HFIP in Organic Synthesis

Chemical Reviews, Год журнала: 2022, Номер 122(15), С. 12544 - 12747

Опубликована: Июль 17, 2022

1,1,1,3,3,3-Hexafluoroisopropanol (HFIP) is a polar, strongly hydrogen bond-donating solvent that has found numerous uses in organic synthesis due to its ability stabilize ionic species, transfer protons, and engage range of other intermolecular interactions. The use this exponentially increased the past decade become choice some areas, such as C–H functionalization chemistry. In review, following brief history HFIP an overview physical properties, literature examples reactions using or additive are presented, emphasizing effect each reaction.

Язык: Английский

---

Dispersion and Steric Effects on Enantio-/Diastereoselectivities in Synergistic Dual Transition-Metal Catalysis

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(4), С. 1971 - 1985

Опубликована: Янв. 20, 2022

Comprehensive computational studies were carried out to explore the mechanisms of enantioselective Cu/Pd and stereodivergent Cu/Ir dual-catalytic syntheses α,α-disubstituted α-amino acids (α-AAs). A chiral copper azomethine ylide undergoes facile α-allylation with racemic π-allylpalladium species or stereopure π-allyliridium complex stereoconvergently stereodivergently furnish single/double stereocenters, respectively. Stereoselectivity at α-center is controlled by facial selectivity respect prochiral nucleophile. Despite apparently similar transition-state assemblies, models distortion/interaction analyses disclose versatile modes stereoinduction wherein can face-selectively intercept metal−π-allyl intermediates utilizing attractive dispersion interactions and/or sterically caused distortions. Generation β-stereocenter in system relies on a stereospecifically generated allyliridium electronically branched-to-linear selectivity, while dual yields linear monochiral product due steric factors π–π stacking interactions. The demonstrate molecular level how ligand-encoded information transferred α-/β-sites resulting α-AAs mode regio-/stereoselection altered differences transition-metal-stabilized coupling partners. To facilitate stereoselective catalysis, suite analytical tools extract controlling for asymmetric induction demonstrated.

Язык: Английский

---

Recent developments on 1,2-difunctionalization and hydrofunctionalization of unactivated alkenes and alkynes involving C–S bond formation

Organic Chemistry Frontiers, Год журнала: 2023, Номер 10(5), С. 1322 - 1345

Опубликована: Янв. 1, 2023

Functionalization of alkenes/alkynes is a highly effective route to achieve molecular complexity. This review summarizes recent progresses on the 1,2-difunctionalization/hydrofunctionalization unactivated with C−S bond formation.

Язык: Английский

---

Enantioselective Construction of Axially Chiral Amino Sulfide Vinyl Arenes by Chiral Sulfide‐Catalyzed Electrophilic Carbothiolation of Alkynes

Angewandte Chemie International Edition, Год журнала: 2020, Номер 59(12), С. 4959 - 4964

Опубликована: Янв. 22, 2020

The enantioselective construction of axially chiral compounds by electrophilic carbothiolation alkynes is disclosed for the first time. This transformation enabled use a Ts-protected bifunctional sulfide catalyst and Ms-protected ortho-alkynylaryl amines (Ts=tosyl; Ms=mesyl). Both arylthiolating trifluoromethylthiolating reagents are suitable this reaction. obtained products vinyl-aryl amino sulfides can be easily converted into biaryl sulfides, sulfoxides, amines, other valuable difunctionalized compounds.

Язык: Английский

---

Catalytic, Enantioselective Sulfenofunctionalization of Alkenes: Development and Recent Advances

Angewandte Chemie International Edition, Год журнала: 2020, Номер 59(45), С. 19796 - 19819

Опубликована: Май 26, 2020

The last decade has witnessed a burgeoning of new methods for the enantioselective vicinal difunctionalization alkenes initiated by electrophilic sulfenyl group transfer. addition sulfenium ions to results in generation chiral, non-racemic thiiranium ions. These highly reactive intermediates are susceptible attack myriad nucleophiles stereospecific ring-opening event afford anti 1,2-sulfenofunctionalized products. practical application ion transfer been enabled advances field Lewis base catalysis. This Review will chronicle initial discovery and characterization followed determination their configurational stability challenges developing variants. Once framework reactivity established, critical analysis pioneering studies be presented. Finally, comprehensive discussion modern synthetic applications categorized around type nucleophile employed sulfenofunctionalization.

Язык: Английский

---

Chiral Selenide/Achiral Sulfonic Acid Cocatalyzed Atroposelective Sulfenylation of Biaryl Phenols via a Desymmetrization/Kinetic Resolution Sequence

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(7), С. 2943 - 2952

Опубликована: Фев. 10, 2022

Enantioselective synthesis of axially chiral sulfur-containing biaryl derivatives through the electrophilic sulfenylation phenols has been achieved for first time. This catalytic asymmetric system, which involves sequential desymmetrization and kinetic resolution, is enabled by a combination novel 3,3'-disubstituted BINOL-derived selenide catalyst an achiral sulfonic acid. Control experiments computational studies suggest that multiple noncovalent interactions between cocatalysts substrate, especially network hydrogen bond interactions, play crucial role in determining enantioselectivity reactivity.

Язык: Английский

---

Chalcogen bonding catalysis

Chemical Society Reviews, Год журнала: 2023, Номер 53(2), С. 586 - 605

Опубликована: Дек. 7, 2023

Catalysts play a major role in chemical synthesis, and catalysis is considered to be green economic process. Catalysis dominated by covalent interactions between the catalyst substrate. The design of non-covalent catalysts came into limelight only recently. Hydrogen bonding (HB) are well established among catalysts, including asymmetric HB catalysts. Though halogen (XB) its version gaining admiration, chalcogen (ChB) budding stage. This tutorial review will focus on recently evolved emphasis given chiral molecules. Since successful enantioselective yet reported, this basics catalysis, chalcogenide rigidification transition states ChB, stabilization cations chalcogens, details unsuccessful enantioseparation racemic molecules using existence ChB biomolecules.

Язык: Английский

---

Rh(III)-Catalyzed Atroposelective C–H Selenylation of 1-Aryl Isoquinolines

ACS Catalysis, Год журнала: 2024, Номер 14(8), С. 6009 - 6015

Опубликована: Апрель 5, 2024

Rhodium(III)-catalyzed atroposelective C–H selenylation of 1-aryl isoquinolines has been achieved. The direct reaction between and 2-(phenylselanyl)isoindoline-1,3-dione in the presence chiral SCpRh(III) complex afforded a series axially isoquinoline selenides up to 95% yield 96% ee. features mild conditions broad substrate scope. DFT calculations revealed that C–Se bond formation step proceeds through formal SN2 pathway.

Язык: Английский

---

Asymmetric Synthesis with Organoselenium Compounds – The Past Twelve Years

Chemistry - A European Journal, Год журнала: 2024, Номер 30(21)

Опубликована: Янв. 11, 2024

Abstract The discovery and synthetic applications of novel organoselenium compounds their reactions proceeded rapidly during the past fifty years such processes are now carried out routinely in many laboratories. At same time, growing demand for new enantioselective provided challenges. convergence selenium chemistry asymmetric synthesis led to key developments 1970s, although majority early work was based on stoichiometric processes. More recently, greater emphasis has been placed greener catalytic variations, along with a deeper understanding mechanisms. present review covers literature this field from 2010 2023 encompasses mediated by chiral selenium‐based reagents, auxiliaries, especially, catalysts. Protocols achiral conjunction other species catalysts, as well that controlled substrates, also included.

Язык: Английский

---

Atroposelective Electrophilic Sulfenylation ofN‐Aryl Aminoquinone Derivatives Catalyzed by Chiral SPINOL‐Derived Sulfide

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(42)

Опубликована: Авг. 30, 2022

Atroposelective electrophilic sulfenylation of N-aryl aminoquinone derivatives has been achieved for the first time. This transformation is enabled by a new chiral 6,6'-disubstituted SPINOL-derived sulfide catalyst, which was synthesized and then successfully explored catalyzing enantioselective reactions. Various axially sulfur-containing diarylamine were readily obtained in moderate to excellent yields with enantioselectivities. A class relatively flexible stereogenic C-N axes easily constructed. The experimental results computational study suggested that an intramolecular N-H⋅⋅⋅S hydrogen bond important stability axis, consistent our hypothesis. Density functional theory calculations revealed origin atroposelectivity underscored importance catalyst rigidity this reaction.

Язык: Английский

---