Pd(II)-Catalyzed Enantioselective C(sp³)–H Arylation toward P-Stereogenic Dialkylphosphinamides

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(9), P. 7213 - 7219

Published: April 24, 2024

Transition-metal-catalyzed enantioselective C–H functionalization has emerged as a promising method for the synthesis of P-stereogenic phosphorus compounds. However, previous reports are limited to C(sp2)–H bonds aryl phosphine derivatives. Herein, Pd(II)-catalyzed arylation more challenging C(sp3)–H toward dialkylphosphinamides is achieved through desymmetrization gem-diethyl groups. Various obtained with high enantioselectivities using 3,3′-CN2-H8-BINOL chiral ligand. The synthetic potential this methodology highlighted by gram-scale preparation and further derivatizations.

Language: Английский

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Bis-CF₃-bipyridine Ligands for the Iridium-Catalyzed Borylation of N-Methylamides

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 7112 - 7120

Published: April 16, 2025

Language: Английский

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Recent synthetic methodology advancements towards all-carbon quaternary center formation and applications

Tetrahedron, Journal Year: 2025, Volume and Issue: unknown, P. 134711 - 134711

Published: May 1, 2025

Language: Английский

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Enantio-divergent C–H borylation with two different ligands from a single chiral source

Science China Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 23, 2024

Language: Английский

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Pd(II)-Catalyzed Desymmetrizing gem-Dimethyl C(sp³)–H Alkenylation/Aza-Wacker Cyclization Directed by PIP Auxiliary

Organic Letters, Journal Year: 2024, Volume and Issue: 26(21), P. 4457 - 4462

Published: May 22, 2024

Desymmetrization of

Language: Английский

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Catalytic Enantioselective (3+2) Annulations of Nucleophilic Thioacyl Rh(I)-Carbenes with Achmatowicz Rearrangement Products

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(11), P. 8949 - 8957

Published: May 28, 2024

The cycloaddition and annulation reactions of Achmatowicz rearrangement products (ARPs) are critically important to the construction molecular complexity total synthesis natural products. However, this field is still blemished by shortage enantioselective (3+2) ARPs. Herein, we report highly enantio-, diastereo-, regioselective annulations ARPs with nucleophilic α-thioacyl Rh(I)-carbenes under Rh(I)/(R)-BINAP catalysis, producing bicyclic dihydrothiophenes multiple functionalities, three continuous chiral centers, five prochiral centers in up 97% yields 99:1 er. Mechanistically, migratory insertion following anticoordination suggested determine enantio- regioselectivities accounts for character Rh(I)-carbenes. DFT calculations revealed that enantioinduction originates from steric discrimination (R)- (S)-ARPs ligand.

Language: Английский

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Substrate-directed C(sp³)–H borylation via transition metal catalysis: expanding the toolbox for C–H functionalization

Catalysis Science & Technology, Journal Year: 2024, Volume and Issue: 14(19), P. 5488 - 5504

Published: Jan. 1, 2024

Organoborons play a crucial role in organic synthesis, easing the construction of C–C and C–X bonds, which turn sensitize C(sp 3 )–H borylation reactions.

Language: Английский

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The Difference in Ir-Catalyzed C(sp²)–H and C(sp³)–H Bond Activation Assisted by a Directing Group: Cyclometalation via Cis- or Trans-Chelation?

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(38), P. 17626 - 17638

Published: Sept. 5, 2024

Iridium-catalyzed C-H borylation of aromatic and aliphatic hydrocarbons assisted by a directing group was theoretically investigated. Density functional theory (DFT) calculations revealed both Ir-catalyzed C(sp

Language: Английский

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Theoretical Insight into the Multiple Roles of the Silyl-Phenanthroline Ligand in Ir-Catalyzed C(sp³)–H Borylation

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 6, 2024

Silyl-phenanthroline (NN′Si) ligand ancillary iridium-catalyzed C(sp3)–H borylation is investigated theoretically. Density functional theory calculations clearly disclose that the (NN′Si)IrV(H)(Bpin)3 (NN′Si = 6-[(di-tert-butylsilyl)methyl]-1,10-phenanthroline) complex a resting state, and (NN′Si)IrIII(Bpin)2 serves as an active species in catalytic cycle. The remarkably high activity of this type catalyst arises from rapid reductive elimination HBpin to generate (NN′Si)IrIII(Bpin)2. silyl group plays crucial role accelerating hydride-migration elementary step, which allows isomerization (NN′Si)IrV(R)(H)(Bpin)2 intermediate achieve C(sp3)–B afford borylated product. Although with thermodynamically unfavorable, Ir-dihydride (NN′Si)IrV(H)2(Bpin)2 generated after product formation slightly more stable than resting-state cycle, important driving force for reaction. Such success was not attained by many other traditional bidentate ligands. unique regioselectivity n-butyl ethyl ether 2-methylheptane, induced NN′Si-pincer ligand, well reproduced underlying reason selectivity elucidated.

Language: Английский

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Enantioselective α-C(sp³)–H Borylation of Masked Primary Alcohols Enabled by Iridium Catalysis

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 18, 2024

Functional group-directed site- and enantioselective C(sp3)–H functionalization of alcohols or masked represents a formidable challenge. We herein report the first example iridium-catalyzed asymmetric α-C(sp3)–H borylation primary alcohol-derived carbamates by judicious choice directing groups. A variety chiral borylated were obtained with good to high enantioselectivities. also demonstrated synthetic utility taking advantage highly transformable feature C–B bonds leaving ability carbamates.

Language: Английский

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