Organocatalytic Aza-Michael/Mannich Cascade Reaction: Synthesis of Enantioenriched 3,3′-Spirooxindole γ-Lactams DOI
Xiaotong Li,

Heng-Zhi Tian,

Xing‐Wen Sun

и другие.

The Journal of Organic Chemistry, Год журнала: 2022, Номер 88(12), С. 7839 - 7843

Опубликована: Июнь 28, 2022

Highly enantioselective synthesis of 3,3′-spirooxindole γ-lactams with three contiguous stereocenters (two quaternary) was achieved. The aza-Michael/Mannich cascade reaction α-imine-β-oxobutanamides and methyleneindolinones catalyzed by a bifunctional diaminocyclohexane-derived thiourea catalyst gave the desired products in moderate to good yields (up 78%), diastereoselectivities 10:1 dr), excellent enantioselectivities >99% ee). A gram-scale some transformations were also carried out.

Язык: Английский

Electrochemically‐Driven Organocatalytic Enantioselective Oxidative Coupling of Tetrahydroisoquinolines and Acrylaldehyde DOI Open Access

Qiying Zhang,

Luxin Li, Songlin Wang

и другие.

Advanced Synthesis & Catalysis, Год журнала: 2023, Номер 365(20), С. 3455 - 3460

Опубликована: Авг. 24, 2023

Abstract An electrochemically‐driven organocatalytic enantioselective oxidative coupling of tetrahydroisoquinolines and acrylaldehyde was developed. Various chiral C1‐alkenyl derivatives were obtained with 69–86% yields 93:7–96:4 er. Notable features this reaction include asymmetric organocatalysis (5.0 mol% β‐ICD as catalyst), electricity the oxidant, air atmosphere, undivided cell. This synthetic route offers access to various optically active C1‐substituted derivatives.

Язык: Английский

Процитировано

5
Stereoelectronic Effect in the Reaction of α-Methylene Lactones with Tertiary Phosphines and Its Application in Organocatalysis DOI
Alexey V. Salin,

Andrey A. Shabanov,

Khasan R. Khayarov

и другие.

The Journal of Organic Chemistry, Год журнала: 2023, Номер 88(16), С. 11954 - 11967

Опубликована: Авг. 4, 2023

The kinetic data indicate that the addition of tertiary phosphines to α-methylene lactones in acetic acid is strongly accelerated comparison reactions related open-chain esters. Six-membered α-methylene-δ-valerolactone exhibited a more pronounced rate increase than five-membered α-methylene-γ-butyrolactone. use α-methylene-γ-butyrolactam as nitrogen analogue α-methylene-γ-butyrolactone resulted total loss reaction acceleration. observed reactivities were rationalized by DFT calculations at RwB97XD/6-31+G(d,p) level theory, showing intramolecular interaction between phosphonium and enolate oxygen centers provided locked s-cis-geometry heterocycles plays an important role stabilization intermediate zwitterions. reactivity also controlled conformational flexibility heterocycle. geometries and, especially, six-membered lactone cycles are slightly changed upon nucleophilic attack phosphine, leading stabilizing stereoelectronic effect Ρ···Ο interaction. phosphine significantly distorts initial geometry heterocycle, making unfavorable. application enhance efficiency phosphine-catalyzed Michael Pudovik was demonstrated.

Язык: Английский

Процитировано

2
Organocatalytic Aza-Michael/Mannich Cascade Reaction: Synthesis of Enantioenriched 3,3′-Spirooxindole γ-Lactams DOI
Xiaotong Li,

Heng-Zhi Tian,

Xing‐Wen Sun

и другие.

The Journal of Organic Chemistry, Год журнала: 2022, Номер 88(12), С. 7839 - 7843

Опубликована: Июнь 28, 2022

Highly enantioselective synthesis of 3,3′-spirooxindole γ-lactams with three contiguous stereocenters (two quaternary) was achieved. The aza-Michael/Mannich cascade reaction α-imine-β-oxobutanamides and methyleneindolinones catalyzed by a bifunctional diaminocyclohexane-derived thiourea catalyst gave the desired products in moderate to good yields (up 78%), diastereoselectivities 10:1 dr), excellent enantioselectivities >99% ee). A gram-scale some transformations were also carried out.

Язык: Английский

Процитировано

3