Organic Letters, Год журнала: 2023, Номер 25(41), С. 7562 - 7566
Опубликована: Окт. 6, 2023
Stereoselective synthesis of bicyclic cyclopentanones was achieved by sequential Tf2O-catalyzed decarboxylation and intramolecular [3 + 2] cycloaddition reactions cyclic enol carbonates bearing an alkene unit. Four stereogenic centers in the obtained cyclopentanone were stereoselectively constructed. This method could be applied to various fused products moderate-to-good yields.
Язык: Английский
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
Процитировано
27
ACS Catalysis, Год журнала: 2025, Номер unknown, С. 5796 - 5805
Опубликована: Март 25, 2025
The transition metal-catalyzed asymmetric [n + 2] cycloaddition reaction with oxy-substituted ketene intermediates remains a synthetic challenge due to the limited availability of suitable precursors. Herein, we report visible-light-driven, palladium-catalyzed [4 vinyl benzoxazinanones siloxyketene intermediates, generating structurally diverse chiral quinolinone derivatives satisfactory diastereo- and enantioselectivities. transient generation siloxyketenes from α-ketoacylsilylanes through visible-light-induced Brook rearrangement is important for success present cycloaddition. 13C-labeling experiments reveal pathway involving [1,3]-silyl migration process. side arm effects BOX ligand silyl steric hindrance α-ketoacylsilanes play crucial roles in stereoselectivity control, theoretical calculations provide insights into stereochemical outcome reaction.
Язык: Английский
Процитировано
1
Organic Letters, Год журнала: 2024, Номер 26(15), С. 3310 - 3315
Опубликована: Апрель 8, 2024
A catalyst system consisting of a chiral phosphoramidite ligand and Pd2(dba)3·CHCl3 causes the decarboxylation 5-vinyloxazolidine-2,4-diones to generate amide-containing aza-π-allylpalladium 1,3-dipole intermediates, which are capable triggering dearomatization 3-nitroindoles for diastereo- enantioselective [3+2] cycloaddition, leading formation series highly functionalized pyrroloindolines containing three contiguous stereogenic centers with excellent results (up 99% yield, 88:12 dr, 96% ee).
Язык: Английский
Процитировано
7
Coordination Chemistry Reviews, Год журнала: 2024, Номер 526, С. 216354 - 216354
Опубликована: Дек. 6, 2024
Язык: Английский
Процитировано
7
The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(7), С. 5019 - 5028
Опубликована: Март 19, 2024
In this paper, we reported the palladium-catalyzed formal [5 + 4] cycloaddition reactions between 4-vinyl-4-butyrolactones (VBLs) and azadienes. Under mild reaction conditions, a wide range of benzofuran-fused 9-membered heterocyclic compounds had been provided in moderate to excellent yields with exclusive regioselectivities diastereoselectivities. The practical applicability synthesis was demonstrated through scale-up further transformation.
Язык: Английский
Процитировано
6
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
Процитировано
12
Organic Letters, Год журнала: 2024, Номер 26(10), С. 2057 - 2061
Опубликована: Март 1, 2024
In this paper, palladium-catalyzed [3 + 2] cycloaddition of 4-vinyl-4-butyrolactones with ketenes generated from easily available acyl chlorides was achieved. With Pd2(dba)3·CHCl3/XantPhos as the catalyst, reaction proceeded smoothly under mild conditions, affording a series 2,3-dihydrofurans in moderate to high yields. The scale-up and further transformations products are demonstrated, plausible mechanism is proposed well.
Язык: Английский
Процитировано
5
ACS Catalysis, Год журнала: 2022, Номер 12(5), С. 2722 - 2728
Опубликована: Фев. 10, 2022
Palladium/boron-catalyzed allylic substitution of vinylethylene carbonates with water provides a powerful approach for the enantioselective synthesis tertiary C–O bond. Density functional theory calculations in present work show that nucleophilic attack via distinctive type chelation-assisted inner-sphere pathway is responsible experimentally observed regio- and enantioselectivities. The chelation between hydroxyl group boronate moiety Pd center enables exclusive branched-regioselectivity. enantioselectivity was rationalized terms lone pair---π repulsive interaction O atom chelated phenyl ring ligand.
Язык: Английский
Процитировано
19
Advanced Synthesis & Catalysis, Год журнала: 2022, Номер 364(22), С. 3967 - 3972
Опубликована: Окт. 18, 2022
Abstract In this paper, we designed and synthesized 4‐vinyl‐4‐butyrolactone as a precursor to generate the zwitterionic allylpalladium intermediates, which behaved five‐membered all‐carbon synthon in palladium‐catalyzed (5+3) annulation with azomethine imines, giving eight‐membered ring‐fused heterocycles (26 examples, 49% 97% yield, >20:1 dr). magnified image
Язык: Английский
Процитировано
19
Organic Letters, Год журнала: 2022, Номер 24(13), С. 2567 - 2572
Опубликована: Март 28, 2022
A kinetically controllable strategy toward the construction of otherwise challenging nine-membered carbocycles is reported. This Pd-catalyzed decarboxylative procedure utilizes vinyl methylene cyclic carbonates as C5-dipole and allylidenemalononitriles C4-building blocks. The protocol features user-friendly operations with regioselectivity generates CO2 sole byproduct. formation synthetically valuable thermodynamically favored seven-membered was also investigated.
Язык: Английский
Процитировано
18