Enantio‐ and Diastereodivergent Synthesis of Spirocycles through Dual‐Metal‐Catalyzed [3+2] Annulation of 2‐Vinyloxiranes with Nucleophilic Dipoles

Angewandte Chemie International Edition, Год журнала: 2021, Номер 60(47), С. 24941 - 24949

Опубликована: Сен. 17, 2021

The development of efficient and straightforward methods for obtaining all optically active isomers structurally rigid spirocycles from readily available starting materials is great value in drug discovery chiral ligand development. However, the stereodivergent synthesis bearing multiple stereocenters remains an unsolved challenge owing to steric hindrance ring strain. Herein, we report enantio- diastereodivergent through dual-metal-catalyzed [3+2] annulation oxy π-allyl metallic dipoles with less commonly employed nucleophilic (imino esters). A series spiro compounds a pyrroline olefin were easily synthesized manner (up 19:1 dr, >99 % ee), which showed promise as new type N-olefin ligand. Preliminary mechanistic studies also carried out understand process this bimetallic catalysis.

Язык: Английский

---

Recent advances in Pd-catalyzed asymmetric cyclization reactions

Chemical Society Reviews, Год журнала: 2023, Номер 53(2), С. 883 - 971

Опубликована: Дек. 18, 2023

This review aims to collect advancements in enantioselective palladium-catalyzed cyclization reactions over the past eleven years, and it is organized into thirteen sections depending on different types of transformations involved.

Язык: Английский

---

Fungicide-inspired precursors of π-allylpalladium intermediates for palladium-catalyzed decarboxylative cycloadditions

Chemical Science, Год журнала: 2023, Номер 14(11), С. 3024 - 3029

Опубликована: Янв. 1, 2023

Inspired by a fungicide, we designed 5-vinyloxazolidine-2,4-diones as new precursors of π-allylpalladium zwitterionic intermediates and developed palladium-catalyzed asymmetric (5 + 3) cycloaddition with azomethine imines (3 2) 1,1-dicyanoalkenes. Both reactions proceeded smoothly under mild reaction conditions to produce various chiral heterocyclic compounds in high yields excellent enantioselectivities. These results revealed that were type suitable precursor for palladium catalysis will find extensive applications Pd-catalyzed such allylic alkylation.

Язык: Английский

---

Recent advances of Pd-π-allyl zwitterions in cycloaddition reactions

Chinese Chemical Letters, Год журнала: 2023, Номер 34(11), С. 108401 - 108401

Опубликована: Март 30, 2023

Язык: Английский

---

Catalytic Enantioselective α-Allylation of Deconjugated Butenolides with Aza-π-allylpalladium 1,4-Dipoles: Access to Optically Pure 2-Piperidones Bearing an All-Carbon Quaternary Stereocenter

Organic Letters, Год журнала: 2022, Номер 24(45), С. 8348 - 8353

Опубликована: Ноя. 10, 2022

A palladium-catalyzed enantioselective α-allylation of deconjugated butenolides with aza-π-allylpalladium 1,4-diploes, in situ generated from palladium-mediated decarboxylation cyclic carbamates and amide-substituted acyclic carbonates, has been successfully developed. An array enantioenriched 2-piperidones bearing an all-carbon quaternary stereocenter were obtained high yields excellent enantioselectivities (up to 99% yield ee). The utility this method was also showcased by a large-scale reaction synthetic transformations the product.

Язык: Английский

---

4-Vinylbenzodioxinones as a new type of precursor for palladium-catalyzed (4+3) cycloaddition of azomethine imines

Chemical Communications, Год журнала: 2024, Номер 60(11), С. 1436 - 1439

Опубликована: Янв. 1, 2024

Benzo-fused cyclic carbonates were designed and synthesized as a novel type of precursor π-allylpalladium zwitterionic intermediates.

Язык: Английский

---

Stereoselective Synthesis of Polysubstituted Conjugated Dienes Enabled by Photo‐Driven Sequential Sigmatropic Rearrangement

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(24)

Опубликована: Апрель 8, 2024

We here reported a highly stereoselective method for the synthesis of polysubstituted conjugated dienes from α-aryl α-diazo alkynyl ketones and pyrazole-substituted unsymmetric aminals under mild conditions, which was promoted by photo-irridation involved with 1,6-dipolar intermediate quadruple sigmatropic rearrangements, successfully developed. In this transformation, cleavage four bonds recombination five were implemented in one operational step. This protocol provided modular tool constructing amines, pyrazoles α-alkynyl-α-diazoketones one-pot manner. The results mechanistic investigation indicated that plausible reaction path underwent 1,6-sigmatropic rearrangement instead 1,5-sigmatropic rearrangement.

Язык: Английский

---

Enantio‐ and Diastereodivergent Synthesis of Spirocycles through Dual‐Metal‐Catalyzed [3+2] Annulation of 2‐Vinyloxiranes with Nucleophilic Dipoles

Angewandte Chemie, Год журнала: 2021, Номер 133(47), С. 25145 - 25153

Опубликована: Сен. 17, 2021

Abstract The development of efficient and straightforward methods for obtaining all optically active isomers structurally rigid spirocycles from readily available starting materials is great value in drug discovery chiral ligand development. However, the stereodivergent synthesis bearing multiple stereocenters remains an unsolved challenge owing to steric hindrance ring strain. Herein, we report enantio‐ diastereodivergent through dual‐metal‐catalyzed [3+2] annulation oxy π‐allyl metallic dipoles with less commonly employed nucleophilic (imino esters). A series spiro compounds a pyrroline olefin were easily synthesized manner (up 19:1 dr, >99 % ee ), which showed promise as new type N ‐olefin ligand. Preliminary mechanistic studies also carried out understand process this bimetallic catalysis.

Язык: Английский

---

Palladium‐Catalyzed [4+2] Cycloaddition of Hydroxy‐Tethered Allylic Carbonates with Alkenes: Synthesis of Functionalized Tetrahydropyrans

Advanced Synthesis & Catalysis, Год журнала: 2022, Номер 364(12), С. 2060 - 2066

Опубликована: Май 5, 2022

Abstract A palladium‐catalyzed [4+2] cycloaddition of hydroxy‐tethered allyl carbonates with five types electron‐deficient alkenes has been achieved, in which a type new acted as valuable precursors for the formation 1,4‐C,O‐dipole allylpalladium intermediates. The reaction proceeded efficiently under mild conditions to provide corresponding tetrahydropyran derivatives moderate high yields excellent diastereoselectivities. magnified image

Язык: Английский

---

Palladium-Catalyzed Asymmetric (3 + 2) Cycloaddition of 5-Allenyloxazolidine-2,4-Diones with Barbiturate-Derived Alkenes: Synthesis of Spirobarbiturate-γ-Lactams

Organic Letters, Год журнала: 2023, Номер 25(34), С. 6328 - 6333

Опубликована: Авг. 23, 2023

The 5-allenyloxazolidine-2,4-diones had been synthesized as novel precursors of π-allyl palladium zwitterion and were applied in a palladium-catalyzed enantioselective (3 + 2) annulation by using barbiturate-derived alkenes the reaction partner presence an axially chiral phosphoramidite ligand. This proceeded smoothly under mild conditions, affording highly functionalized spirobarbiturate-γ-lactam derivatives excellent yields along with high diastereo- enantioselectivities. scale-up further transformation product also successful.

Язык: Английский

---