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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Cobalt/Salox‐Catalyzed Enantioselective C−H Functionalization of Arylphosphinamides

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(25)

Опубликована: Апрель 6, 2022

Previous methods on CoIII -catalyzed asymmetric C-H activation rely the use of tailor-made cyclopentadienyl-ligated complexes, which require lengthy steps for preparation. Herein, we report an unprecedented enantioselective functionalization enabled by a simple cobalt/salicyloxazoline (Salox) catalysis. The chiral Salox ligands can be easily prepared in one step from salicylonitrile and amino alcohols. A broad range P-stereogenic compounds were synthesized high yields with excellent enantioselectivities (45 examples, up to 99 % yield >99 ee). isolation characterization several intermediates provided insights into generation active catalytic cobalt species, action Salox, mode stereocontrol.

Язык: Английский

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Enantioselective hydrogen-bond-donor catalysis to access diverse stereogenic-at-P(V) compounds

Science, Год журнала: 2022, Номер 376(6598), С. 1230 - 1236

Опубликована: Июнь 9, 2022

The stereoselective synthesis of molecules bearing stereogenic phosphorus(V) centers represents an enduring challenge in organic chemistry. Although stereospecific nucleophilic substitution at P(V) provides a general strategy for elaborating optically active compounds, existing methods accessing the requisite chiral building blocks rely almost entirely on diastereocontrol using auxiliaries. Catalytic, enantioselective synthetically versatile offer alternative approach to stereogenic-at-P(V) targets without requiring stoichiometric quantities control elements. Here, we report hydrogen-bond-donor-catalyzed aryl chlorophosphonamidates and development these products as blocks. We demonstrate that two leaving groups can be displaced sequentially stereospecifically access wide variety compounds featuring diverse patterns.

Язык: Английский

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P-Stereogenic Phosphorus Ligands in Asymmetric Catalysis

Chemical Reviews, Год журнала: 2024, Номер 124(14), С. 8657 - 8739

Опубликована: Июль 2, 2024

Chiral phosphorus ligands play a crucial role in asymmetric catalysis for the efficient synthesis of useful optically active compounds. They are largely categorized into two classes: backbone chirality and P-stereogenic ligands. Most reported belong to former class. Privileged ones such as BINAP DuPhos frequently employed wide range catalytic transformations. In contrast, latter class has remained small family many years mainly because their synthetic difficulty. The late 1990s saw emergence novel with superior enantioinduction ability Rh-catalyzed hydrogenation reactions. Since then, numerous have been synthesized used This Review summarizes thus far, including stereochemical electronic properties that afford high excellent enantioselectivities. Examples reactions use this described together applications construction key intermediates natural products therapeutic agents. literature covered dates back 1968 up until December 2023, centering on studies published later years.

Язык: Английский

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Palladium/Xiao‐Phos‐Catalyzed Kinetic Resolution of sec‐Phosphine Oxides by P‐Benzylation

Angewandte Chemie International Edition, Год журнала: 2021, Номер 60(52), С. 27247 - 27252

Опубликована: Окт. 21, 2021

P-stereogenic tert- and sec-phosphines have wide applications in asymmetric catalysis, materials, pharmaceutical chemistry, however, their practical synthesis still constitutes a significant challenge. Herein, successful kinetic resolution of rac-secondary phosphine oxides via the enantioselective P-benzylation process catalyzed by palladium/Xiao-Phos was designed. Both sec-phosphine were delivered good yield excellent enantiopurity (selectivity factor up to 226.1). The appealing synthetic utilities are further demonstrated facile preparation several valuable P-chiral compounds, precursors bidentate ligands, as well transition metal complexes.

Язык: Английский

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Asymmetric C–H Activation for the Synthesis of P- and Axially Chiral Biaryl Phosphine Oxides by an Achiral Cp*Ir Catalyst with Chiral Carboxylic Amide

ACS Catalysis, Год журнала: 2021, Номер 12(1), С. 193 - 199

Опубликована: Дек. 14, 2021

The catalytic synthesis of P- and axially chiral biaryl phosphine oxides was realized via the Cp*Ir-catalyzed asymmetric C–H coupling tertiary substituted with diarylacetylenes. carboxylic amides were used to control stereoselectivity in activation, enabling construction up 96% ee. Transformation products into trivalent ligands has also been demonstrated.

Язык: Английский

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Copper‐Catalyzed Dynamic Kinetic C−P Cross‐Coupling/Cyclization for the Concise Asymmetric Synthesis of Six‐, Seven‐ and Eight‐MemberedP‐Stereogenic Phosphorus Heterocycles

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(24)

Опубликована: Март 29, 2022

Abstract A copper‐catalyzed asymmetric aryl C−P cross‐coupling/cyclization reaction was successfully developed via dynamic kinetic transformation (DYKAT) under mild conditions. This study provides a general and simple method for the catalytic enantioselective synthesis of stable six‐, seven‐ eight‐membered P‐stereogenic phosphorus heterocycles with excellent enantioselectivities moderate to high yields. One‐pot gram‐scale P‐heterocycle from commercially available materials also accomplished enantioselectivity yield.

Язык: Английский

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Ni-Catalyzed Enantioselective Benzylation of Secondary Phosphine Oxide

Organic Letters, Год журнала: 2022, Номер 24(5), С. 1258 - 1262

Опубликована: Фев. 2, 2022

A nickel-catalyzed benzylic substitution of secondary phosphine oxide was described, affording the dialkylated P-stereogenic tertiary oxides with high to excellent enantioselectivities. The reaction performed under mild conditions commercially available benzyl chlorides and bench stable oxides, exhibiting broad functional group tolerance. It represented a practical example for preparation compounds.

Язык: Английский

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Palladium‐Catalyzed Stereoselective Cleavage of C−P Bond: Enantioselective Construction of Atropisomers Containing a P‐Stereogenic Center

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(47)

Опубликована: Сен. 28, 2022

The transition-metal-catalyzed C-P bond cleavage has emerged as a powerful tool for the formation of both C-C and bond. However, stereoselective is still undeveloped. Herein, we report palladium-catalyzed construction P-stereogenic phosphines stereogenic axis. This protocol enables quick synthesis atropisomers bearing center in high yields, diastereo- enantioselectivities up to 98 % ee, >25 : 1 dr. product able serve chiral catalyst phosphine catalyzed [3+2] cycloaddition allenoates imines, showing great potential present methodology.

Язык: Английский

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Synthesis of P-stereogenic cyclicphosphinic amidesviaelectrochemically enabled cobalt-catalyzed enantioselective C–H annulation

Green Chemistry, Год журнала: 2023, Номер 25(9), С. 3606 - 3614

Опубликована: Янв. 1, 2023

We describe a cobalta-electro-catalyzed enantioselective C–H annulation of arylphosphinamides with alkynes for P-stereogenic compounds via desymmetrization and kinetic resolution processes.

Язык: Английский

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