Photochemical selective difluoroalkylation reactions of bicyclobutanes: direct sustainable pathways to functionalized bioisosteres for drug discovery

Green Chemistry, Год журнала: 2024, Номер 26(9), С. 5512 - 5518

Опубликована: Янв. 1, 2024

Photochemical solvent-controlled difluoromethylation and bromo-difluoromethylation reactions of bicyclobutanes are described. The method provides efficient pathways to obtain difluoroalkyl functionalized bioisosteres for drug discovery.

Язык: Английский

---

Simultaneous Stereoinvertive and Stereoselective C(sp³)–C(sp³) Cross-Coupling of Boronic Esters and Allylic Carbonates

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(20), С. 13719 - 13726

Опубликована: Май 9, 2024

With increasing interest in constructing more three-dimensional entities, there has been growing cross-coupling reactions that forge C(sp3)–C(sp3) bonds, which leads to additional challenges as it is not just a difficult bond construct but issues of stereocontrol also arise. Herein, we report the stereocontrolled enantioenriched boronic esters with racemic allylic carbonates enabled by iridium catalysis, leading formation bonds single or vicinal stereogenic centers. The method shows broad substrate scope, enabling primary, secondary, and even tertiary be employed, can used prepare any four possible stereoisomers coupled product chiral new method, combines simultaneous enantiospecific reaction nucleophile enantioselective electrophile process, offers solution for stereodivergent two C(sp3) fragments.

Язык: Английский

---

Solvent‐Dependent Divergent Cyclization of Bicyclo[1.1.0]butanes

Angewandte Chemie International Edition, Год журнала: 2024, Номер unknown

Опубликована: Дек. 17, 2024

Bicyclo[1.1.0]butanes (BCBs) have recently garnered significant research interest as versatile precursors for synthesizing potential [n.1.1] bioisosteres and multi-functionalized cyclobutanes in a straightforward atom-economical manner. Here, we report solvent-dependent divergent cyclization of BCBs that provides highly diastereospecific decorated oxygen-containing bicyclo[3.1.1]heptanes (BCHeps), which serve meta-substituted arenes. Additionally, an unprecedented 1,2-difunctionalization reaction mode was explored, thus expanding the chemical space arene functionalized cyclobutanes.

Язык: Английский

---

Zwitterionic π-Allyl-Pd Species Enabled [2σ+2π] Cycloaddition Reactions of Vinylbicyclo[1.1.0]butanes (VBCBs) with Alkenes, Carbonyls, and Imines

ACS Catalysis, Год журнала: 2024, Номер 14(24), С. 18799 - 18809

Опубликована: Дек. 11, 2024

Transition-metal-catalyzed cycloaddition reactions of strained small-ring compounds are powerful methods for constructing carbo- and heterocyclic structures medicinal interest. However, the application this strategy to bicyclo[1.1.0]butanes (BCBs), which among most carbocycles known, remains underdeveloped. Herein, we report vinylbicyclo[1.1.0]butane (VBCB) as a platform synthon palladium-catalyzed formal [2σ+2π] with various 2π-components, enabling synthesis BCHs, oxa-BCHs, aza-BCHs under identical reaction conditions. The zwitterionic π-allyl-Pd species generated through activation VBCBs is key circumventing potential carbene reactivity serves common intermediate cycloadditions diverse 2π-systems, including alkenes, aldehydes, ketones, imines. Notably, by utilizing Pd2(dba)3 an anthracene-derived Trost ligand, wide array BCHs bearing two vicinal chiral centers has been prepared in highly diastereo-, enantioselective manner. generality practicality method have demonstrated broad substrate scope, scale-up reactions, versatile transformation multiple functional groups into BCH scaffolds. Preliminary mechanistic studies support formation species.

Язык: Английский

---

Visible Light Promoted de Mayo Type Reaction of Bicyclo[1.1.0]butanes

Chemistry - A European Journal, Год журнала: 2024, Номер 30(68)

Опубликована: Авг. 23, 2024

Abstract We reported herein a visible light mediated de Mayo‐type reaction between 1,3‐diketones and BCB. The proceeds through [2π+2σ] cycloaddition retro‐aldol sequence, producing cis‐difunctionalized cyclobutanes in high yields with good regio‐ diastereoselectivity.

Язык: Английский

---