.png){kind=icon}
.png){kind=icon}
Return
Stereoselective Higher-Order [10+4]- and [10+6] Cycloadditions Between Two Highly Unsaturated and Ambiphilic π-Addends
.png){kind=icon}
OA
AI
J
A
F
A
R
J
H
K
DOI：10.1002/chem.71093.png)
.png){kind=icon}
.png){kind=icon}
Share.png){kind=icon}
Save
Abstract
En 中文
A fundamental challenge in higher-order cycloadditions (HOCs) is to control multiple layers of selectivity-peri-, regio-, diastereo-, and enantioselectivity. Controlling these selectivities in HOCs is very challenging when they involve two highly unsaturated and ambiphilic pi-addends. Here, we study this complexity in enantioselective aminocatalyzed HOCs between isobenzofulvenes, reacting as 10 pi-components, and 3-oxidopyridinium betaines, reacting as 4 pi- or 6 pi-components. The reaction generates three different products: an allowed [10+4] cycloadduct and two forbidden regioisomeric [10+6] cycloadducts. For the [10+6] reaction pathway, the 3-oxidopyridinium betaine reacts as a 6 pi-component with the fulvene scaffold in unprecedented cycloadditions. The outcome of these cycloadditions exhibits the challenge in controlling the peri- and regioselectivity in complex HOCs involving two highly unsaturated and ambiphilic pi-addends. We demonstrate that it is possible to optimize the cycloadditions toward the selective formation of the [10+4] cycloadduct or the [10+6] cycloadducts. Experimental investigations were conducted in combination with DFT calculations, in order to elucidate the origins of these selectivities.
Keywords:
3-oxidopyridinium betaine
asymmetric organocatalysis
DFT calculations
higher-order cycloaddition
AI Summary
Key information extracted from the uploaded paper, including a brief overview, abstract, background, key highlights, visual analysis, and future outlook.
Journal
C
IF:
3.7
Papers:
3.9W
Citations:
9.6W
Organization
Cited Papers