Recent advances in annulation reactions based on zwitterionic π-allyl palladium and propargyl palladium complexes

Organic Chemistry Frontiers, Год журнала: 2021, Номер 8(13), С. 3475 - 3501

Опубликована: Янв. 1, 2021

Carbocyclic and heterocyclic compounds could be constructed through the palladium-catalyzed annulation reactions of zwitterionic π-allyl palladium or propargyl complexes with unsaturated electrophiles.

Язык: Английский

---

Regiodivergent Synthesis of Spirocyclic Compounds through Pd‐Catalyzed Regio‐ and Enantioselective [3+2] Spiroannulation

Angewandte Chemie International Edition, Год журнала: 2021, Номер 60(11), С. 5806 - 5810

Опубликована: Янв. 21, 2021

Abstract A novel Pd 0 ‐catalyzed highly regio‐ and enantioselective [3+2] spiroannulation reaction has been developed for rapid assembly of a new class [5,5] spirocyclic carbo‐ heterocycles. Notably, the regioselectivity could be dominated by fine‐tuning Pd‐π‐allyl intermediate. An array coupling partners well‐tolerated with excellent regio‐, enantioselectivities. Moreover, potential application this was exemplified several further transformations.

Язык: Английский

---

Highly Diastereo- and Enantioselective Synthesis of Tetrahydrobenzo[b]azocines via Palladium-Catalyzed [4 + 4] Cycloaddition

ACS Catalysis, Год журнала: 2021, Номер 11(5), С. 2684 - 2690

Опубликована: Фев. 12, 2021

The construction of N-heterocyclic eight-membered rings with good regio-, stereo-, and enantioselective control remains a formidable challenge in asymmetric catalysis. Herein, we report palladium-catalyzed [4 + 4] cycloaddition anthranils γ-methylidene-δ-valerolactones the presence Et3B, delivering highly functionalized tetrahydrobenzo[b]azocine derivatives high efficiency diastereoselectivities enantioselectivities (up to 92% yield, 20:1 dr, 99% ee). Moreover, complex substrates derived from natural products (bearing different functionalities) could be well-tolerated catalytic cycloaddition. mild reaction conditions, conjunction broad substrate scope (44 examples), level stereoselectivity, provide great potential build azocine compounds simple building blocks.

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

---

Synthesis of Chiral Endocyclic Allenes and Alkynes via Pd-Catalyzed Asymmetric Higher-Order Dipolar Cycloaddition

Journal of the American Chemical Society, Год журнала: 2024, Номер unknown

Опубликована: Сен. 18, 2024

A Pd-catalyzed asymmetric higher-order dipolar cycloaddition between allenyl carbonates and azadienes is achieved by exploiting novel alkylidene-π-allyl-Pd dipoles. This research provides a modular platform for the synthesis of challenging chiral endocyclic allenes bearing medium-sized heterocyclic motif centrally stereocenter in good yields with high enantio- diastereoselectivities (29 examples, up to 97% yield, 97:3 er >19:1 dr). Experimental computational studies elucidate possible reaction mechanism observed stereochemical results. Based on mechanistic understanding, new π-propargyl-Pd dipole was designed further extend success higher order strategy 10-membered alkynes from propargyl (13 98% yield 94.5:5.5 er).

Язык: Английский

---

Enantio‐, Diastereo‐ and Regioselective Synthesis of Chiral Cyclic and Acyclic gem‐Difluoromethylenes by Palladium‐Catalyzed [4+2] Cycloaddition

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(24)

Опубликована: Март 28, 2022

gem-Difluoromethylene moieties are attractive in medicinal chemistry due to their ability mimic other more ubiquitous functional groups. Thus, effective asymmetric methods for construction highly desirable, especially the industrial production of chiral drugs. Using a Pd-catalyzed [4+2] cycloaddition between substituted-2-alkylidenetrimethylene carbonates and gem-difluoroalkyl ketones, we were able easily access 1,3-dioxanes that contain tetrasubstituted difluoroalkyl stereogenic center cyclic acyclic skeletons. A novel phosphoramidite ligand, which contains bulky 1,1-dinaphthylmethanamino moiety, was developed provide products high yield with excellent enantio-, diastereo-, regioselectivity. Strikingly, gem-difluoro substitution pattern promotes reaction, pentafluoroethylketone, an α,α-difluorinated β-ketoester, β-ketosulfone suitable substrates this method.

Язык: Английский

---

Palladium-Catalyzed Enantioselective Cycloaddition of Carbonylogous 1,4-Dipoles: Efficient Access to Chiral Cyclohexanones

Journal of the American Chemical Society, Год журнала: 2020, Номер 142(52), С. 21645 - 21650

Опубликована: Дек. 18, 2020

A novel palladium-mediated carbonylogous 1,4-dipole was developed by in situ deprotonation. By using our own-developed C2-unsymmetric phosphoramidite as supporting ligand, this dipole applied to the asymmetric synthesis of chiral cyclohexanones via a catalytic [4+2] cycloaddition. Electron-deficient allylic carbonate used generate highly reactive dipoles for first time, and diverse array stable precursors explored elaboration cyclohexanones. general mechanism reaction process stereochemical outcome proposed, which can be useful designing predicting future transformation.

Язык: Английский

---

A Double Deprotonation Strategy for Cascade Annulations of Palladium–Trimethylenemethanes and Morita–Baylis–Hillman Carbonates to Construct Bicyclo[3.1.0]hexane Frameworks

Angewandte Chemie International Edition, Год журнала: 2021, Номер 60(25), С. 13913 - 13917

Опубликована: Апрель 8, 2021

Here we report that the chemoselective activation of Tsuji's 2-(cyanomethyl)allyl carbonates to generate palladium-trimethylenemethane 1,3-dipoles via a deprotonation strategy can be realized in presence Morita-Baylis-Hillman from substantial activated ketones. The following SN 2'-addition enables formation new 1,3-dipole species having an alkene moiety through second process, which then undergo cascade [1+2]/[3+2] annulations furnish complex bicyclic [3.1.0]hexane frameworks three contiguous quaternary stereogenic centers with good excellent enantioselectivity. Moreover, by using benzoyl aldehyde-derived substrates, [1+4]/[3+2] annulation sequence is similarly developed produce fused cyclopenta[b]furan architectures.

Язык: Английский

---