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, Год журнала: 2024, Номер 63(38), С. 17626 - 17638

Опубликована: Сен. 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

Язык: 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, Год журнала: 2024, Номер unknown

Опубликована: Дек. 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.

Язык: 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, Год журнала: 2024, Номер unknown

Опубликована: Дек. 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.

Язык: Английский

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Merging Ring-Opening 1,2-Metallate Shift with Asymmetric C(sp³)–H Borylation of Aziridines

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(28), С. 18879 - 18885

Опубликована: Июль 5, 2024

Chiral secondary alkyl amines with a vicinal quaternary stereocenter are undoubtedly important and ubiquitous subunits in natural products pharmaceuticals. However, their asymmetric synthesis remains formidable challenge. Herein, we merge the ring-opening 1,2-metallate shift iridium-catalyzed enantioselective C(

Язык: Английский

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氢原子转移介导的C(sp3)-H键选择性硼基化

Scientia Sinica Chimica, Год журнала: 2024, Номер 54(9), С. 1445 - 1454

Опубликована: Июль 11, 2024

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