newly designed chiral cobalt catalysts, which enables straightforward construction 1-methylcyclohexenes with diversified functionalities. The utility this methodology is highlighted by concise enantioselective product, β-bisabolene. versatility reaction products further demonstrated multifarious derivatizations.

Язык: Английский

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Porphyrin covalent organic framework for photocatalytic synthesis of tetrahydroquinolines

Chinese Chemical Letters, Год журнала: 2022, Номер 33(10), С. 4559 - 4562

Опубликована: Янв. 31, 2022

Язык: Английский

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Bifunctional ligand enabled selective alkoxycarbonylation of aliphatic alkenes

Journal of Catalysis, Год журнала: 2022, Номер 409, С. 98 - 104

Опубликована: Апрель 9, 2022

Язык: Английский

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