In(III)-Catalyzed 1,2-Hydrophosphorylation of 3-Alkynyl-3-hydroxyisoindolinones to 3,3-Disubstituted Isoindolinones Featuring Both Phosphoryl and Alkynyl Groups at the C3-Position

The Journal of Organic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Янв. 23, 2025

We report a highly regioselective 1,2-addition of P(O)-H compounds to the in situ generated β,γ-alkynyl-α-ketimine derived from 3-alkynyl-3-hydroxyisoindolinones, which provided general protocol for preparation 3,3-disubstituted isoindolinones featuring both phosphoryl and alkynyl groups at quaternary carbon center. The use only 2-5 mol % an inexpensive catalyst (In(ClO4)3·8H2O or Bi(OTf)3) allowed smooth output desired products under mild conditions (25 °C, 0.5-24 h) with broad substrate scope (35 examples) up >99% yield. obtained could be further elaborated based on alkyne moiety. initial asymmetric trial indicated that BINOL-derived CPA enable enantioselective induction 46% yield 77% ee.

Язык: Английский

---

Brønsted Acid Catalyzed Friedel–Crafts Alkylation of Naphthols with In Situ Generated Naphthol-Derived ortho-Quinone Methides: Synthesis of Chiral and Achiral Xanthene Derivatives

The Journal of Organic Chemistry, Год журнала: 2023, Номер 88(5), С. 3159 - 3172

Опубликована: Фев. 23, 2023

We disclose herein an enantioselective protocol for the Brønsted acid catalyzed addition of naphthols to in situ generated naphthol-derived ortho-quinone methides (o-QMs) followed by intramolecular cyclization, which delivers substituted chiral xanthene derivatives, a one-pot reaction sequence under mild conditions. This process serves convert ortho-hydroxyl benzylic alcohols into reactive o-QMs using phosphoric (CPA) catalyst. Moreover, it is helpful controlling enantioselectivity carbon-carbon bond-forming event via hydrogen-bonding cyclization. Additionally, first time, we observe C(sp2)-C(sp3) bond cleavage synthesis achiral (sigma plane containing) derivatives good excellent yields.

Язык: Английский

---

Asymmetric Cycloaddition/Annulation Reactions by Chiral Phosphoric Acid Catalysis: Recent Advances

European Journal of Organic Chemistry, Год журнала: 2022, Номер 2022(34)

Опубликована: Авг. 1, 2022

Abstract Asymmetric cycloaddition/annulation reactions have contributed greatly to the synthesis of a variety novel cyclic compounds used in organic synthesis, natural product material science, and chemical biology. Thus, chiral phosphoric acid‐catalyzed asymmetric cycloaddition received attention synthetic community design new vital synthesize complex molecules for past two decades. Although several review articles on organocatalyzed can be found literature, there has been no specific CPA‐catalyzed reactions. Herein, most recent research progress acid catalyzed [3+2], [4+2], [2+2], [3+3], [4+3], [4+1] annulation, 1,3‐dipolar cycloadditions compiled analyzed demonstrate importance catalysis or annulation

Язык: Английский

---

Dehydrative alkynylation of 3-hydroxyisoindolinones with terminal alkynes for the synthesis of 3-alkynylated 3,3-disubstituted isoindolinones

Organic & Biomolecular Chemistry, Год журнала: 2024, Номер 22(17), С. 3453 - 3458

Опубликована: Янв. 1, 2024

A HOTf or Fe(OTf) 3 -catalyzed dehydrative alkynylation of 3-hydroxyisoindolinones with terminal alkynes was developed, which represents a brand-new procedure for the synthesis 3-alkynylated 3,3-disubstituted isoindolinones.

Язык: Английский

---

Asymmetric Cascade Dearomatization–Cyclization Reaction of Tryptamines with β,γ-Alkynyl-α-imino Esters: Access to Hexahydropyrrolo[2,3-b]indole-Containing Tetrasubstituted α-Amino Allenoates

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(14), С. 10148 - 10162

Опубликована: Июль 3, 2024

An organocatalytic enantio- and diastereoselective synthesis of hexahydropyrrolo[2,3-

Язык: Английский

---

Triflic Acid-Mediated Condensation of Phthalimide with Diaryl Ethers as a Route to Spiro-Isoindolinones: Mechanistic Insights and Related Reactions

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(21), С. 15931 - 15940

Опубликована: Окт. 15, 2024

Phthalimide and N-phenylphthalimide smoothly condense with di-p-tolyl ether in triflic acid (CF3SO3H, TfOH) to obtain the corresponding spiro[isoindoline-1,9′-xanthen]-3-ones. Structural analogs of phthalimide, such as phthalic anhydride 1,3-indandione (but not saccharin), show similar reactivity. In contrast, N-(tetrafluoropyridin-4-yl)phthalimide reacts DTE by an alternative pathway, yielding isobenzofuran dispiro derivative. The mechanistic aspects these reactions are discussed on basis situ NMR theoretical (DFT) studies, providing insights key intermediacy O,O-diprotonated forms starting compounds.

Язык: Английский

---

Chiral phosphoric acid-catalyzed reaction between C-alkynyl imine precursor and thiol: Access to highly enantioenriched alkynyl isoindolinones with N,S-ketal framework

Tetrahedron Letters, Год журнала: 2022, Номер 112, С. 154230 - 154230

Опубликована: Ноя. 11, 2022

Язык: Английский

---

Substrate Controlled [3+3] Relay Catalytic Cyclization of α‐(3‐Isoindolinonyl) Propargylic Alcohols with 5‐Aminoisoxazoles

Asian Journal of Organic Chemistry, Год журнала: 2024, Номер 13(6)

Опубликована: Март 12, 2024

Abstract Two different skeletons have been constructed by cyclization of α‐(3‐isoindolinonyl) propargylic alcohols with 5‐aminoisoxazoles bearing N ‐substituents under the relay catalysis Brønsted acid and Lewis acid. This method provided spiro‐isoindolinone‐dihydropyridines moderate to high yields (up 99 %) as well isoxazolo[4,5‐b]pyridines in good 86 %). The structures two products were determined X‐ray crystal structural analyses. Moreover, fluorescence testing proved that one exhibited aggregation induced emission (AIE) effect. Finally, control experiments revealed possible reaction mechanism.

Язык: Английский

---

Enantioselective intramolecular tandem cyclization of o-alkynylbenzamides: generation of enantioenriched CF₃-containing spiro-isoindolinone-indoles

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(9), С. 2591 - 2599

Опубликована: Янв. 1, 2024

Enantioselective intramolecular tandem cyclization of dielectrophile–dinucleophile assembled o -alkynylbenzamides provided a variety spiro-isoindolinone-indoles in low to moderate yields with good enantioselectivities.

Язык: Английский

---

Organocatalytic C_sp2–O Amination of Quinolin-4(1H)-ones with 3-Alkynyl-3-hydroxyisoindolinones

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(12), С. 9086 - 9091

Опубликована: Май 30, 2024

The Brønsted acid catalytic Csp2–O amination of quinolin-4(1H)-ones with 3-alkynyl-3-hydroxyisoindolinones as animation reagents has been developed. cascade dehydration/conjugate addition/intramolecular annulation/ring-opening reaction proceeded smoothly to afford a broad scope aminated products high efficiency. Furthermore, the enantioselective construction Csp2–N atropisomers was also investigated in presence chiral phosphoric acid. Importantly, this work not only realized organocatalytic but laid foundation for directly asymmetric synthesis atropisomers.

Язык: Английский

---